tagungsband die 22. kalorimetrietage · and how to distinguish them by itc 17:00 p. schmidt, m....
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Anton Paar GmbHAnton Paar Strasse 208054 GrazAustriaTelefon: +43 316 257 0Telefax: +43 316 257 [email protected]
C3 PROZESS- UND ANALYSENTECHNIK GmbH Peter-Henlein-Str. 20D-85540 Haar b. MünchenTelefon: 089/45 60 06 70Telefax: 089/45 60 06 [email protected]
DR. KRAUSE GmbHAhornstraße 28 – 32Haus 5514482 PotsdamTelefon: 0331 740 01 05Telefax: 0331 704 66 29dr.krause.software@isafem.dewww.isafem.dewww.selbstentzuendung.com
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Linseis Messgeraete GmbHVielitzerstr. 4395100 SelbTelefon: +49 (0) 9287/880 0Telefax: +49 (0) 9287/704 [email protected]
Malvern Instruments GmbH Rigipsstr. 1971083 HerrenbergTelefon: + 49 (0) 7032 97770Telefay: + 49 (0) 7032 77854 [email protected]://www.malvern.com
Mettler-Toledo GmbHOckerweg 335396 GießenTelefon: +49 (0)641 507-444www.mt.com/TA-FDSC
Die 22. Kalorimetrietage werden unterstützt von:
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig2 / 162 3/ 162
Die 22. Kalorimetrietage werden unterstützt von: . . . . . . . . .Umschlag
Impressum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2
Inhaltsverzeichnis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3
Grußwort . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4
Allgemeine Hinweise und Lageplan . . . . . . . . . . . . . . . . . . . . . . . . . .6
Busplan – Linie 433 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8
Busplan – Linie 461 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
Tagungsprogramm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10
Rahmenprogramm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .19
Liste der Vorträge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .21
Kurzfassungen der Vorträge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .27
Firmenanzeigen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .84
Liste der Posterbeiträge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .97
Kurzfassungen der Posterbeiträge . . . . . . . . . . . . . . . . . . . . . . . . .101
Autorenliste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .149
Ankündigung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .159
Die 22. Kalorimetrietage werden unterstützt von: . . . . . . . . .Umschlag
Inhaltsverzeichnis
Veranstalter• Gesellschaft für Thermische Analyse e. V.• Physikalisch-Technische Bundesanstalt
Programmkomitee• Prof. Dr. H. Bunjes,
Braunschweig• Dr. M. Feist, Berlin• Prof. Dr. H. Heerklotz• Dr. J. Lerchner, Freiberg• Prof. Dr. F. Mertens, Freiberg• Dr. S. Neuenfeld, Darmstadt
• Dr. S. Sarge, Braunschweig• Prof. Dr. C. Schick, Rostock• Dr. J. Seidel. Freiberg• Prof. Dr. med. D. Singer,
Hamburg• Prof. Dr. G. Wolf, Freiberg
Lokale OrganisationD. KlausPhysikalisch-Technische BundesanstaltBundesallee 10038116 Braunschweig
VeranstaltungsortPhysikalisch-Technische BundesanstaltSeminarzentrumBundesallee 10038116 Braunschweig
TagungsbüroTelefon: (0531) 592-9784Fax: (0531) 592-3305E-Mail: [email protected]: www.kalorimetrietage.ptb.de
Impressum
Herausgeber und Verlag:Physikalisch-Technische BundesanstaltISNI: 0000 0001 2186 1887Bundesallee 10038116 Braunschweig
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Aber wir dürfen nicht die Fähigkeiten anderer Methoden, die ebenfalls thermodynamische Eigenschaften zu ermitteln erlauben, unterschätzen, wie der Vortrag von Prof. Span über die Ermittlung kalorischer Eigenschaften aus Zustandsgleichungen eindrucksvoll zeigt. Auch sonst stellen wir fest, dass modellbasierte Rechenverfahren zur Ermittlung thermodynamischer und kinetischer Daten an Popularität gewinnen. Lassen Sie uns aber nicht vergessen, dass diese Verfahren im besten Fall als semi-empirisch anzusehen sind, vollständige ab-initio-Verfahren sind weiterhin sehr aufwendig und unzuverlässig. Und am Ende entscheidet immer das Experiment. Deshalb lassen Sie uns zuversichtlich in die Zukunft schauen und der Wissenschaft, Industrie und Gesellschaft weiterhin durch die Ermittlung richtiger und zuverlässiger Informationen für den Energieumsatz in biologischen, chemischen, physikalischen und technischen Systemen dienen.In diesem Sinne wünschen wir allen Teilnehmern der 22. Kalorimetrietage einen interessanten und lehrreichen Aufenthalt in Braunschweig.
Grußwort
Die 22. Kalorimetrietagevom 7. bis 9. Juni 2017 in Braunschweig
Mit den diesjährigen 22. Kalorimetrietagen wollen wir einen weiteren Schritt in die Zukunft machen. Sie werden bemerken, dass die Mehrzahl der Vorträge und Poster, auch die sonstige Kommunikation – mit Ausnahme dieses Grußwortes – in der aktuellen universellen Wissenschaftssprache, in Englisch, präsentiert werden. In gewisser Weise ist dies bedauerlich, weil es unseren muttersprachlich englisch aufgewachsenen Kollegen einen grundsätzlichen Vorteil in Diskussionen, Auseinandersetzungen und Rechtsstreitigkeiten gibt. Insofern begrüßen wir den Vorschlag eines Kollegen der Bundesanstalt für Materialforschung und -prüfung, sprachlich zwei Schritte zurückzugehen und Latein wieder als universelle Wissenschaftssprache zu etablieren, wie es bis ca. 1800 auch tatsächlich der Fall war. Latein ist eine mächtige und fl exible Sprache, wie über mehr als 2000 Jahre bewiesen wurde, und würde es erlauben, wie in Frankreich und Island für die dortigen Sprachen üblich, neue Ideen, neue Konzepte, neue Sachverhalte und neue Produkte präzise abzubilden oder durch intelligente Wortschöpfungen auszudrücken. Damit wäre auf der sprachlichen Ebene Chancengleichheit hergestellt.Leider eine Utopie.Deswegen gehen wir den Weg, zunächst beide Sprachen, Deutsch und Englisch, gleichberechtigt zu behandeln und zu beobachten, wohin die Kalorimetrietage steuern.
Keine Utopie ist, dass diesmal mit den angemeldeten 42 mündlichen und 28 Postervorträgen ein besonders vielfältiger Eindruck in das Potential unseres Arbeitsgebietes vermittelt wird. Insbesondere die Anwendung kalorimetrischer Methoden in der Biologie, Medizin und Pharmazie erscheint zukunftsträchtig.
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HörsaalVorträge
Empfang
Eingang
Seminarraum AVorträge
Seminarraum BPoster
Thas
s
Setaram
TA Instruments
C3
Anton P
aar
Union I
nstru
ments
Prosen
se
Mettler
Toled
o
Netzsch
Dr. Krause
Perkin Elmer
Linseis
Malvern
Allgemeine Hinweise und Lageplan
Die Plenar- und Hauptvorträge sowie ein Teil der Kurzvorträge fi nden im Hörsaal statt, der andere Teil der Kurzvorträge im Seminarraum A. Die Firmenpräsentationen und die Posterausstellung befi nden sich im Foyer des Seminarzentrums bzw. im Seminarraum B.
Das Mittagessen kann in der Kantine der PTB eingenommen werden.
Parkplätze befi nden sich ausreichend unweit des Seminarzentrums auf dem Gelände. Für Mittwoch- und Donnerstagabend ist ein Bustransfer von der PTB in die Innenstadt eingerichtet.Die Linien 433 und 461 bedienen tagsüber die PTB im 30-Minuten Takt.
Ausfahrt
A
B
C
EinfahrtBundesallee nach Lehndorf
Bund
esal
lee
nach
Wat
enbü
ttel
Anmeldung
Kantine
Seminarzentrum
P
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Busplan – Linie 461
- PTB- Bundesallee- Paracelsusstraße- Pfleidererstraße- von Pawelsches Holz- Saarbrückener Straße- Saarplatz- Ottweilerstraße- Hildesheimer Straße- Rudolfplatz- Kälberwiese- Maienstraße- Madamenweg- Johannes-Selenka-Platz- Cyriaksring- Luisenstraße- Europaplatz- Am Wassertor (Volkswagen-Halle)- John-F.-Kennedy-Platz- Campestraße- Braunschweig Hauptbahnhof
6.136.156.166.176.186.196.206.216.236.256.266.276.286.296.316.326.336.346.366.376.40
6.43 18.43alle30Min
6.45 18.456.46 18.466.47 18.476.48 18.486.49 18.496.50 18.506.51 18.516.53 18.536.55 18.556.56 18.566.57 18.576.58 18.586.59 18.597.01 19.017.02 19.027.03 19.037.04 19.047.06 19.067.07 19.077.10 19.10
PTB – Hauptbahnhof
Hauptbahnhof – PTB- Braunschweig Hauptbahnhof- Campestraße- John-F.-Kennedy-Platz- Fr.-Wilhelm-Platz- Europaplatz- Luisenstraße- Cyriaksring- Johannes-Selenka-Platz- Madamenweg- Maienstraße- Kälberwiese- Hildesheimer Straße- Ottweilerstraße- Saarplatz- Saarbrückener Straße- von Pawelsches Holz- Pfleidererstraße- Paracelsusstraße- Bundesallee- PTB
5.325.335.35
6.246.256.27
6.206.216.236.256.266.276.296.306.316.326.336.366.376.386.396.406.416.426.436.45
6.50 19.20alle30Min
6.51 19.216.53 19.236.55 19.256.56 19.266.57 19.276.59 19.297.00 19.307.01 19.317.02 19.327.03 19.337.06 19.367.07 19.377.08 19.387.09 19.397.10 19.407.11 19.417.12 19.427.13 19.437.15 19.45
PTB – Pockelsstraße
Pockelsstraße – PTB
Busplan – Linie 433
- PTB
- Paracelsusstraße
- Saarplatz
- Hildesheimer Straße
- Amalienplatz
- Hamburger Straße
- Hans-Sommer-Straße
5.43
5.47
5.50
5.54
5.57
6.00
6.10
6.13
6.17
6.20
6.24
6.27
6.30
6.40
6.43
6.47
6.50
6.54
6.57
7.00
7.10
7.13
7.17
7.20
7.24
7.27
7.30
7.40 alle alle
7.43
7.47
7.50
7.54
7.57
8.00
8.10
8.13
8.17
8.20
8.40 11.40
8.43 11.43
8.47 11.47
8.50 11.50
8.54 11.54
8.57 11.57
9.00 12.00
18.10
18.13
18.17
18.20
18.24
18.27
18.30
- von Pawelsches Holz 5.45 6.15 6.45 7.15 7.45 8.15 8.45 11.45 18.15
- Bundesallee 6.12 6.42 7.12 60 307.42 8.12 8.42 11.42 18.12
- Pfleidererstraße 5.44 6.14 6.44 7.14Min Min
7.44 8.14 8.44 11.44 18.14
- Saarbrückener Straße
- Ottweilerstraße
- Rudolfplatz
5.46
5.48
5.52
6.16
6.18
6.22
6.46
6.48
6.52
7.16
7.18
7.22
7.46
7.48
7.52
8.16
8.18
8.22
8.46 11.46
8.48 11.48
8.52 11.52
18.16
18.18
18.22
- Maschplatz
- Pockelsstraße
5.55
5.58
6.25
6.28
6.55
6.58
7.25
7.28
7.55
7.58
8.55 11.55
8.58 11.58
18.25
18.28
- Bültenweg- Pockelsstraße- Hamburger Straße- Maschplatz- Amalienplatz- Rudolfplatz- Hildesheimer Straße- Ottweilerstraße- Saarplatz- Saarbrückener Straße- von Pawelsches Holz- Pfleidererstraße- Paracelsusstraße- Bundesallee- PTB
6.006.016.046.056.076.096.116.126.136.146.156.166.176.186.20
6.30 8.00alle30min
alle60min
alle30min
6.31 8.016.34 8.046.35 8.056.37 8.076.39 8.096.41 8.116.42 8.126.43 8.136.44 8.146.45 8.156.46 8.166.47 8.176.48 8.186.50 8.20
12.0012.0112.0412.0512.0712.0912.1112.1212.1312.1412.1512.1612.1712.1812.20
18.3018.3118.3418.3518.3718.3918.4118.4218.4318.4418.4518.4618.4718.4818.50
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Tagungsprogramm
Thursday, 08.06.2017
Lecture hall
Chair: E. Wilhelm
09:00J. Orava (Cambridge, UK)
Chalcogenides for Phase-Change Memory Applications
09:45
S. H. Dürrstein, C. Kappler, I. Neuhaus, M. Malow, H. Michael-Schulz, M. Gödde (Ludwigshafen/Bonn)
Vergleich verschiedener Messmethoden zum thermischen Verhalten von Dicumylperoxid (40 %) in Ethylbenzol – modellbasierte Vorhersage adiabater Induktionszeiten sowie der SADT und Vergleich mit dem UN H.1-Test
10:15 Instrument presentation / Poster presentation / Coffee break
Tagungsprogramm
Wednesday, 07.06.2017
Lecture hall
13:00 Welcome address
Chair: W. Hemminger
13:30A. Nicolaus (Braunschweig)
The SI unit kilogram: the new defi nition and it’s realization on the basis of fundamental constants
14:15N. Barros (Santiago de Compostela, Spain)
The role of calorimetry in assessing the impact of climate change on the global carbon cycle
15:00 Instrument presentation / Poster presentation / Coffee break
Chair: N. Barros
16:00R. Span (Bochum)
Caloric Properties from Empirical Fundamental Equations of State
16:30H.Y. Fan, H. Heerklotz (Freiburg)
Three types of biomembrane effects of surfactants and how to distinguish them by ITC
17:00P. Schmidt, M. Reschke, A. Wolf, A. Efi mova (Cottbus)
ThermoPhIL: Thermochemical Investigations of Phase Formation Processes in Ionic Liquids
17:30S. Vidi, M. Brütting, S. Hiebler, C. Rathgeber (Würzburg)
Calorimetric Measurements of Phase Change Materials (PCM)
18:00 Transfer to city
20:00 Informal meeting at Rheinische Republik
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Tagungsprogramm
Thursday, 08.06.2017
Seminar room A
Tagungsprogramm
Thursday, 08.06.2017
Lecture hall
Energetics (Chair: F. Mertens) Materials (Chair: W. Kunze)
11:00N. Gorodylova, P. Šulcová (Pardubice, Czech Republic)
Reactivity of ZrOCl2∙8H2O and its application for the synthesis of NASICON framework phosphates
11:00G. Kaiser, C. Straßer (Selb)
Einfl uss von Nukleierungsmitteln auf die Kristallisation von Polypropylen (PP)
11:20F. Taubert, R. Hüttl, J. Seidel, F. Mertens (Freiberg)
Determination of thermodynamic properties of lithium monosilicide based on calorimetric and hydrogenation experiments
11:20
E. Hempel, J.E.K. Schawe, St. Ziegelmeier (Schwerzenbach, Switzerland)
Determination of the thermal short time stability of polymers by fast scanning calorimetry
11:40
C. Thomas, G. Balachandran, N. Mayer, R. Hüttl, J. Seidel, F. Mertens (Freiberg)
Determination of the enthalpy of mixing in the binary system LiFePO4–FePO4 at 25 °C
11:40
R. Androsch, C. Schick (Rostock)
Interplay between the Relaxation of the Glass of Random L/D Lactide Copolymers and Homogeneous Crystal Nucleation: Evidence for Segregation of Chain Defects
12:00
V. Becattini, T. Motmans, A. Zappone, C. Madonna, A. Haselbacher, A. Steinfeld (Zurich, Switzerland)
Determination of specifi c heat capacity of rocks by DSC before and after high-temperature thermal cycling
12:00B. Yang, Y. Gao, C. Schick (Rostock)
Can homogenous nucleation be controlled in a metallic glass?
12:20 Lunch break 12:20 Annual meeting of GEFTA members
Chair: H. Heerklotz
13:50
O. Braissant, A. Solokhina, D. Brueckner, G. Bonkat, D. Wirz (Allschwil, Switzerland)
Combination of tunable diode laser absorption spectroscopy and isothermal microcalorimetry for life sciences
14:20T. Maskow (Leipzig)
Calorimetry of Microbial Utilization of Electrical and Photon Energy
14:50U. Schröder (Braunschweig)
Electrifi ed Microbiology – Bacteria full of Potential!
15:20 Instrument presentation / Poster presentation / Coffee break
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Tagungsprogramm
Thursday, 08.06.2017
Seminar room A
Tagungsprogramm
Thursday, 08.06.2017
Lecture hall
Biology (Chair: T. Maskow) Safety Assessment (Chair: S. Neuenfeld)
16:20C. Ortmann (Eschborn)
Die Mikrokalorimetrie als nicht-invasive Methode zur Charakterisierung des Metabolismus
16:20
M. Lünne, A. Knorr, K.-D. Wehrstedt (Berlin)
Vorhersage der selbstbeschleunigenden Zersetzungstemperatur (SADT) für organische Peroxide aus DSC-Messungen
16:40J. Lerchner, C. Lanaro, P.L.O. Volpe, F. Mertens (Freiberg)
A chip calorimetry based method for the real-time monitoring of red blood cell sickling
16:40T. Willms, H. Kryk, J. Oertel, U. Hampel (Dresden)
The decomposition of tert.-butyl hydroperoxide studied by differential scanning calorimetry
17:00E. Roese, H. Bunjes (Braunschweig)
Investigating Drug Release from Triglyceride Nanoparticles into Physiological Media by DSC
17:00J. Burelbach, U. Hess (München)
Tests with Adiabatic Calorimeters
17:20
M. Marenchino (Herrenberg)
Turning up the heat on protein stability characterization. Differential Scanning Calorimetry for the regulated environment
17:20G. Krause (Potsdam)
DSC Validierung. Vergleich der Meßwerte mit der Auswertung
17:40A. Abdelaziz, D.H. Zaitsau, T. Mukhametzyanov, S.P. Verevkin, C. Schick (Rostock)
Flash DSC study of the melting behavior of Cytosine17:40
S. Stones (Bletchley, England)
Micro Reaction Calorimetry. Newer Applications for the Chemical & Pharmaceutical Industry
18:00 Transfer to city
19:00 Guided city tour or guided visit to Herzog Anton Ulrich-Museum
20:30 Conference dinner with presentation by G. Krause: Der wahre Grund, warum die Titanic untergehen mußte
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Tagungsprogramm
Friday, 09.06.2017
Seminar room A
Tagungsprogramm
Friday, 09.06.2017
Lecture hall
New Methods (Chair: C. Schick) Thermodynamics (Chair: P. Schmidt)
09:00G. Bartl (Braunschweig)
Interferometric determination of thermal expansion on material measures
09:00E. Wilhelm (Wien, Österreich)
Solubility Parameters: A Versatile Concept
09:20C. Bläker, C. Pasel, M. Luckas, F. Dreisbach, D. Bathen (Duisburg)
Kopplung von kalorimetrischen und volumetrischen Adsorptionsmessungen
09:20
D.H. Zaitsau, S.P. Verevkin (Rostock)
Through solution to the gas phase: Evaluation of the enthalpy of vaporization for thermally unstable ionic compounds with the help of solution calorimetry
09:40
T. Husemann, S. Schwarz, G. Henriques, N. Bertram, J.K. Krüger (Seelze-Letter)
Thermal excitation, optical response: Sheds a new light on thermal analysis by TORC
09:40D. Walter, E. Haibel (Gießen)
Carbonate formation in oxidic lanthanum compounds – Isothermal calorimetry
10:00A. Omelcenko, H. Wulfmeier, H. Fritze (Clausthal)
Thin-Film Calorimeter Based on High-Temperature Stable Piezoelectric Resonators
10:00
T. Haug (Karlsruhe)
Thermodynamische Modellierung eines Prozesskalorimeters zur kontinuierlichen Bestimmung des Wobbe-Index von Brenngasen
10:20H.K. Cammenga (Braunschweig)
Thermochemische Erkenntnisse über die Sorption, das Rösten und das Quenchen von Kaffeebohnen
10:20F.J. Perez-Sanz (Braunschweig)
Comparison of Calorifi c Value Measurements of Biogas Reference and Field Calorimeters
10:40 Instrument presentation / Poster presentation / Coffee break
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Wednesday, 07.06.2017
20:00 Informal meeting at Rheinische RepublikNeue Straße 10, 38100 Braunschweig (self-paying basis)
Thursday, 08.06.2017
19:00Guided city tour or guided visit to Herzog Anton Ulrich-MuseumMeeting points: Burgplatz and museum entrance, resp.
20:30 Conference dinner at restaurant Al DuomoRuhfäutchenplatz 1, 38100 Braunschweig
RahmenprogrammTagungsprogramm
Friday, 09.06.2017
Lecture hall
Chair: D. Walter
11:30P. Dumas (Illkirch-Graffenstaden)
Kinetic ITC methods in the fi eld of biology
12:00R. Leithner (Braunschweig)
Druckluftspeicherkraftwerke
12:45 Farewell address Burgplatz, Al Duomo
Schloss
Bohlweg
Magnitorwall
Münzstraße
Steinweg
Theater
Rheinische Republik
Herzog A. U.-Museum
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Liste der Vorträge
Abdelaziz, Amir (Rostock)
Flash DSC study of the melting behavior of Cytosine(A. Abdelaziz, D.H. Zaitsau, T. Mukhametzyanov, S.P. Verevkin, C. Schick)
Barros, Nieves (Santiago de Compostela, Spain)
The role of calorimetry in assessing the impact of climate change on the global carbon cycle
Bartl, Guido (Braunschweig)
Interferometric determination of thermal expansion on material measures
Becattini, Viola (Zurich, Switzerland)
Determination of specifi c heat capacity of rocks by DSC before and after high-temperature thermal cycling(V. Becattini, T. Motmans, A. Zappone, C. Madonna, A. Haselbacher, A. Steinfeld)
Bläker, Christian (Duisburg)
Kopplung von kalorimetrischen und volumetrischen Adsorptionsmessungen(C. Bläker, C. Pasel, M. Luckas, F. Dreisbach, D. Bathen)
Braissant, Olivier (Allschwil, Switzerland)
Combination of tunable diode laser absorption spectroscopy and isothermal microcalorimetry for life sciences(O. Braissant, A. Solokhina, D. Brueckner, G. Bonkat, D. Wirz)
Bunjes, Heike (Braunschweig)
Investigating Drug Release from Triglyceride Nanoparticlesinto Physiological Media by DSC(E. Roese, H. Bunjes)
Cammenga, Heiko K. (Braunschweig)
Thermochemische Erkenntnisse über die Sorption, das Rösten und das Quenchen von Kaffeebohnen
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Liste der Vorträge
Kaiser, Gabriele (Selb)
Einfl uss von Nukleierungsmitteln auf die Kristallisation von Polypropylen (PP)(G. Kaiser, C. Straßer)
Knorr, Annett (Berlin)
Vorhersage der selbstbeschleunigenden Zersetzungstemperatur (SADT) für organische Peroxide aus DSC-Messungen(M. Lünne, A. Knorr, K.-D. Wehrstedt)
Krause, Gerhard (Potsdam)
Der wahre Grund, warum die Titanic untergehen mußte
Krause, Gerhard (Potsdam)
DSC Validierung. Vergleich der Meßwerte mit der Auswertung
Lerchner, Johannes (Freiberg)
A chip calorimetry based method for the real-time monitoring of red blood cell sickling(J. Lerchner, C. Lanaro, P.L.O. Volpe, F. Mertens)
Leithner, Reinhard (Braunschweig)Druckluftspeicherkraftwerke
Marenchino, Marco (Herrenberg)
Turning up the heat on protein stability characterization. Differential Scanning Calorimetry for the regulated environment
Maskow, Thomas (Leipzig)
Calorimetry of Microbial Utilization of Electrical and Photon Energy
Nicolaus, Arnold (Braunschweig)
The SI unit kilogram: the new defi nition and it’s realization on the basis of fundamental constants
Liste der Vorträge
Dumas, Philippe (Illkirch-Graffenstaden)
Kinetic ITC methods in the fi eld of biology
Gödde, Markus (Ludwigshafen)
Vergleich verschiedener Messmethoden zum thermischen Verhalten von Dicumylperoxid (40%) in Ethylbenzol – modellbasierte Vorhersage adiabater Induktionszeiten sowie der SADT und Vergleich mit dem UN H.1-Test(S. Dürrstein, C. Kappler, I. Neuhaus, M. Malow, H. Michael-Schulz, M. Gödde)
Gorodylova, Nataliia (Pardubice, Czech Republic)
Reactivity of ZrOCl2∙8H2O and its application for the synthesis of NASICON framework phosphates(N. Gorodylova, P. Šulcová)
Haug, Torsten (Karlsruhe)
Thermodynamische Modellierung eines Prozesskalorimeters zur kontinuierlichen Bestimmung des Wobbe-Index von Brenngasen
Heerklotz, Heiko (Freiburg)
Three types of biomembrane effects of surfactants and how to distinguish them by ITC(H.Y. Fan, H. Heerklotz)
Hempel, Elke (Schwerzenbach, Switzerland)
Determination of the thermal short time stability of polymers by fast scanning calorimetry(E. Hempel, J.E.K. Schawe, St. Ziegelmeier)
Hess, Uwe (München)
Tests with Adiabatic Calorimeters(J. Burelbach, U. Hess) Husemann, Tobias (Seelze-Letter)
Thermal excitation, optical response: Sheds a new light on thermal analysis by TORC(T. Husemann, S. Schwarz, G. Henriques, N. Bertram, J.K. Krüger)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig24 / 162 25/ 162
Taubert, Franziska (Freiberg)
Determination of thermodynamic properties of lithium monosilicide based on calorimetric and hydrogenation experiments(F. Taubert, R. Hüttl, J. Seidel, F. Mertens)
Thomas, Christian (Freiberg)Determination of the enthalpy of mixing in the binary system LiFePO4–FePO4 at 25 °C(C. Thomas, G. Balachandran, N. Mayer, R. Hüttl, J. Seidel, F. Mertens)
Vidi, Stephan (Würzburg)
Caloric Measurements of Phase Change Materials (PCM)(S. Vidi, M. Brütting, S. Hiebler, C. Rathgeber) Walter, Dirk (Gießen)
Carbonate formation in oxidic lanthanum compounds – Isothermal calorimetry(D. Walter, E. Haibel)
Wilhelm, Emmerich (Wien, Österreich)
Solubility Parameters: A Versatile Concept
Willms, Thomas (Dresden)
The decomposition of tert.-butyl hydroperoxide studied by differential scanning calorimetry(T. Willms, H. Kryk, J. Oertel, U. Hampel)
Yang, Bin (Rostock)
Can homogenous nucleation be controlled in a metallic glass?(B. Yang, Y. Gao, C. Schick)
Zaitsau, Dzmitry H. (Rostock)
Through solution to the gas phase: Evaluation of the enthalpy of vaporization for thermally unstable ionic compounds with the help of solution calorimetry(D.H. Zaitsau, S.P. Verevkin)
Liste der Vorträge
Omelcenko, Alexander (Clausthal)
Thin-Film Calorimeter Based on High-Temperature Stable Piezoelectric Resonators(A. Omelcenko, H. Wulfmeier, H. Fritze )
Orava, Jiri (Cambridge, UK)Chalcogenides for Phase-Change Memory Applications
Ortmann, Christian (Eschborn)
Die Mikrokalorimetrie als nicht-invasive Methode zur Charakterisierung des Metabolismus
Pérez-Sanz, Fernando J. (Braunschweig)
Comparison of Calorifi c Value Measurements of Biogas Reference and Field Calorimeters
Schick, Christoph (Rostock)
Interplay between the Relaxation of the Glass of Random L/D Lactide Copolymers and Homogeneous Crystal Nucleation: Evidence for Segregation of Chain Defects(R. Androsch, C. Schick)
Schmidt, Peer (Cottbus)
ThermoPhIL: Thermochemical Investigations of Phase Formation Processes in Ionic Liquids
Schröder, Uwe (Braunschweig)
Electrifi ed Microbiology – Bacteria full of Potential!
Span, Roland (Bochum)
Caloric Properties from Empirical Fundamental Equations of State
Stones, Steve (Bletchley, England)
Micro Reaction Calorimetry. Newer Applications for the Chemical & Pharmaceutical Industry
Liste der Vorträge
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig 27/ 162
Tagungsband
Die 22.Kalorimetrietage
Kurzfassungen der Vorträge
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Flash DSC study of the melting behavior of Cytosine
A. Abdelaziz1,2, D.H. Zaitsau2,3; T. Mukhametzyanov4 S.P. Verevkin2,3, C. Schick1,2,4
1 University of Rostock, Institute of Physics, Albert-Einstein-Str. 23-24, 18051 Rostock,
Germany2 University of Rostock, Faculty of Interdisciplinary Research,
Competence Centre CALOR, Albert-Einstein-Str. 25, 18051 Rostock, Germany3 University of Rostock, Institute of Chemistry, Dr-Lorenz-Weg 1, 18051 Rostock,
Germany4 Kazan Federal University, 18 Kremlyovskaya Street, Kazan 420008,
Russian Federation
We report, for the first time, the melting
behavior of cytosine, one of the nucleo-
bases, building blocks of DNA and RNA
sequences.
Cytosine is known to decompose during
the melting process, this makes the appli-
cation of conventional calorimetric meth-
ods meaningless for investigation of the
melting of this thermally instable biomole-
cule.
With the help of Mettler Toledo flash
DSC1, the sample of solid cytosine was
heated with a scanning rate of 6000 K·s-1
above the proposed temperature of fusion.
No obvious evidence of cytosine decom-
position was observed. Upon quenching,
with high cooling rate a partial verification
was observed.
Several experiments were carried out in
order to get reliable values of fusion tem-
perature, fusion enthalpy, as well as the
glass transition temperature and the spe-
cific heat capacity of liquid cytosine - re-
ported for the first time.
Amir Abdelaziz
BD
A
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Interferometric determination of thermal expansion on
material measures
Guido Bartl
Physikalisch-Technische Bundesanstalt (PTB), Bundesallee 100, 38116 Braunschweig,
Germany
The realisation and dissemination of the
SI base unit metre is part of the legal as-
signment of a national metrology institute
like PTB. Therefore the length of material
measures (usually in the form of gauge
blocks) is determined with high precision
by special imaging interferometers which
have been developed for this purpose.
The focus of the research activities is on
the reduction of the measurement uncer-
tainty in order to meet the demands of in-
dustry with regard to decreasing produc-
tion tolerances. Consequently the temper-
ature as an important parameter has to be
monitored precisely when the absolute
length of a sample body is measured. The
measurement of the absolute length of a
material depending on the temperature (or
time) allows the determination of its ther-
mal expansion (or stability over time). In-
stead of measuring differential length
changes the absolute length as a function
of temperature in the interval from 7 K up
to 330 K can be investigated with a result-
ing uncertainty on the order of 10-9/K.
Such high-accuracy knowledge of the
temperature-dependent thermal expan-
sion is required for the development and
characterisation of ultra-stable materials,
for instance in the semiconductor industry,
precision optics, or aerospace applica-
tions. The capabilities – and limitations –
of the available interferometers will be pre-
sented.
The role of calorimetry in assessing the impact of climate
change on the global carbon cycle.
Nieves Barros
Dept. Applied Physics, Faculty of Physics, University of Santiago de Compostela, Spain
Climate change is one of the biggest chal-
lenges facing scientists worldwide nowa-
days. Interdisciplinary knowledge is of
paramount importance to climate change
research, because climate directly affects
all aspects of life on earth: from natural
and experimental sciences, to economics,
social sciences and human health.
The research needed to adapt life on
earth to the predicted effect of climate on
our planet, and to mitigate to some extent
its impact on human life and on human
society, will require many different scien-
tific disciplines working together in close
collaboration.
The predictions are worrisome. According
to the European Environmental Agency
(EEA 2008), the Intergovernmental Panel
on Climate Change (IPCC), and the World
Health Organization (WHO) the global
average surface temperature is projected
to increase between 1.4 and 5.8 ºC this
century. The Artic sea ice is melting at a
rate of 2.7 % per decade, and mountain
glaciers are contracting. Both impact sea
levels, which have increased 1.8 mm per
year since 1961.
The number of people at risk of flooding
by coastal storms is projected to increase
from the current 75 million to 200 million.
But this is not all. All these issues directly
impact human health due to extreme heat
and cold, changes in air and water quality,
and changes in the ecology of infectious
diseases. At the core of these threats to
human health lies the effect of
temperature on two of the vital primary
resources on earth: soil and water.
On the face of the aforementioned impact
of climate change on all living systems, we
should be measuring the effect of temper-
atures on life. We should monitor what
happens to a certain living system with
increasing or decreasing temperatures,
when those temperatures hit extreme cold
or hot levels, and when the exposure time
to such extreme temperatures raises. This
measuring and monitoring is the object of
biocalorimetry.
Latest calorimetric devices allow us to
monitor changes in the metabolic rates of
living systems under changing tempera-
tures continuously and in real time, mak-
ing these experimental phases faster and
easier than other methods, and opening a
wide range of useful scientific applications
in this age of changing global climate.
These applications not only involve the
study of soil, plants, microorganisms and
pathogens that threat human food sup-
plies. They also involve studying how to
fight such pathogens and the role of tem-
perature on them.
On the whole, calorimetry can and should
make key contributions to our knowledge
about the real impact of temperature on
life. This basic knowledge is essential to
provide the best strategies to preserve
human welfare and safety under the cli-
mate change conditions.
Guido BartlNieves Barros
A
DF
B
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig32 / 162 33/ 162
Kopplung von kalorimetrischen und volumetrischen
Adsorptionsmessungen
M. Sc. C. Bläker1* , Dr. rer. nat. C. Pasel1, Dr. Ing. M. Luckas1,
Dr.-Ing. Frieder Dreisbach2, Prof. Dr.-Ing. Dieter Bathen1,3,
1 Thermische Verfahrenstechnik Universität Duisburg-Essen, Duisburg, Deutschland2 Rubotherm GmbH, Bochum, Deutschland3 Institut für Energie- und Umwelttechnik e.V. (IUTA), Duisburg, Deutschland
* E-Mail: [email protected]
Die Auslegung von technischen Adsorpti-
onsprozessen basiert im Wesentlichen auf
der Messung von Reinstoffisothermen und
Durchbruchskurven. Da Temperaturände-
rungen einen starken Einfluss auf die
Durchbruchskurven haben, erfordert die
Modellierung und Auslegung von Adsorp-
tionsprozessen eine möglichst genaue
Kenntnis der Adsorptionswärme. Diese ist
eine Funktion des Bedeckungsgrads, so-
dass eine simultane Messung von Adsorp-
tionsenthalpie und Beladung wünschens-
wert ist.
Ziel dieses Projektes ist daher die Ent-
wicklung eines Messverfahrens zur Kopp-
lung von kalorimetrischen und volumetri-
schen Gleichgewichtsmessungen in ei-
nem Gerät.
Ein volumetrisches Adsorptionsmessgerät
wird durch einen kalorimetrischen
Messaufbau erweitert, mit dem die Druck-
differenz zwischen zwei identischen Gas-
volumina in einem Wasserbad mit defi-
nierter Temperatur gemessen wird. Bei
der Adsorption steigt in der Messzelle
aufgrund der Sorptionswärme die Tempe-
ratur. Der resultierende Wärmestrom
durch das Gasvolumen in das Wasserbad
induziert einen einseitigen Temperatur-
und Druckanstieg im Gasvolumen. Aus
der Druckdifferenzkurve lässt sich nach
einer Kalibrierung die Sorptionswärme
berechnen.
Die simultane Messung von volumetri-
schen und kalorimetrischen Adsorptions-
messungen ist eine zeitsparende Metho-
de, welche konsistente Werte liefert. Ab-
bildung 1 zeigt beispielhaft die simultan
gemessenen Adsorptionsisothermen
(links) und Adsorptionsenthalpien (rechts)
der n-Alkane Ethan bis n-Hexan an einem
13X Zeolithen bei 25°C. Diese Studie un-
terstreicht die Beladungsabhängigkeit der
Adsorptionsenthalpie und erlaubt Rück-
schlüsse auf die Wechselwirkungen sowie
die Mechanismen bei der Adsorption.
Determination of specific heat capacity of rocks by DSC
before and after high-temperature thermal cycling
Viola Becattini1, Thomas Motmans1, Alba Zappone2, Claudio Madonna2,
Andreas Haselbacher1, Aldo Steinfeld1
1 Department of Mechanical and Process Engineering, ETH Zurich, 8092 Zurich,
Switzerland2 Department of Earth Sciences, ETH Zurich, 8092 Zurich, Switzerland
Rocks are considered an attractive stor-
age material for thermal-energy storage
(TES) at high temperatures. However, the
literature lacks detailed experimental data
on the effects of thermal cycling on the
thermophysical and mechanical properties
of rocks. The first objective of our study
was to fill this gap in the literature through
a quantitative assessment of the effects of
thermal cycling on the specific heat capac-
ity of selected rocks using a temperature
range and a heating rate that are repre-
sentative of a TES at steady cycling.
Six types of rocks of Alpine origin were in-
vestigated, five of which were previously
used in experiments with a lab-scale and
a pilot-scale TES. The rocks were classi-
fied as mafic rocks, felsic rocks, calcare-
ous sandstones, limestones, quartz-rich
conglomerates, and serpentinite. The
rocks were thermally cycled between
about 100 and 600 °C with a heating rate
of 2.6 °C/min. Measurements of the spe-
cific heat capacity were performed by
differential scanning calorimetry (DSC) be-
fore thermal cycling as well as after 20 cy-
cles.
Thermal cycling was found to lead to de-
crease in the specific heat capacity of the
rocks. This effect is explained by chemical
reactions such as mineral dehydration
starting at about 400 °C, decarbonation of
calcite, and deserpentinization above
about 600°C, leading to a loss of volatiles
(H2O and CO2) from rock samples. The
different extents in the decrease of the
specific heat capacity of each rock are at-
tributed to its initial mineralogical content
(i.e., abundance of hydrate minerals
and/or calcite). Establishing a quantitative
correlation between the amount of vola-
tiles lost and the decrease in the specific
heat capacity was not feasible due to the
heterogeneity of the rock population. The
development of such correlation will be
the goal of a future study on homogene-
ous standard rocks.
Christian Bläker
A
DF
B
Viola Becattini
Abb. 1:Adsorptionsisothermen (links) und Adsorptionsenthalpie (rechts) von n-Alkanen
an einem 13X Zeolithen bei 25°C
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Combination of tunable diode laser absorption spectroscopy
and isothermal microcalorimetry for life sciences.
Olivier Braissant1*, Anna Solokhina1, David Brueckner1,2, Gernot Bonkat1,3, Dieter Wirz1
1 Center of Biomechanics & Biocalorimetry, University Basel, Gewerbestr. 14,
CH-4123 Allschwil, Switzerland2 F. Hoffmann – La Roche, Ltd., Sterile Drug Product Manufacturing, Wurmisweg,
CH-4303 Kaiseraugst, Switzerland3 Alta Uro AG, Centralbahnplatz 6, CH-4051 Basel, Switzerland
* E-Mail: [email protected]
Isothermal microcalorimetry (IMC) is a
very sensitive technique to assess mi-
cro-organisms metabolism and monitor
their growth when even at low concentra-
tion. Isothermal microcalorimetry provides
re-al-time insights on the metabolic activity
or microbes and is very useful to assess
shift in metabolism for example. However
due to the label-free nature of the meas-
urement performed mostly using sealed
vials (except for flow-through instruments),
it is sometime difficult to get additional
insights.
In this context tunable diode laser absorp-
tion spectroscopy (TDLAS) is a valuable
addition to the conventional IMC meas-
urement as it allows to monitor the
head-space concentration of gases in the
calorimetry vials. In our recent laboratory
work we have investigated the two
technologies separately to perform sterility
assessment of pharmaceutical products.
In addition, we used these techniques in
combination to perform calorespirometric
analyses on liquid culture and biofilms
grown on nylon membranes.
Our work indicate that metabolism can be
investigated accurately using the two
methodologies in parallel to combine
metabolic heat production data with oxy-
gen consumption and carbon dioxide
production data. In addition, it appears that
combining the 2 methods is valuable as
less work is needed compared to the
conventional use of the NaOH or chro-
mogenic CO2 traps. For biofilms and liquid
cultures gas measurement and metabolic
heat measurements fitted with each other
and with the biology of the investigated
microorganisms.
Investigating Drug Release from Triglyceride Nanoparticles
into Physiological Media by DSC
Elin Roese, Heike Bunjes
Technische Universität Braunschweig, Institut für Pharmazeutische Technologie &
Zentrum für Pharmaverfahrenstechnik, Mendelssohnstr. 1, 38106 Braunschweig
Colloidal aqueous dispersions of triglycer-
ides can be used as carriers for poorly
water-soluble, lipophilic drugs in order to
make such drugs available for the patient,
e.g. by intravenous injection. Beside the
drug incorporation capacity of the triglyc-
eride particles their drug release proper-
ties after injection are of high importance
with regard to their use as intravenous
carrier systems. In order to characterize
the release behavior in vitro, adequate
release conditions have to be established
that should resemble the physiological
situation as closely as possible. For ex-
ample, useful aqueous media to study the
release behavior of lipophilic drugs after
intravenous injection should contain lipo-
philic acceptor components (mimicking,
e.g., lipoproteins or other colloidal ingredi-
ents of blood) that can take up released
drug. In practice, however, release inves-
tigations with such particle-containing re-
lease media are often complicated by the
similar size of drug carrier and acceptor
particles making separation of these two
particle fractions difficult. Using a newly
developed DSC method, it is possible to
study drug release from colloidal carrier
particles without separation of donor and
acceptor particles if certain preconditions
are fulfilled. The method relies on measur-
ing the crystallization temperature of
trimyristin carrier nanoparticles. The crys-
tallization temperature of these particles
decreases linearly with increasing concen-
tration of incorporated drug and thus in-
creases upon drug release. Supercooled
liquid trimyristin nanoparticles loaded with
the lipophilic drug substances fenofibrate,
orlistat, tocopherol acetate or
ubidecarenone were investigated in three
release media with increasing complexity
and similarity to physiological conditions: a
rapeseed oil nanoemulsion, porcine serum
and blood. A clear correlation between the
release behavior and the lipophilicity of
the incorporated drug substance was ob-
served. The higher the logP value, the
slower was the drug release. The extent of
drug release was controlled by partition
phenomena as reflected in a more pro-
nounced release into the rapeseed oil
emulsion compared to serum and blood.
Roese E., Bunjes H., Drug release studies from lipid nanoparticles in physiological media
by a new DSC method, J. Control. Rel. 256 (2017) 92–100.
Heike BunjesOlivier Braissant
A
DF
B
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Kinetic ITC methods in the field of biology
P. Dumas
Institut de génétique et de biologie moléculaire et cellulaire (IGBMC),
1 Rue Laurent Fries, 67400 Illkirch-Graffenstaden, France
E-Mail: [email protected]
Classical ITC experiments involve
multiple injections of a molecule B
into a cell containing a molecule A.
Upon interaction of A and B follow-
ing A + B C (characterized by
the equilibrium constant
Ka = kon / koff), there is emission or
absorption of heat and the calorim-
eter measures in real time the cor-
responding heat power (in µcal / s).
We have developed a method to
recover kon and koff from the shape
of each injection curve of a classi-
cal ITC titration experiment [1]. By
using ITC in a classical way, this
kind of information is systematically
lost by the integration of the injec-
tion power curves. However, by
using kinetic equations one can
relate the kinetics of the reaction to
the heat power produced or ab-
sorbed during the reaction. Several
technical problems need to be
solved to take into account the fi-
nite injection and mixing times of
compound B into the measurement
cell, as well as the finite response
time of the instrument (see illustra-
tion at http://www-ibmc.u-
strasbg.fr:8080/webMathematica/ki
nITCdemo/).
Ideally, kinITC experiments are
performed at different tempera-
tures. Using of the van ’t Hoff equa-
tion allows to link the measured ΔH
to the temperature variation of the
corresponding equilibrium con-
stant Ka.. This is also a link to the
kinetic parameters to be deter-
mined since Ka = kon /koff.
We also developed a simplified,
and yet very efficient version of this
method using data at a single tem-
perature [2]. It is based on the vari-
ation from injection to injection of
the time needed to return to base-
line. The resulting ‘Equilibration
Time Curve’ (ETC) allows deriv-
ing kon and koff as soon as Ka is
known from the classical pro-
cessing of the ITC experiment. The
method is now available in the
software AFFINImeter
(http://www.affinimeter.com).
Importantly, the full kinITC tech-
nique can cope with two-step kinet-
ic schemes. This will be illustrated
with the binding of a ligand to an
RNA followed by complete RNA
folding. Both thermodynamic and
kinetic information could be derived
for each individual step [3].
Thermochemische Erkenntnisse über die Sorption,
das Rösten und das Quenchen von Kaffeebohnen
Heiko K. Cammenga
Technische Universität Braunschweig
Rohkaffeebohnen kommen aus den Er-
zeugerländern schon viele Jahre zu uns
nicht mehr in „atmungsaktiven“ Jutesä-
cken, sondern in Containern. An Deck der
Riesenfrachter durchlaufen die Kaffee-
bohnen die unterschiedlichen Klimazonen,
und die Temperaturwechsel während der
Schiffspassage führen zu Desorption
(warme Umgebung) und Resorption (kalte
Umgebung) von Wasser. Das kann zu
ungleicher Feuchteverteilung der Bohnen
im Container (unten besonders feucht!)
und schließlich zu einer Schimmelbildung
führen (mit Aflatoxin-Entstehung!). Wir
haben darum die H2O-Sorptionsiso-
thermen und -kinetik als Funktion von
Temperatur und Feuchte erstmals sehr
genau ermittelt.
Rohkaffee wird vor dem Einsatz als Ge-
nussmittel bekanntlich geröstet, ein Pro-
zess, der komplexe chemische und ther-
mische Effekte in der Bohne zur Folge
hat, die wir detailliert untersucht haben.
Neben dem Verlust von sorbierten und im
weiteren Verlauf auch chemisch gebun-
denen Wassers (endotherme Prozesse)
führen chemische (endotherme und
exotherme) Vorgänge zu Reaktionen, aus
denen die große Geschmacks- und Aro-
mafülle erlesener Röstkaffees resultiert.
Dabei fungiert die einzelne, intakt bleiben-
de Kaffeebohne als ein Mini-Reaktions-
kessel, den nur wenige Röstreaktionspro-
dukte verlassen können (z.B. H2O, CO2,
CO, Essig- und Propionsäure, u.a.m),
wohingegen selbst so leichtflüchtige In-
haltsstoffe wie das Coffein die Bohne nur
zum ganz geringen Anteil verlassen kön-
nen. Wir haben die Thermochemie des
Röstvorgangs untersucht, wobei wir viele
äußere Parameter variiert haben (Heizra-
te, Temperaturbereich, Umgebung: Luft
oder Stickstoff, …). Früher haben wir die
Prozesse im Bohneninneren („Autoklav“)
nur im Hinblick auf die thermisch bedingte
Veränderung der Zellstruktur hin interpre-
tiert, heute meine ich, dass das komplexe
Stoffgemisch schließlich einen plastischen
Zustand erreicht, aus dem beim schnellen
Abschrecken der Bohne, Quenchen ge-
nannt, eine amorphe Matrix entsteht. Ers-
te Hinweise lieferte der Temperaturverlauf
der Wärmekapazität von der grünen bis
zur durchgerösteten Kaffeebohne. Ferner
haben wir zur Interpretation u.a. REM-
und NMR-Aufnahmen herangezogen.
Nach dem Röstvorgang müssen die Kaf-
feebohnen (ähnlich wie weichgekochte
Eier) möglichst schnell abgekühlt werden,
um ein unkontrolliertes Nachrösten zu
unterbinden. Dieses Quenchen erfolgte
früher in der Regel durch Übersprühen mit
kaltem Wasser unter Umwälzung des
Röstguts. Eine thermodynamische Bilan-
zierung zeigte jedoch, dass es effektiver
sein sollte, mit siedendem Wasser abzu-
kühlen - und so ist es tatsächlich!
Philippe Dumas
BC
GH
D
A
Heiko K. Cammenga
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig38 / 162 39/ 162
Vergleich verschiedener Messmethoden zum thermischen
Verhalten von Dicumylperoxid (40%) in Ethylbenzol –
modellbasierte Vorhersage adiabater Induktionszeiten sowie
der SADT und Vergleich mit dem UN H.1-Test
Steffen H. Duerrstein1, Claudia Kappler1, Isabel Neuhaus1, Marcus Malow2,
Heike Michael-Schulz2, Markus Gödde*1
1 BASF SE, GCP/RS, 67056 Ludwigshafen, Germany2 BAM Bundesanstalt für Materialforschung und –prüfung, Unter den Eichen 87,
12205 Berlin, Germany
* E-Mail: [email protected]
Experimentelle Basis für die sicherheits-
technische Beurteilung exothermer Reak-
tionen sind je nach Fragestellung ver-
schiedene thermoanalytische Messverfah-
ren wie DSC, Reaktionskalorimetrie (RC),
adiabate Kalorimetrie, Calvetkalorimetrie
(z.B. C80), Mikrokalorimetrie (z.B. TAM).
Um eine hohe Verlässlichkeit der Aussa-
gen zu garantieren, sind regelmäßige Ka-
librierungen unerlässlich. Nach ISO 17025
für akkreditierte Prüflaboratorien müssen
regelmäßig Eignungsprüfungen und Teil-
nahmen an Ringversuchen nachgewiesen
werden.
Normalerweise werden kalorische Mess-
verfahren durch Schmelzen von Reinstof-
fen, Referenzreaktionen und elektrische
Heizer kalibriert. Die BASF Sicherheits-
technik verwendet seit Jahren eine 40%-
ige Lösung von Dicumylperoxid (DCP) in
Ethylbenzol zur Ermittlung der Leistungs-
kenngrößen eigener adiabater Kalorime-
ter.
Im Rahmen der vorliegenden Studie
wurde das thermische Verhalten der Per-
oxidlösung mit weiteren kalorimetrischen
Methoden untersucht und die Ergebnisse
untereinander verglichen. Als Messtechni-
ken wurden neben der adiabaten Kalori-
metrie verschiedene Messungen in DSC,
C80, TAM und RC herangezogen. Der
Vergleich der Messmethoden untereinan-
der erfolgte anhand der Arrheniusauftra-
gung des jeweils (maximal) detektierten
Wärmestroms im Temperaturbereich von
80°C bis 130°C. Abbildung 1 zeigt zum ei-
nen die gute Übereinstimmung der Mess-
größen aus DSC, C80, RC bei 120°C und
130°C. Zum anderen wird deutlich, dass
auch die Extrapolierbarkeit der Wärme-
ströme zu höheren und tieferen Tempera-
turen zulässig ist, wie die Resultate aus
TAM und dem adiabaten Experiment bele-
gen.
Zusätzlich zu den experimentellen Unter-
suchungen, wurde auf Basis dynamischer
Wärmestromkurven aus DSC und C80 ein
formalkinetisches Modell entwickelt (Soft-
ware: Netzsch Thermokinetics 3.1). Die
gemessenen Kurven bei unterschiedlichen
Heizraten wurden mit einem formalkineti-
schen Modell beschrieben. Die abgeleite-
ten kinetischen Größen wurden im Fol-
genden herangezogen, um Wärmeströme
und adiabate Induktionszeiten für ver-
schieden Temperaturen zu simulieren und
mit den verschiedenen Experimenten zu
vergleichen. Aus den Ergebnissen wird
deutlich, dass sich das kinetische Modell
[1] Burnouf D, Ennifar E, Guedich S, Puffer-Enders B, Hoffmann G,
Bec G., Disdier F., Baltzinger M., Dumas P (2012) JACS 134, 559-565
[2] Dumas P., Ennifar E., Da Veiga C. et al. (2016) Methods in
Enzymology, Vol. 567, Chap. 7, 157-179
[3] Guedich S., Puffer-Enders B., Baltzinger M. et al. (2016) RNA Biology,
13, 373-390
Markus Gödde
DC
HK
G
B
Philippe Dumas (Forts.)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig40 / 162 41/ 162
Reactivity of ZrOCl2∙8H2O and its application for the
synthesis of NASICON framework phosphates
Nataliia Gorodylova*, Petra Šulcová
Department of Inorganic Technology, University of Pardubice, Pardubice, Czech Republic
* E-Mail: [email protected]
This contribution is devoted to the reactivi-
ty of zirconium oxychloride octahydrate,
ZrOCl2∙8H2O, and its application for the
synthesis of a series of framework NA-
SICON phosphates Li1+xCrxZr2-x(PO4)3. In
particular, thermal transformation of indi-
vidual ZrOCl2∙8H2O and its complex inter-
action with phosphate, carbonate and ox-
ide mixtures will be discussed.
Experimental: Thermal transformation of
the individual components and the reac-
tion mixtures was investigated using TG-
DTA analysis (20-1200 °C). Evolution of
the phase composition during heating was
analysed using powder XRD analysis.
Combination of both techniques helped to
understand the mechanism of the for-
mation of the solid solutions and the
chemical processes taking place in the
mixtures during heating.
Results: Typically, decomposition of indi-
vidual ZrOCl2∙8H2O starts at 70 °C with
elimination of eight molecules of its crys-
talline water, while above 230 °C it under-
goes thermal hydrolysis leading to elimi-
nation of HCl and formation of ZrO2. The
temperature range and kinetics of the
mentioned processes highly depends on
the experimental conditions (i.e. atm.
pressure, humidity).
Thermal behaviour of ZrOCl2∙8H2O and
(NH4)2HPO4 mixture changes dramatically
in comparison with the typical behaviour of
the individual compounds. The typical
features of thermal behaviour of this mix-
ture are the following: dehydration of
ZrOCl2∙8H2O (endothermic effect at
160 °C, step-like mass loss between
70-230 °C) accompanied with interaction
between ZrOCl2∙8H2O and (NH4)2HPO4 in
molar ratio 1:2 leading to the formation of
NH4Cl, NH4H2PO4 and ZrO2; release of
ammonia and dehydration of NH4H2PO4
starts above 200 °C (gradual mass loss);
sublimation and decomposition of NH4Cl
(endothermic effect at 350 °C, step-like
mass loss between 310 and 410 °C).
When additional carbonate and oxide are
included in the mixture composition, its
thermal behaviour becomes even more
complex and at the same time it still highly
depends on the ratio between the
ZrOCl2∙8H2O and (NH4)2HPO4 compo-
nents. Accordingly, with increase of sub-
stitution degree x in the (0.5+x/2)Li2CO3-
(2-x)ZrOCl2∙8H2O-(x/2)Cr2O3-3(NH4)2HPO4
mixture from 0 to 2, the mechanism of the
formation of the solid solutions changes
dramatically. In particular, the mixtures
with x < 2, undergo similar interaction as
two-component ZrOCl2∙8H2O-
2(NH4)2HPO4 mixture leading to the for-
mation of NH4Cl, NH4H2PO4 and ZrO2 at
low temperatures (< 160 °C), which in-
volves lesser and lesser part of the mix-
ture with increase of x and the corre-
sponding decrease in ZrOCl2∙8H2O con-
tent. However, with increase of x and the
corresponding decrease of ZrOCl2∙8H2O
content in the mixture, the indicated pro-
cess becomes less dominant. In other
hervorragend eignet, um das reale Verhal-
ten der Probe über einen weiten Tempera-
turbereich hinweg hinreichend genau zu
beschreiben.
Ferner wurde auf Basis der kinetischen In-
formationen die SADT (self-accelerating
decomposition temperature) für ein
200-Liter Fass nach Semenov und mittels
zeitabhängiger Rechnungen (CFD) vor-
hergesagt und anschließend mit einem
1:1- Durchgehexperiment verglichen
(UN H.1-Test).
Zusammenfassend ergibt sich ein konsis-
tentes Bild zwischen den einzelnen mess-
verfahren und der Simulation.
Damit qualifiziert sich die Lösung von Di-
cumylperoxid in Ethylbenzol als Referenz-
substanz für Eignungsprüfungen verschie-
denster kalorischer Messverfahren in si-
cherheitstechnischen Prüflaboratorien.
80 100 120 1400,01
0,1
1
10
100
1000C80DSCRCTAMadiab. Exp.Simulation (DSC,C80)lineare Extrapolation
ma
xim
ale
rW
ärm
est
rom
[W/k
g]
Temperatur [°C]
Abbildung 1: Arrhenius-Auftragung des Wärmestroms gegen die Temperatur für die
exotherme Zersetzung von Dicumylperoxid (40%) in Ethylbenzol aus Simulation und Ex-
periment. Als experimentelle Werte wurden die maximalen Wärmeströme der Messungen
aus DSC, C80, TAM, RC sowie der Wärmestromverlauf einer adiabaten Messungen her-
angezogen.
Markus Gödde (Forts.) Nataliia Gorodylova
DC
HK
G
B
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Thermodynamische Modellierung eines Prozesskalorimeters
zur kontinuierlichen Bestimmung des Wobbe-Index von
Brenngasen
Torsten Haug
UNION Instruments GmbH, Zeppelinstrasse 42, 76185 Karlsruhe
Die größten Probleme bei der kontinuierli-
chen Messung des Wobbe-Index von Ga-
sen sind die Einflüsse von Umgebungs-
bedingungen wie Temperatur und Druck.
Diese beeinflussen die Messung und kön-
nen zu großen Messfehlern führen.
Durch eine Modellierung des Systems
können sowohl temperaturbedingte Mess-
fehler stark reduziert werden als auch die
Ansprechzeit der Messung stark be-
schleunigt werden.
hand, unreacted amount of (NH4)2HPO4 is
increased and the corresponding effect of
elimination of its ammonia becomes more
and more prominent. The mixture with x =
2 can be characterised with typical behav-
iour of the mixtures of (NH4)2HPO4 with
oxides or carbonates. Thus, it can be con-
cluded, when both ZrOCl2∙8H2O and
(NH4)2HPO4 are present in the reaction
mixture, the interaction between these two
components became the dominant feature
of the thermal transformation, while other
processes play the minor role.
In most cases, calcination at 1200 °C dur-
ing 6 h was sufficient for the formation of
solid solutions; formation of LiZr2(PO4)3
required calcination at 1300 °C,
Li3Cr2(PO4)3 - 1150 °C.
Acknowledgment: The authors would like to thank for the financial support to Grant
Agency of Czech Republic (No. 16-06697S).
Nataliia Gorodylova (Forts.) Torsten Haug
GC
KL
H
D
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Three types of biomembrane effects of surfactants and how
to distinguish them by ITC
H.Y.Fan1, H. Heerklotz1,2
1 Leslie Dan Faculty of Pharmacy, University of Toronto2 Inst. Pharmaceutical Sciences, University of Freiburg
Lipid-detergent-systems have important
applications, for example in pharmaceu-
tics and membrane protein studies. Fur-
thermore, principal phenomena observed
in such systems (e.g., membrane curva-
ture stresses, nonlamellar phases, etc.)
play key roles also for drugs and biomole-
cules interacting with cell membranes.
Detergents that can “flip” across the mem-
brane spontaneously follow the scenario
described by the three-stage-model, typi-
cally. It has been shown long ago that ITC
is the superior method to characterize
such systems (Heerklotz et al., Chem.
Phys. Lett., 1995). Detergents that do not
cross the membrane built up asymmetry
stress by inserting into the outer leaflet
only. This stress can lead to transient
membrane failure or, “cracking in” of the
detergent, which again is detected by ITC
(Heerklotz, Biophys. J. 2001) and followed
by the well-known 3-stage behaviour. Al-
ternatively, the stress can oppose further
insertion of surfactant. For example, do-
decyl-lysophosphatidylcholine (Fan et al.,
Langmuir 2016) and digitonin (Fan and
Heerklotz, J. Coll. Interf. Sci., 2017) are
staying out of the membrane beyond a
certain stress and form micelles that do
not equilibrate with the liposomes for
hours.
Heiko Heerklotz
Determination of the thermal short time stability of polymers
by fast scanning calorimetry
E. Hempel1*, J.E.K. Schawe1, St. Ziegelmeier2
1Mettler-Toledo GmbH, Sonnenbergstrasse 74, CH-8603 Schwerzenbach, Switzerland2 Rapid Technologies Center, BMW Group, Knorrstrasse 147, D-80788 Munich, Germany
* E-Mail: [email protected]
Thermogravimetric analysis (TGA) is a
standard technique to measure the ther-
mal stability of polymeric materials. This
technique is not sensitive for degradation
steps which are not related to mass loss.
However, such reactions can significantly
influence the mechanical behavior of ma-
terial. In this contribution we introduce the
technique of stability estimation by crystal-
lization analysis (SECA) and pseudo TGA
which uses differential scanning calorime-
try (DSC). SECA measures the influence
of decomposition on crystallization kinet-
ics. This technique is very sensitive to
decomposition. Using fast scanning calo-
rimetry, SECA determines the short time
thermal stability of semi-crystalline poly-
mers. This property is essential for fast
polymer processing like selective laser
sintering or welding [1].
[1] J.E.K. Schawe, St. Ziegelmeier, Thermochimica Acta 623 (2016) 80–85.
Elke Hempel
GC
KL
H
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Tests with Adiabatic Calorimeters
James Burelbach1, Uwe Hess2
1 Fauske and Associates, Burr Ridge, IL, USA, E-Mail: [email protected] Prosense GmbH, München, E-Mail: [email protected]
Various types of calorimeters with signif-
icant design differences are used for
different applications. DSCs, for in-
stance, are scanning twin-cells heat-flow
calorimeters that are widely used for
material testing and chemical reaction
screening. But their application range is
limited because of relatively small sam-
ple sizes. Reaction calorimeters, on the
other hand, are made to determine heat
flow characteristics of liquid phase reac-
tions under various experimental condi-
tions. Sample containers are not relative-
ly small sample pans but reactors that
offer sufficient volume for process devel-
opment related investigations and space
for corresponding peripheral devices like
additional sensors or dosing devices.
Usually, reaction calorimeters are heat
flow calorimeters without reference cells
and are run more or less isothermally.
Results obtained in lab environments by
DSCs and reaction calorimeters, how-
ever, can not be simply scaled up. In so
called upset scenarios (e.g. loss of cool-
ing) nearly all heat of reaction is kept in
the reaction mixture and none is dissi-
pated. In order to represent such a situa-
tion in a lab experiment, sample contain-
ers may accumulate almost no heat.
Consequently, they must be low weight
(phi factor ~ 1) and heat flows have to be
suppressed (adiabatic conditions). Adia-
batic calorimeters are designed to fulfill
these conditions. Typical adiabatic calo-
rimeters have maximum heating rates of
600 K/min allowing test cell surroundings
to heat up as rapidly as run away reac-
tions. Fast pressure tracking prevents
light weight test cells from rupturing.
Adiabatic calorimeters measure adia-
batic temperature rises. With a proper
design they allow tests under various
experimental conditions as well as the
characterization of flow characteristics in
case of emergency venting. Subsequent
calculations determine heats of reac-
tions, kinetic parameters (e.g. activation
energy) and chemical safety parameters
(e.g. TMR). Measured self heating rates
are used in vent sizing calculations for
emerging relief systems (ERS).
C. Askonas and J. Burelbach, North American Thermal Analysis Society, 28th Annual
Conference, Orlando, 2000, “The versatile VSP 2: A tool for adiabatic thermal analysis
and vent sizing applications”
J.L. Leung, H.K. Fauske and H.G. Fisher, Thermochimica Acta 1986, 104, 13 - 29
Uwe Hess
Thermal excitation, optical response: Sheds a new light on
thermal analysis by TORC
T. Husemann1, S. Schwarz, G. Henriques1, N. Bertram1, J.K. Krüger
1 Anton Paar OptoTec GmbH, Lise-Meitner-Str. 6, 30926 Seelze-Letter, Germany
Phase transitions play a key role in many
industrial applications: For example glass
transitions and melting points govern the
production of plastics and also determine
the mechanical properties of adhesives
and coatings.
Several phase transitions are easily
measurable with commercially available
instruments. Other phase transitions –
typically second order phase transitions or
glass transitions – are more difficult to
detect.
However, scientists are faced with exper-
imental challenges such as complicated
sample preparation, choice of matching
crucibles for sample and reference, ther-
mal contact of crucibles, and limitation of
sample properties. The novel technique
TORC (thermo-optical oscillating refrac-
tion characterization) is not subject to the
above obstacles. The revolutionary tech-
nique utilizes a modulated thermal excita-
tion and analysis the optical response in
the refractive index [1]. This sheds light on
temperature- and time-dependent pro-
cesses e.g. melting, glass transition, as
well as curing. Furthermore it grants ac-
cess to one of the fundamental suscepti-
bilities, namely the thermal expansion co-
efficient by using the Lorentz-Lorenz rela-
tion [2,3].
By discussing adhesive and polymer ap-
plications of the innovative measuring
principle at the example of epoxy curing
and the glass transition of polyvinyl ace-
tate, we demonstrate the potential of the
technique for research and development,
as well as quality management.
[1] Müller, U., Philipp, M., Thomassey, M., Sanctuary, R., Krüger, J. K. (2013). Tempera-
ture modulated optical refractometry: A quasiisothermal method to determine the dy-
namic volume expansion coefficient. Thermochimica Acta, 555, 17-22.
[2] Lorentz, H. A. (1880). Ueber die Beziehung zwischen der Fortpflanzungsgeschwin-
digkeit des Lichtes und der Körperdichte. Annalen der Physik, 245(4), 641-665.
[3] Lorenz, L. (1880). Ueber die Refractionsconstante. Annalen der Physik, 247(9),
70-103.
Tobias Husemann
GC
KL
H
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Einfluss von Nukleierungsmitteln auf die Kristallisation von
Polypropylen (PP)
Dr. Gabriele Kaiser, Claire Straßer
NETZSCH-Gerätebau, Selb
Nukleierungsmittel werden Polypropylen
in geringer Konzentration zugesetzt, um
ein früheres Erstarren der Polymer-
schmelze zu erreichen. Dadurch kann z.B.
das entsprechende Formteil schneller aus
dem Spritzgießwerkezug entnommen wer-
den. Des Weiteren sind Nukleierungsmit-
tel in der Lage, die Größe der entstehen-
den Kristallite des Polymerwerkstoffs zu
beeinflussen und wirken sich so auch auf
seine mechanischen Eigenschaften aus.
Durch den Zusatz von sogenannten
Clarifiern werden die entstehenden Sphä-
rulite so klein, dass sichtbares Licht nicht
mehr gestreut wird; das teilkristalline Po-
lypropylen erscheint transparent.
Um das Verhalten eines isotaktischen Po-
lypropylens mit und ohne Nukleierungs-
mittel während des Abkühlens zu untersu-
chen, wurden sowohl dynamische als
auch isotherme Kristallisations-experi-
mente mittels DSC vorgenommen. Die in
den Isothermphasen gewonnenen DSC-
Kurven wurden anschließend einer kineti-
schen Auswertung (unter Verwendung
des Software-Moduls NETZSCH Thermo-
kinetics) unterworfen. Auf deren Basis las-
sen sich Vorhersagen für das Kristallisati-
onsverhalten der Materialien bei definier-
ten Isothermtemperaturen ableiten und
Rückschlüsse auf die Verarbeitungsbedin-
gungen ziehen.
Für isotherme Kristallisationsexperimente
wird der Kunststoff zunächst aufgeschmol-
zen und dann sehr rasch auf eine vorge-
wählte Temperatur abgekühlt. Derartige
Messungen stellen einen hohen Anspruch
an die eingesetzte DSC, da zu niedrige
Kühlraten bereits zu einer vorzeitigen Kris-
tallisation führen können. Durch Einsatz
eines Ofens mit niedriger thermischer
Masse lassen sich die notwendigen, ho-
hen Kühlraten auch in einer Wärmestrom-
DSC realisieren.
Gabriele Kaiser
HC
LM
K
G
Vorhersage der selbstbeschleunigenden Zersetzungstempe-ratur (SADT) für organische Peroxide aus DSC-Messungen
M. Lünne, A. Knorr, K.-D. Wehrstedt
Bundesanstalt für Materialforschung und -prüfung, BAM Unter den Eichen 87, 12205 Berlin
Für den sicheren Transport eines ther-misch instabilen Stoffes oder Stoffgemi-sches in der vorgesehenen Verpackung ist die selbstbeschleunigende Zerset-zungstemperatur (Self-Accelerating De-composition Temperature, SADT) ein we-sentlicher sicherheitstechnischer Parame-ter. Sie ist nicht nur vom Stoff selbst, son-dern auch von der Umgebungstemperatur, der Zersetzungskinetik, der Versand-stückgröße und den Wärmeübertragungs-eigenschaften aus der Kombination von Stoff und Verpackung abhängig. Die SADT, bestimmt für ein 50-kg Ver-sandstück, ist ebenso eine Entschei-dungshilfe, ob es sich bei einem Stoff um einen selbstzersetzlichen Stoff handelt. Für die Bestimmung der SADT werden in den Empfehlungen für die Beförderung gefährlicher Güter, speziell im Handbuch über Prüfungen und Kriterien [1], vier ver-schiedene Prüfverfahren vorgeschlagen. Alle Prüfungen erfordern einen Zeitauf-wand von mindestens einem Tag bis zu mehreren Tagen, wenn nicht Wochen, um die Prüfkriterien zu erfüllen. Es kann des-halb wünschenswert sein, schon in einem frühen Stadium von sicherheitstechni-schen Untersuchungen die SADT eines potentiell thermisch instabilen Stoffes oh-ne großen zeitlichen Aufwand zu bestim-men.
Ein klassisches Screening-Verfahren, um Stoffe mit geringem Material- und Zeitauf-wand zu charakterisieren ist die Differenti-al Scanning Calorimetry (DSC). Wie be-reits Malow und Wehrstedt [2] für einige flüssige organische Peroxide zeigen konn-ten, kann bei Anwendung eines definier-ten Kriteriums für die Bestimmung der Onset-Temperatur in der DSC eine SADT berechnet werden, die im Vergleich zum experimentell bestimmten Wert geringe Abweichungen besitzt. In der vorliegenden Arbeit wird die Metho-dik für weitere organische Peroxide ange-wendet, wobei nicht nur flüssige Stoffe, sondern auch Feststoffe einbezogen wer-den. Im Ergebnis zeigt sich unter Berück-sichtigung eines zusätzlichen Sicherheits-abstandes von 5 K bis auf eine Ausnahme ein gutes Abbild zur gemessenen SADT. Zudem wird der Einfluss möglicher Fehler der für die Berechnung notwendigen Ein-gangsgrößen betrachtet. Dazu zählen neben der Bestimmung der Onset-Temperatur, die Aktivierungsenergie und die Dichte oder Schüttdichte. Es bleibt zu prüfen, ob die Berechnung auch für verdünnte Lösungen anwendbar ist. Zudem wäre es wünschenswert, die Berechnung auf potentiell selbstzersetzli-che Stoffe zu erweitern.
Annett Knorr
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig50 / 162 51/ 162
[1] UN Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria, section 28, 6th revised ed., United Nations, New York and Geneva 2015. Deutsche Übersetzung: Empfehlungen für die Beförderung gefährlicher Güter - Handbuch über Prüfungen und Kriterien, urn:nbn:de:kobv:b43-393162
[2] M. Malow, K. D. Wehrstedt, Prediction of the self-accelerating decomposition tem-perature (SADT) for liquid organic peroxides from differential scanning calorimetry (DSC) measurements, J. Haz. Mat., A 120 (2005) 21-24.
Annett Knorr (Forts.)
Der wahre Grund, warum die Titanic untergehen mußte Dr.-Ing. G. Krause
Dr. Krause GmbH, Ahornstr. 28-32, Haus 55, D-14482 Potsdam Tel.: +49 331 740 01 05, Fax: +49 331 704 66 29, E-Mail: [email protected]
Am 14. April 1912 kollidierte die Titanic um 23:40 ca. 300 Seemeilen südöstlich von Neufundland mit einem Eisberg. Die als unsinkbar geltende Titanic verschwand 2 Stunden und 40 Minuten später in den Fluten des Nordatlantiks. Die eigentliche Ursache für den Untergang ist schon vor der Abfahrt der Titanic aus dem Hafen von Southampton zu suchen. Dies geht aus alten Unterlagen hervor. Hier spielt die Aussage eines
Überlebenden eine große Rolle, der als Feuerwehrmann auf der Titanic Dienst hatte. Der Vortrag beschäftigt sich auf wissenschaftlicher Grundlage mit Vorkommnissen auf der Titanic und betreibt sozusagen Unfallforschung im Nachherein und gibt Anregungen zur Vermeidung derartiger Unfälle in der Zukunft.
Gerhard Krause
HC
LM
K
G
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Druckluftspeicherkraftwerke
Reinhard Leithner
TU Braunschweig – Institute of Energy and Process Systems Engineering Franz-Liszt-Straße 35, 38106 Braunschweig
Gerhard Krause Reinhard Leithner
DSC Validierung
Vergleich der Meßwerte mit der Auswertung
Dr.-Ing. G. Krause
Dr. Krause GmbH, Ahornstr. 28-32, Haus 55, D- 14482 Potsdam
Tel.: +49 331 740 01 05, Fax: +49 331 704 66 29, E-Mail: [email protected]
Kalorimetrische Messungen dienen zur
experimentellen Bestimmung physikali-
scher und kinetischer Parameter einer
chemischen Substanz. Aus diesen Stoff-
werten werden sicherheitstechnische
Schlußfolgerungen gezogen, die für die
Produktion, Lagerung und Transport der
Substanz von großer Bedeutung sind.
Zu den etablierten Versuchsmethoden
gehört u.a. DSC. Die Versuchsdauer ist
bei DSC aufgrund der hohen Heizraten
gering und die eingesetzte Probenmasse
beträgt nur einige Milligramm. Die Ver-
suchsauswertungen unterscheiden sich.
DSC Versuche werden üblicherweise
nach der Modellvorstellung von Friedmann
und/oder nach Ozawa-Flynn-Wall (OFW)
ausgewertet. Das führt zur sog. modell-
freien Analyse.
An Hand eines praktischen Beispiels wer-
den diese Unterschiede in der Auswertung
erläutert. Ein chemischer Stoff wurde DSC
Versuchen mit fünf unterschiedlichen
Heizraten unterworfen. Die Versuchser-
gebnisse werden nach beiden Methoden
ausgewertet. Das wesentliche Auswer-
teergebnis besteht in dem sog. Energie-
plot, der die Abhängigkeit der scheinbaren
Aktivierungsenergie E/R und des präex-
ponentiellen Faktors k0 vom Umsatzgrad
zeigt. Diese Parameter fallen je nach
Auswertemethode deutlich unterschiedlich
aus.
Mit den so ermittelten kinetischen Para-
metern wird zum Schluß eine Validierung
der Auswertung unternommen. Es wird
versucht, mit Hilfe der gewonnenen kineti-
schen Parameter die Meßwerte zu repro-
duzieren. Die Reproduktion wird den ex-
perimentellen Ergebnissen gegenüberge-
stellt.
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A chip calorimetry based method for the real-time monitoring of red blood cell sickling J. Lerchner1, C. Lanaro2, P.L.O. Volpe3, F. Mertens1
1 TU Bergakademie Freiberg, Institute Physical Chemistry, Germany 2 University of Campinas, Center of Hematology, Brazil 3 University of Campinas, Instituto de Quimica, Brazil
Keywords: segmented-flow chip calorimetry; erythrocytes; sickle cell disease
Sickle-cell disease is a hereditary blood disorder characterized by an abnormality in the oxygen-carrying hemoglobin mole-cule in red blood cells. The hemoglobin protein HbS in sickle cell erythrocytes (SS-RBCs) has an abnormality in the ami-no acid sequence of the ß-globulin chain. The hydrophilic glutamic acid is replaced by the hydrophilic valine residual. As a consequence, hydrophilic interactions led to the polymerization of HbS molecules during deoxygenation forming helical fi-bers which group together and induce the characteristic sickle shape of the cells [1]. The formation of the polymer fibers trig-gers a cascade of cellular abnormalities which influence the energy balance of the cells. As recently demonstrated [2], segmented-flow chip calorimetry combines ad-vantages of batch calorimetry (small, spa-tially restricted samples of few micro-liters) and flow-through calorimetry (defined am-bient conditions). In particular, the possi-bility to move and manipulate aggregated sample material inside the system is an attractive feature of this technique which offers new and unique options for a
defined treatment of samples during the measuring process and for the real-time measurement of treatment effects. In the presented contribution we demon-strate a new experimental technique which allows the controlled sickling and de-sickling of SS-RBCs by non-invasive oxygen-nitrogen gas treatment of cell samples in parallel with the calorimetric measuring process. To investigate heat rate changes caused by cell sickling the following experiments have been per-formed: (1) Test of the capability of red blood
cells to sickle caused by anoxic treatment of the samples inside the calorimeter.
(2) Analysis of the short-term response of the cell metabolism to deoxygenation of the sample in order to identify the relevance of the aerobic catabolism of reticulocytes existing in the samples.
(3) Comparison of the heat production rate of sickle cell erythrocyte samples after anoxic treatment and after re-oxygenation.
[1] Goodman, S. R., Daescu, O., et al., Exp. Biol. Medicine 238 (2013) 509 – 518. [2] Lerchner, J.; David, K.; Unger, F.; J. Thermal. Anal. Cal. (2017) 127(2), 1307-1317.
Johannes Lerchner
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Calorimetry of Microbial Utilization of Electrical and
Photon Energy
T. Maskow
Department of Environmental Microbiology, WG Biocalorimetry/Ecothermodynamics,
Helmholtz Centre for Environmental Research-UFZ, 04318 Leipzig, Germany
E-Mail: [email protected]
The most microbial organisms grow
chemoorganoheterotrophically, which
means they use the energy that is chemi-
cally linked to nutrients for biosynthesis,
maintenance of the structures, replication
and growth. The maximum possible
growth efficiencies [1] as well as the
growth rates [2] are determined by ther-
modynamic rules and can be calorimetri-
cally monitored in real time. This is of
great practical importance if, for example,
microorganisms are to be used as pro-
ducers in the chemical industry or for con-
taminant degradation in ecosystems. In-
terestingly, despite the successes of bio-
thermodynamics and calorimetry in the
area of microbial utilization of chemical
sources of energy, non-chemical energy
sources for microbial growth (e.g. light and
electricity) were so far rarely considered.
Here, the energy of photons and electrons
allows the microbial reduction of CO2 and
make bio-reactions feasible which are
thermodynamically not allowed. Potential
reasons for this surprising lack of
knowledge are challenges to develop the
required tailor-made calorimeters and to
quantify very low energy conversion effi-
ciencies in case of photosynthesis.
For these reasons, new photocalorimeters
and bioelectrocalorimeters were devel-
oped and tested. In the case of light ener-
gy, it is now possible to determine the
efficiency of energy conservation as a
function of environmental conditions in
real time with an accuracy and throughput
which is not accessible by other methods.
The measuring principle is demonstrated
at the example of microalgae of industrial
importance (i.e. Chlamydomonas rein-
hardtii). In the case of electrical energy,
we succeeded with our tailor-made calo-
rimeter in quantifying previously unknown
energetic burden for growth on electrodes
(i.e. microbial electrochemical Peltier heat)
[3]. Scheme 1 shows exemplarily the prin-
ciple of a bioelectrocalorimeter. Numerous
applications of the new two calorimetric
techniques are conceivable.
Turning up the heat on protein stability characterization.Differential Scanning Calorimetry for the regulated environment
Dr. Marco Marenchino, Bioscience Consultant
MicroCal, Malvern Instruments
There is an ever-widening range of
biophysical assays which play important
roles in biopharmaceutical development,
but using Differential Scanning
Calorimetry (DSC) to characterize thermal
stability gives reliable and reproducible
gold standard data throughout the
development pipeline.
Due to its versatile nature, DSC finds
multiple uses in stability profiling,
formulation development, manufacturing
support, and biopharmaceutical
comparability and biosimilarity analysis.
Protein HOS characterization is also
becoming expected in regulatory
submissions for new biopharmaceutical
drugs and biosimilars.
This presentation will introduce PEAQ-
DSC, a new generation of MicroCal DSC
systems designed for biopharmaceutical
and core labs, and will detail some case
study examples of the use of MicroCal
DSC in formulation development and
biosimilarity and biocomparability analysis
applications.
Thomas Maskow
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Marco Marenchino
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The SI unit kilogram: the new definition and its realization on
the basis of fundamental constants
Arnold Nicolaus
Physikalisch-Technische Bundesanstalt (PTB), Bundesallee 100, 38116 Braunschweig,
Germany
At present, the International Prototype of
the Kilogram, IPK, a 125 years old small
cylinder of platinum-iridium, still defines
the SI unit of mass. For 2018 it is pro-
posed to redefine four of the seven SI
units, in fact on the base of fundamental
constants. This is e.g. already done with
the length unit meter which is referred to c,
the velocity of light. For the kilogram the
Avogadro experiment provides an oppor-
tunity to link the kilogram to the atomic
mass constant mu by counting atoms in a
given amount of mass – here a kilogram of
a 28Si single crystal. And Avogadro’s num-
ber which is the number of entities in a
mole would be the related fundamental
constant. But how to “count” 1025 atoms as
the age of the universe is only 1017 sec-
onds? The solution is a crystal – a very
good crystal of best purity, highest quality
and perfection of crystalline order. With
this it is possible to calculate the number
of atoms if we only know the distance of
the atoms in the crystal and if we know the
macroscopic dimension of an artifact of
this crystal. For the determination of Avo-
gadro’s constant, a sphere made from a
silicon crystal was chosen. Silicon crys-
tals, which occur face-centered cubic, in
high perfection are available since the
early seventies due to semiconductor in-
dustries and the form of a sphere was se-
lected as the obvious form of a cube failed
because of the stability of its edges.
Fig. 1 National Pt-Ir kilogram prototype and 28Si single crystal sphere
Scheme 1: Illustration of the
bioelectrocalorimeter and a
simplified flow of metabolites,
electrons, ions and heat during
Geobacter biofilm growth on
acetate (Ac-). Details are given
in [3].
[1] Liu, J. S.; Vojinović, V.; Patiño, R.; Maskow, T.; von Stockar, U. Thermochim. Acta
2007, 458, 38-46.
[2] Desmond-Le Quemener, E.; Bouchez, T. ISME J 2014.
[3] Korth, B.; Maskow, T.; Picioreanu, C.; Harnisch, F. Energy Environ. Sci. 2016, 9,
2539-2544.
Thomas Maskow (Forts.) Arnold Nicolaus
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From each crystal of about 5 kg two
spheres can be produced. They are manu-
factured with outstanding perfection – they
reach small deviations from roundness, at-
tain extreme small roughness and show
no subsurface damage of the crystal lat-
tice. These spheres have to be measured
for mass and volume. For the mass the
sphere is compared to the national proto-
type of kilogram, a Pt-Ir cylinder. As vol-
ume, surface and material of sphere and
cylinder is distinctly different, numerous
measurements against sorption artifacts
and transfer standards are necessary. For
the volume of the sphere an
optical interferometer is used. It consists in
the main of two high performance objec-
tives with spherical reference faces which
spacing is determined. In a second step
the sphere is inserted in this spherical
spacing and the resulting gaps between
sphere and the respective objective are
measured. This interferometer resolves
deviations from roundness in the sub-nm
range and yields full topographies of the
silicon spheres. As this interferometer is
unique rare and interesting images of the
high precision spheres of the Avogadro
project will be presented.
In a first step it is necessary to measure
the Avogadro constant, NA, with best un-
certainty so that, after fixing this value, in
future the mass of an artifact will be deter-
mined through the fixed value of NA.
For the measurement of the Avogadro
constant four quantities are to be deter-
mined:
=ெ∙౩౦౨
∙௩౫ౙ∙౩౦౨,
with n = 8 the number of atoms per cubic
unit cell.
Herein the quotient of macroscopic vol-
ume Vsphere and the volume of the unit cell
vuc of silicon atoms gives the number of at-
oms of that sphere, and molar mass MSi
and mass of the sphere msphere taking into
account the mass of the entity so that the
number of atoms per mole is derived.
The measurements are divided into crystal
measurements which determine parame-
ters typical for the whole silicon crystal,
here the molar mass and the volume of
the unit cell, and the properties which are
related to the artifact produced from the
crystal, here mass and volume of a test
sphere.
To determine the molar mass with a reso-
lution of better than 10-7 it is necessary to
use isotope enriched material. In natural
resources silicon consists of 92.23% 28Si,
4.67% 29Si and 3.1% 30Si, so it was de-
cided to strike up a cooperation with Rus-
sian institutes to obtain silicon better than
99.99% 28Si – with the drawback of a price
of about 1 Mio € per 1 kg sphere. For this
material a new method, the isotope dilu-
tion mass spectrometry IDMS, could re-
duce the uncertainties for the molar mass
determination to some few parts in 109.
For the volume of the unit cell of silicon
the lattice parameter is determined by
combined X-ray and optical interferometry.
Three thin probes of the crystal are ar-
ranged in a Laue interferometer where an
X-ray beam is split and recombined from
the first two plates so that the X-ray inter-
ference can be observed with the third
plate, the analyzer. For this the analyzer is
moved and its movement measured with
an optical interferometer. The uncertainty
for the unit cell volume reached 7×10-9.
Fig. 2 28Si single crystal sphere in the sphere interferometer of PTB
Arnold Nicolaus (Forts.) Arnold Nicolaus (Forts.)
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which cover almost the whole area of the electrodes, are used to precisely deter-mine the fR response to defined heating pulses thereby calibrating the system. The use of such energy pulses directly
simulates temperature effects of PT and enables extensive thermodynamic charac-terization of heat transfer mechanisms in the resonators.
Fig. 1: Scheme of system setup (left);
resonator with heating structure (middle top); sample holder (mid-dle bottom); photograph of TFC setup (right).
Fig. 2: Resonance frequency of an LGS resonator after heating pulse ap-plication; cooling data fitted with an exponential decay function
Thin-Film Calorimeter Based on High-Temperature Stable Piezoelectric Resonators
Alexander Omelcenko, Hendrik Wulfmeier, Holger Fritze
Technische Universität Clausthal, Institut für Energieforschung und Physikalische Technologien
Thin-Film Calorimetry (TFC) is a meas-urement technique which allows for in-situ analysis of thermal properties such as phase transformation temperatures and enthalpies of thin films and thin-film sys-tems. The key component of the TFC sys-tem presented here are piezoelectric res-onators of langasite (La3Ga5SiO14, LGS) or catangasite (Ca3TaGa3Si2O14, CTGS) single crystals. They are operated as high-ly sensitive temperature sensor. In addi-tion, the resonators also enable gravimet-ric investigations via crystal microbalance technique. The piezoelectric resonators are operated in thickness shear mode at their reso-nance frequency fR which is ~5 MHz. Their resonance frequency is strongly tempera-ture dependent which can be approximat-ed by a parabolic function for LGS. Here, temperature coefficients αT,LGS of ~100 Hz K-1 and ~400 Hz K-1 at 200 °C and 1000 °C are observed, respectively. For CTGS a linear decrease for CTGS with αT,CTGS ~190 Hz K-1 is observed. These strong temperature dependencies enable highly precise determination of temperature fluctuations caused by e.g. phase transformations of thin films depos-ited onto the resonators. Precisely controlled heating ramps of 1-10 K min-1 (deviations of ±0.05 K) are applied via a tube furnace from room temperature up to 1000 °C. As the temperature of the furnace increases, the temperature of the resonators, follows closely the heating
ramp. An S-type thermocouple, located 0.5 mm underneath the resonator ensures precise temperature control. Any genera-tion or consumption of heat by a thin film induces changes with respect to the undis-turbed resonance frequency. The vibrating volume of the resonator shows either en-hanced decrease of fR in the case of an exothermic phase transformation (PT) or a reduced decrease in the case of an endo-thermic PT. This frequency deviation ΔfR in the case of a PT is used to calculate the absolute temperature change ΔT and to determine the enthalpy ΔH of the deposit-ed thin films. For this purpose the deposit-ed mass on the resonator has to be known precisely. As the fR of the resonator is also sensitive to the mass load on the electrode, crystal microbalance technique is used to determine the mass of a thin film. It is calculated directly from the fR before and directly after deposition at a given temperature. The effect can be used during high-temperature analysis, too. Mass loss or gain of a thin film, e.g. due to sublimation or oxidation is observable as an increase or decrease of fR, which dif-fers from the otherwise undisturbed fre-quency. The described thermodynamic system capabilities are demonstrated using Sn films which are deposited on LGS and CTGS resonators. The underlying elec-trodes are insulated by an Al2O3 (400 nm) diffusion barrier from the active material. Furthermore, platinum heating structures,
Alexander Omelcenko Alexander Omelcenko (Forts.)
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Chalcogenides for Phase-Change Memory Applications
Jiri Orava
Department of Materials Science and Metallurgy, University of Cambridge,
27 Charles Babbage Rd., Cambridge CB3 0FS, UK
E-Mail: [email protected]
Chalcogenide phase-change (PC) mate-
rials, exemplified by Ge2Sb2Te5 (GST)
and (Ag,In)-doped Sb2Te3 (AIST), have
been widely studied for their use in opti-
cal (DVD, Blu-ray™) and electrical
(phase-change random-access memory,
PC-RAM) data recording. More recently,
displays and synaptic switches, exploit-
ing respectively the high contrast in re-
flectance and resistance upon reversible
glass-to-crystal transitions, have been at-
tracting increasing attention. In the case
of PC-RAM, a single long and low-power
electrical pulse heats the glass above its
glass-transition temperature, Tg, crystal-
lizing it, which is a rate-limiting step of
the memory operation taking <100 ns
(Fig. 1). Glass is obtained by heating the
crystal with short and high-power pulse
and consequent rapid quenching of the
liquid (critical cooling rates
1091011 K s1).
For the memory to be commercially suc-
cessful, several conflicting requirements
must be met. Focus of the talk is mainly
on crystallization, which must be fast, but
the glass should not crystallize sponta-
neously at elevated temperatures. This
requirement can be met by the presence
of a fragile-to-strong crossover on cool-
ing the liquid [1,2]. The glass should also
not undergo structural relaxations, which
would for example influence the interme-
diate states during long-term depression
in synaptic switching.
While there is on-going research to find
the ‘best-performance’ composition,
priming of the supercooled liquid (Fig. 2),
in other words a pre-structural ordering
by an auxiliary pulse before the main
crystallization voltage (SET), has been
shown to be a promising alternative in
reducing crystallization times to less than
10‒9 s [3].
We will discuss a theoretical description
of pre-bias priming. While priming may
look contradicting the classical nuclea-
tion theory (CNT) from studies of silicate-
based glasses, it can be shown that
priming can be well described in terms of
CNT with the particular thermodynamic
properties of PC chalcogenides. An at-
tempt is made to link crystallization kinet-
ics from atomistic simulations and exper-
iments using thermodynamic and time-
dependent CNT descriptions. Two chal-
cogenide PC systems are considered,
each with distinct input parameters for
the temperature-dependent viscosity in
the calculations of transient and steady-
state nucleation rates. Firstly, GST is
taken to exemplify a high-fragility liquid
with crystal growth partly decoupled from
viscosity. Secondly, the influence of a
fragile-to-strong crossover on crystalliza-
tion will be considered in liquid AIST. We
also hint on the origin of fading of such
effect, i.e. the priming effects relaxes
when there is an unbiased period be-
tween the auxiliary and the main pulse.
Jiri Orava Jiri Orava (Forts.)
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We may show that photocrystallization,
at temperatures which are just fraction of
Tg, a reversible growth of crystalline
phase, which may be difficult to obtain
by traditional thermal annealing from su-
percooled liquid, can be induced. This is
unlike the thermal crystallization in opti-
cal disks (CD-RW, DVD), where alike in
PC-RAM the glass is heated with a laser
above its Tg to crystallize it, and above
its Tm to amorphize it.
Understanding and controlling the tem-
perature dependence of atomic mobility,
i.e. the kinetic term in nucleation and
crystal-growth rates, can pave the way
for trimming the PC-RAM switching times
to less than 1 ns, ultimately leading to
devices that are more power-efficient.
Fig. 1 Schematic of the phase-change pro-
cesses in PCM and optical disk me-
dia with the corresponding atomic ar-
rangements (Tx is the crystallization
temperature, and Tm is the melting
temperature).
Fig. 2 Schematic of a pre-bias priming in
PC-RAM. A variety of combinations
of pulse lengths and powers have
been used, with or without a delay
time, t, which is the period without
any applied bias. ‘LO’ and ‘HI’ stand
for low- and high-power pulses, re-
spectively.
[1] J. Orava, D.W. Hewak and A.L. Greer, “Fragile-to-strong crossover in supercooled
liquid Ag-In-Sb-Te studies by ultrafast calorimetry”, Adv. Funct. Mater. 25 (2015)
4851.
[2] J. Orava, H. Weber, I. Kaban and A.L. Greer, “Viscosity of liquid Ag-In-Sb-Te: Evi-
dence of a fragile-to-strong crossover”, J. Chem. Phys. 144 (2016) 194503.
[3] T. Lee, D. Loke, K.-J. Huang, W.-J. Wang, and S.R. Elliott, “Tailoring transient-amor-
phous states: Towards fast and power-efficient phase-change memory and neuro-
morphic computing”, Adv. Mater. 26 (2014) 7493.
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig66 / 162 67/ 162
Comparison of Calorific Value Measurements of
Biogas Reference and Field Calorimeters
Fernando José Pérez-Sanz
Physikalisch-Technische Bundesanstalt (PTB), Bundesallee 100, 38116 Braunschweig,
Germany
Biogas is a valuable energy source more
often used either directly as fuel or fed into
a biomethane upgrade plant for latter
injection into the natural gas grid. For a fair
trade, a better performance and to improve
the efficiency of the different processes
where biogas is involved is important to
know the calorific value of the gas mixture.
Techniques like gas chromatographic
analysis are too expensive for small and
medium biogas producers and other
affordable techniques like infrared
spectroscopy are lacking of accuracy. That
leave the way open for direct calorimetry
measurements.
Two commercial field calorimeters (Union
Instrument CWD2005 and Cuttler-Hammer
recording calorimeter) were under study.
Different reference mixtures were designed
to study the effect of different
thermodynamic properties (density,
viscosity, calorific value, composition…) on
the measurement process. Two different
calibration standard (ISO 6143 and DIN
51899) were applied and compared to find
the best strategy attending the calibration
procedure, time of calibration, number of
calibration gases and algorithm of
calibration.
A biogas sample was measured using the
LNE reference calorimeter and the two field
calorimeters with the two calibration
standards and the results are compared.
Fernando J. Pérez-Sanz
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Die Mikrokalorimetrie als nicht-invasive Methode zur
Charakterisierung des Metabolismus
Christian Ortmann
TA Instruments - Helfmann Park 10, 65760 Eschborn
Seit langem ist die Kalorimetrie bekannt
und bewährt als direktester Zugang zum
Energiebedarf lebender Organismen, zur
Bestimmung der Stoffwechselraten höhe-
rer Organismen ebenso wie zum Wachs-
tum von Mikroorganismen. Moderne Kalo-
rimeter erreichen eine früher nie geglaub-
te Sensitivität, so dass heute nicht nur der
Metabolismus kleiner (Insekten, Crusta-
ceen) und kleinster Tiere wie parasiti-
schen Egeln (u.a. Schistosoma, Fasciola)
mittels Mikrokalorimetrie untersucht wird,
sondern auch Mikroorganismen und deren
Wachstum (Protozoen, Bakterien oder
Pilze). Inzwischen kann man nicht nur
sehr kleine Wärmeflüsse rasch detektie-
ren, aktuelle Kalorimeter ermöglichen
auch einen hohen Probendurchsatz. Dies
hat insbesondere klinische Relevanz auf-
grund immer weiter fortschreitender Re-
sistenzen, so dass neben den notwendi-
gen Kontrollen stets auch gleich mehrere
Pharmazeutika auf Wirksamkeit und Effi-
zienz simultan getestet werden können. In
allen Disziplinen ist ein hoher Probenum-
fang Voraussetzung für eine bessere sta-
tistische Absicherung der Ergebnisse. In
der Praxis kann dies manche Arbeit um
Monate verkürzen.
Allen kalorimetrischen Anwendungen ist
gemeinsam, dass sie als nicht-invasive
Methode erlauben, die Organismen an-
schließend weiteren Untersuchungen zu-
zuführen. Im Anschluss an die Bestim-
mung von Stoffwechselleistungen können
so beispielsweise später Metabolite extra-
hiert werden und die verbleibenden Nähr-
lösungen untersucht werden, so dass man
umfassende Bilanzen erstellen kann. Kein
Wunder also, dass in zahlreichen wissen-
schaftlichen Disziplinen wieder vermehrt
auf die Kalorimetrie zurückgegriffen wird.
Dieser Vortrag wird einige Beispiele dazu
aufzeigen.
Christian Ortmann
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ThermoPhIL: Thermochemical Investigations of Phase Formation Processes in Ionic Liquids Peer Schmidt*, Monika Reschke, Adrian Wolf, Anastasia Efimova
BTU Cottbus - Senftenberg / Faculty of Environment and Sciences * E-Mail: [email protected]
During the last decade, a great progress has been achieved in the variety of appli-cation of ionic liquids in inorganic synthe-sis [1, 2]. The advantage of ionic liquid based synthesis is mainly founded on low melting temperatures of IL. Despite the low temperature, high reactivity of inorgan-ic solids in ILs can be observed. Thus, soft synthesis conditions can be applied in synthesis and even low temperature met-astable materials are attainable [3]. Never-theless, systematic investigations with the conception of ionic liquids and ionic liquid mixtures as flux systems with temperature and composition dependent physico-chemical properties are lacking to date. As a main topic, the formation of element allotropes and compounds of group XV and XVI elements is presented. As almost all the elemental syntheses succeeded by an electrochemical reduction of the binary oxides, the idea grew to estimate electro-chemical potentials [4] of oxidic precursors for directed reduction towards the ele-ments. For this purpose, complex Cal-PhaD modeling has been realized to ac-count for both complex gas phase equilib-ria which lead to defining p(O2), and pos-sible sublimation reactions of elements or compounds (p(i)). In accordance to ther-mochemical modeling, the reduction of the oxides of As, Sb, Bi, Se, and Te succeeds by application of the reaction system NaBH4/[C4mim]BF4. The reduction also proceeded also without reduction agent in
the temperature range 9 = 225 °C ... 300 °C. Thus, the ionic liquid itself func-tioned as a reduction agent. Referring to this finding, we analyzed the thermal behavior of the applied IL. Prob-lematically, commonly applied methods for determination of thermal decomposition temperature (TG/DSC) vary in a range of up to 50 K. Thus, we have applied and optimized a kinetic model for determina-tion of time dependent thermal stability of ionic liquids: Maximum Operation Tem-perature (MOT) [5]. The MOT value de-scribes the maximum temperature (with a mass loss less than 1%) for application of an ionic liquid in a given period of time. As a conclusion, the thermal stability of IL is much lower as expected based on stand-ard TG experiments and the thermal de-composition of IL can influence the reac-tion mechanism of materials synthesis. Furthermore, reaction systems in IL’s have been investigated, where the optimum reaction temperature is determined by the composition of the flux system and the melting temperature of the respective mix-ture. Thus, reaction systems of ionic liquid halido metalates (here [C4mim]AlCl4) with higher contents of the metal salt (AlCl3) usually require higher reaction tempera-ture. Almost equimolar mixtures ([C4mim]AlCl4) are applicable near room temperature, due to their low melting point.
Peer Schmidt
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Interplay between the Relaxation of the Glass of Random L/D
Lactide Copolymers and Homogeneous Crystal Nucleation:
Evidence for Segregation of Chain Defects
Rene Androsch1, Christoph Schick2,3
1 Center of Engineering Sciences, Martin Luther University Halle-Wittenberg,
06099 Halle/Saale2 Institute of Physics and Competence Center CALOR, University of Rostock,
Albert-Einstein-Str. 23-24, 18051 Rostock3 Kazan Federal University, 18 Kremlyovskaya street, Kazan 420008, Russian Federation
Random L isomer rich copolymers of
poly(lactic acid) containing up to 4% D
isomer co units have been cooled from the
molten state to obtain glasses free of
crystals and free of homogeneous crystal
nuclei. The kinetics of enthalpy relaxation
and the formation of homogeneous crystal
nuclei have then been analyzed using fast
scanning chip calorimetry. It has been
found that the relaxation of the glass
toward the structure/enthalpy of the
supercooled liquid state is independent of
the presence of D isomer co units in the
chain. Formation of homogeneous crystal
nuclei in the glassy state requires the
completion of the relaxation of the glass.
However, nucleation is increasingly
delayed in the random copolymers with
increasing D isomer chain defect
concentration. The data show that the
slower formation of homogeneous crystal
nuclei in random L/D lactide copolymers,
compared to the homopolymer, is not
caused by different chain segment
mobility in the glassy state but by the
segregation of chain defects in this early
stage of the crystallization process.
Christoph Schick
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Electrified Microbiology – Bacteria full of Potential!
Uwe Schröder
Institute for Environmental and Sustainable Chemistry, TU Braunschweig, Hagenring 30,
38106 Braunschweig, Germany.
E-Mail: [email protected]
Bacteria that can conduct produce,
consume and electrons? This is not just a
fancy idea, but it is the basis for novel
microbial electrochemical technologies.
The last decade has seen tremendous
progress in the development of these
technologies: Microbial fuel cells produce
electricity from wastewater, microbial
electrosynthesis may provide access to
the reduction of carbon dioxide. A central
role play electrochemically active
microbial biofilms, in which extracellular
electron transfer wires the microbial
metabolism to electrodes.
How does microbial extracellular electron
transfer work? And what is needed to
bring the idea of microbial electrochemical
technologies to application? This lecture
gives an overview about new insights and
developments in the field of microbial
electrochemistry, highlights recent trends
and discusses future needs.
Uwe Schröder
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Acknowledgement: This work has been supported by the priority program 1708 of Ger-man Research Foundation – DFG. Experimental equipment has been funded by the Eu-ropean Regional Development Fund, EFRE-Brandenburg, Project No. 80155970).
[1] D. Freudenmann, S. Wolf, M. Wolff, C. Feldmann, Angew. Chem. Int. Ed. 2011, 50, 11050.
[2] E. Ahmed, M. Ruck, Coord. Chem. Rev. 2011, 255, 2892. [3] M. Heise, M. Ruck, Z. Anorg. Allg. Chem. 2012, 638, 1568. [4] M. Schöneich, A. Hohmann, P. Schmidt, F. Pielnhofer, F. Bachhuber, R. Weihrich, O.
Osters, M. Köpf, T. Nilges, Z. Krist. 2016, DOI 10.1515/zkri-2016-1966. [5] A. Efimova, L. Pfüzner, P. Schmidt, Thermochim. Acta 2015, 604, 129.
Peer Schmidt (Forts.)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig72 / 162 73/ 162
Experience shows that fundamental equa-
tions of state based on highly accurate
density and speed of sound data describe
caloric properties like heat capacities
more accurately than the available experi-
mental data. For diluted gas states this
statement and its limits can easily be
proven. However, for higher density and
correspondingly large residual effects
these relations become more complex. To
date it is not possible to base traceable
uncertainty statements for caloric proper-
ties on deviations observed for densities
or speeds of sound. Mathematical ap-
proaches can be derived, but to verify or
to falsify their applicability, comprehensive
sets of highly accurate data for heat ca-
pacities or enthalpy differences would be
required at least for some reference fluids.
[1] R. Span and W. Wagner: A new equation of state for carbon dioxide covering the
fluid region from the triple point temperature to 1100 K at pressures up to 800 MPa.
J. Phys. Chem. Ref. Data 25, 1509 - 1596 (1996).
[2] R. Span, E. W. Lemmon, R. T Jacobsen, W. Wagner and A. Yokozeki: A reference
equation of state for the thermodynamic properties of nitrogen for temperatures from
63.151 K to 1000 K and pressures to 2200 MPa. J. Phys. Chem. Ref. Data, 29,
1361 - 1433 (2000).
[3] W. Wagner and A. Pruß: The IAPWS formulation 1995 for the thermodynamic prop-
erties of ordinary water substance for general and scientific use. J. Phys. Chem. Ref.
Data 31, 387 - 535 (2002).
[4] E. W. Lemmon and R. T Jacobsen: A new functional form and new fitting techniques
for equations of state with application to pentafluoroethane (HFC-125). J. Phys.
Chem. Ref. Data 34, 69 - 108 (2005).
[5] O. Kunz and W. Wagner: The GERG-2008 wide-range equation of state for natural
gases and other mixtures: An expansion of GERG-2004. J. Chem. Eng. Data 57,
3032 - 3091(2012).
[6] J. Gernert and R. Span: EOS–CG: A Helmholtz energy mixture model for humid
gases and CCS mixtures. J. Chem. Thermodyn. 93, 274 - 293 (2016).
[7] International Association for the Properties of Water and Steam (IAPWS): Revised
release on the IAPWS formulation 1995 for the thermodynamic properties of ordinary
water substance for general and scientific use (2014).
[8] International Organization for Standardization (ISO): ISO 20765-2:2015, Natural gas
– Calculation of thermodynamic properties – Part 2: Single-phase properties (gas, liq-
uid, and dense fluid) for extended ranges of application (2015).
[9] E. W. Lemmon, M. L. Huber, and M. O. McLinden: NIST Standard Reference Data-
base 23: Reference fluid thermodynamic and transport properties – REFPROP, ver-
sion 9.1. National Institute of Standards and Technology, Standard Reference Data
Program, Gaithersburg, 2013.
[10] R. Span and W. Wagner: On the extrapolation behavior of empirical equations of
state. Int. J. Thermophys., 18, 1415 - 1443 (1997).
Roland Span (Forts.)
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Caloric Properties from Empirical Fundamental
Equations of State
Roland Span
Ruhr-Universität Bochum
For well measured, technically and scien-
tifically relevant fluids and fluid mixtures
empirical multiparameter formulations in
form of fundamental equations of state
have been established as reference for
thermodynamic properties. Well known
examples for reference equations of state
are those for carbon dioxide [1], nitrogen
[2], and water [3] – equations of state for
fluids with excellent data sets, which are
frequently applied not only in technical ap-
plications but also for calibration pur-
poses. A number of fluids that are only rel-
evant for technical applications are de-
scribed with very high accuracy today, too;
in particular this is true for some refriger-
ants [4]. Among the mixture models, the
development of accurate property models
based on multiparameter fundamental
equations of state has focused on natural
gas [5] and CO2-rich [6] mixtures. Some of
these models were formally accepted as
international standards [7, 8], others have
been established as de facto standards by
the scientific community and by interna-
tionally used software products [9].
The drawback of empirical multiparameter
equations of state is that they can only
achieve high accuracy for fluids, for which
accurate experimental data are available.
Studies on suitable mathematical struc-
tures for fundamental equations of state,
the use of algorithms optimizing their
mathematical structure, and finally the use
of constraints in nonlinear fitting [4] have
significantly improved the numerical stabil-
ity of multiparameter equations of state
[10]. They extrapolate well and yield
reasonably accurate results in (limited) re-
gions without data as well. However, mul-
tiparameter equations of state still depend
on the availability of accurate experi-
mental data in broad ranges of states, and
estimates for the uncertainty of property
values calculated from such equations can
only be established by comparison to ex-
perimental data.
A crucial advantage of fundamental equa-
tions of state is that values for all thermo-
dynamic properties are calculated from
derivatives or from a combination of deriv-
atives of a single surface spanning over
temperature and density, respectively over
temperature, density and composition for
mixtures. Different properties calculated
from a fundamental equation of state are
not necessarily accurate, but they are al-
ways consistent to each other. As a con-
sequence, fundamental equations of state
can be based on data for those properties
that can be measured with highest accu-
racy.
Today, multiparameter fundamental equa-
tions of state are mostly based on density
and speed of sound data at homogeneous
states. Highly accurate equipment for den-
sity [11, 12],and speed of sound [13, 14]
measurements has been developed to
provide the required data for pure fluids
and mixtures. Beside this, accurate infor-
mation on vapour-liquid equilibria is man-
datory to precisely describe the location of
the phase boundary. Extensive data sets
have been provided for pure reference flu-
ids and a number of mixtures.
Roland Span
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig74 / 162 75/ 162
THT UK THT INC THT CHINA THT INDIAThermal Hazard Technology Thermal Hazard Technology Thermal Hazard Technology Thermal Hazard Technology1 North House, Bond Avenue 49 Boone Village # 130 Rm 1115, 775 Long, No 1 Si Ping Road 808, Eighth Floor, Tower-IBletchley, Milton Keynes MK1 1SW Zionsville, IN 46077 Shanghai 200092 Pearls Omaxe, NetaJi Subhash PlaceUnited Kingdom USA P.R. China PitamPura, Delhi-110034, IndiaPhone: +44 1908 646800 Phone: +1 317 222 1904 Phone: + 86 21 58362582 Phone: +91 11 4701 0775Fax: +44 1908 645209 Fax: +1 317 660 2092 Fax: +86 21 58362581 Fax: +91 11 4701 0775
E-mail: [email protected] Web: www.thermalhazardtechnology.com
Micro Reaction CalorimetryNewer Applications for the Chemical & Pharmaceutical Industry
Steve Stones
Thermal Hazard Technology
A micro reaction calorimeter has applica-
tions far beyond scale-up and reaction
calorimetry itself. A micro reaction calo-
rimeter is also a scanning calorimeter (a
large volume DSC), an isothermal calo-
rimeter (sensitive enough for stability
studies), a properties calorimeter (for
heat of solution, mixing and specific
heats) and an isothermal titration
calorimeter.
Data from heat capacity measurements
and heat production from microbes will
be presented. The gas flow option to
study Carbon Capture involving the exo-
thermic reaction that occurs when CO2
gas is absorbed by an amine solution will
also be discussed.
Steve Stones
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[11] R. Kleinrahm and W. Wagner: Measurement and correlation of the equilibrium liquid
and vapour densities and the vapour pressure along the coexistence curve of me-
thane. J. Chem. Thermodynamics 18, 739 – 760 (1986).
[12] M. Richter, R. Kleinrahm, R. Lentner, and R. Span: Development of a special single-
sinker densimeter for cryogenic liquid mixtures and first results for a liquefied natural
gas (LNG). J. Chem. Thermodyn. 93, 205 - 221 (2016).
[13] J.P.M. Trusler and M. Zarari: The speed of sound and derived thermodynamic prop-
erties of methane at temperatures between 275 K and 375 K and pressures up to
10 MPa. J. Chem. Thermodyn. 24, 973 – 991 (1992).
[14] K. Meier and S. Kabelac: Speed of sound instrument for fluids with pressures up to
100 MPa. Rev. Scien. Instrum. 77, 123903 - 123908 (2006).
Roland Span (Forts.)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig76 / 162 77/ 162
Determination of the enthalpy of mixing in the binary
system LiFePO4–FePO4 at 25 °C
C. Thomas1, G. Balachandran2, N. Mayer3, R. Hüttl1, J. Seidel1, F. Mertens1
1 Institute of Physical Chemistry, TU Bergakademie Freiberg, Leipziger Str. 29,
D-09599 Freiberg2 Institute for Applied Materials – Energy Storage Systems, Karlsruhe Institute of
Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen3 Institute for Applied Materials – Applied Materials Physics, Karlsruhe Institute of
Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen
Lithium iron phosphate (LiFePO4) is
known for its capability to deintercalate
lithium ions reversibly [1] as well as for its
high thermal stability. Thus, LiFePO4 is
discussed to be a promising cathode ma-
terial for the application in lithium ion bat-
teries (LIB). In comparison with other
cathode materials, such as LiCoO2 and
Li(Co1/3Ni1/3Mn1/3)O2 [2], lithium iron phos-
phate possesses several benefits: low
price, low toxicity, small volume change of
about 7 % and a high theoretic specific
capacity of 170 mA h g–1.
During the cycling process of a battery
LiFePO4 undergoes a sequence of com-
plex chemical reactions. The group of
Yamada [3] proved that LiFePO4 and
FePO4 are partly miscible into each other
at room temperature. Thus, solid solution
phases are formed while charging (delithi-
ation cathode reaction) or discharging
(lithiation cathode reaction) a LIB [4] until
phase separation takes place. The width
of the miscibility gap in this system de-
pends on both temperature [5] and the
primary crystallite size [6, 7]. Ne-
vertheless, besides these phenomenolog-
ical considerations a detailed calorimetric
investigation focussed on the thermody-
namics of the mixing behaviour of this
binary system is still missing.
This contribution focuses on the determi-
nation of the enthalpy of mixing in the sys-
tem LiFePO4–FePO4 via isothermal titra-
tion calorimetry (ITC) by applying a ther-
mal activity monitor system (TAM 2277)
from Thermometric at 25 °C. In order to
account for the influence of the particle
size on the mixing enthalpy, two samples
with significantly different particle size dis-
tributions are investigated. The lithiation
reaction of FePO4 is carried out by adding
of the dissolved reducing agent lithium
iodide stepwise into a dispersion of the
solid in acetonitrile. All of the calorimetric
results are generally in good accordance
with additionally conducted equilibrium cell
potential measurements.
The ITC method turns out to be a new
promising research tool in order to investi-
gate redox reaction induced phase transi-
tion processes of lithium intercalating
compounds as well as the enthalpy of mix-
ing in the LiFePO4–FePO4 system. Com-
pared to cell potential measurements, it
offers an opportunity to access enthalpic
changes directly. Thus, it complements
results gained by electrochemical studies
and provides new insights for a better un-
derstanding of electrode reactions in LIB.
Christian Thomas
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Determination of thermodynamic properties of lithium mono-
silicide based on calorimetric and hydrogenation experiments
Franziska Taubert, Regina Hüttl, Jürgen Seidel, Florian Mertens
TU Bergakademie Freiberg, Institute of Physical Chemistry, Leipziger Str. 29,
09599 Freiberg
Key words: LiSi, heat capacity, entropy, hydrogenation equilibrium, enthalpy of formation
The increasing demand for more efficient
energy sources in portable devices and
electric vehicles represents a major chal-
lenge for battery research and technology.
Silicon and the lithium silicides have at-
tracted increasing attention for use as an-
ode material in future Lithium-Ion-Batter-
ies (LIB) in view of costs and capacity. A
consistent thermodynamic description of
the Li-Si-system including phase and elec-
trochemical equilibria is of great im-
portance for the battery development as
well as for the basic understanding of the
system.
The phase diagram has been studied in
literature for a very long time, but only few
reliable experimental thermodynamic data
was reported. Motivated by this situation
we reported the heat capacities and entro-
pies of the five stable phases Li17Si4,
Li16.42Si4, Li13Si4, Li7Si3 und Li12Si7 [1,2]
and determined recently the enthalpy of
formation of Li7Si3 und Li12Si7 by linking of
the hydrogen equilibrium pressures
peq(H2) from hydrogenation measurements
in a Sievert´s type apparatus with the pre-
cise heat capacity and entropy data of the
appropriate lithium silicides [3].
The aim of this study is the experimental
determination of the heat capacity, en-
tropy and enthalpy of formation of LiSi.
These measurements require a phase
pure sample that was synthesized by me-
chanical alloying. The LiSi was character-
ized by means of XRD, DSC and chemical
analysis. The heat capacity of LiSi was
measured using two different calorimeters.
In the low temperature region from 2 K to
300 K a Physical Properties Measurement
System (PPMS, Quantum Design) based
on a relaxation technique was used,
whereas the measurements at higher tem-
perature (300 K to 740 K) were performed
in a DSC 111 (Setaram) applying the Cp-
by-step method. The measurements at
low temperature permit the calculation of
the standard entropies, as well as elec-
tronic and lattice contributions to the heat
capacity. The enthalpy of formation of LiSi
was computed based on the combination
of hydrogenation investigations in a Sie-
verts apparatus with the heat capacity and
entropy data. The results of this work rep-
resent a significant contribution towards a
reliable thermodynamic data set for the Li-
Si-system.
[1] D. Thomas, M. Abdel-Hafiez, T. Gruber, R. Hüttl, J. Seidel, A. U. B. Wolter, B. Büch-
ner, J. Kortus, F. Mertens, J. Chem. Thermodyn. 2013, 64, 205–225.
[2] D. Thomas, M. Zeilinger, D. Gruner, R. Hüttl, J. Seidel, A. U. Wolter, T. F. Fässler, F.Mertens, J Chem Thermodyn 2015, 85, 178–190.
[3] D. Thomas, N. Bette, F. Taubert, R. Hüttl, J. Seidel, F. Mertens, Journal of Alloys and
Compounds 2017, 704, 398–405.
Franziska Taubert
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Calorimetric Measurements of Phase Change Materials
(PCM)
Stephan Vidi, Michael Brütting, Stefan Hiebler, Christoph Rathgeber
Bavarian Center for Applied Energy Research (ZAE Bayern)
Phase change materials (PCM) are play-
ing an increasing role on our way to a
more energy efficient society. In buildings,
where they are used in encapsulated form
or in composite building materials, they
can act as a short time temperature buffer
or as a thermal energy storage, thus act-
ing as passive conditioning elements.
Similar usage can be found in the automo-
tive sector. PCM do also increase energy
efficiency when used as thermal storages
in non-continuous industrial processes.
Other uses for PCM are the buffering of
temperature peaks in electronic devices
and the transport of perishable goods,
where they again act as a temperature
buffer. In all these applications the exact
knowledge of the thermal properties of
PCMs will allow for the design of applica-
tions with a higher energy efficiency and
lower costs.
One of the essential parameters is the la-
tent heat of the PCM, i.e. the amount of
heat stored or released during the phase
change. When using differential scanning
calorimetry (DSC), the most widespread
caloric measuring technique, to measure
PCM, some problems arise. These are
strong supercooling in many cases due to
small sample sizes, difficulties in the prep-
aration of small, representative samples
(e.g. hygroscopic salt hydrates) and corro-
sion with hermetic tight crucibles. Also
hysteresis in the enthalpy-temperature
curves due to the thermal conductivity of
the samples and depending on the speed
of the measurement, is problematic. In-
creased efforts were made to minimize
these problems on different levels. First
measuring recipes have been developed
within the framework of the PCM RAL
quality assurance RAL-GZ 896 in order to
minimize uncertainties in the measured
enthalpy values and to improve tempera-
ture accuracy for DSC measurements on
weakly supercooling PCM. These include
the preparation of the samples and set
rules for the determination of a suitable
heating and cooling rate. The IEA task 42
/ Annex 29 then expanded on the rules
given by the RAL procedure adding a cali-
bration of the DSC, suggestions for sam-
ple preparation and suggestions for an im-
proved analysis.
Finally different measuring methods have
been developed in the last years focusing
on the measurement of larger samples,
with sizes close to the ones in applications
and with different geometries. The most
prominent new method in the PCM com-
munity is the T-History method, due to its
relatively simple setup and evaluation.
Other methods have also been examined,
such as the macro-DSC method, heat-flow
meter calorimetry and bath calorimeters.
This expands the measurement capabili-
ties to encapsulated materials, strongly in-
homogeneous materials and samples with
almost arbitrary shapes and most im-
portantly to application sized samples.
Stephan Vidi
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[1] A. K. Padhi, K. S. Nanjundaswamy, J. B. Goodenough, J. Electrochem. Soc. 1997,
144, 1188– 1194.
[2] J. W. Fergus, J. Power Sources 2010, 195, 939–954.
[3] A. Yamada, H. Koizumi, S.-I. Nishimura, et al., Nat. Mater. 2006, 5, 357.
[4] Y. Orikasa, T. Maeda, Y. Koyama, H. Murayama, K. Fukuda, H. Tanida, H. Arai, E.
Matsubara,Y. Uchimoto,Z. Ogumi, J. Am. Chem. Soc. 2013, 135, 5497-5500.
[5] J. L. Dodd, B. Fultz, R. Yazami, ECS Transactions 2006, 1, 27–38.
[6] G. Kobayashi, S.-I. Nishimura, M.-S. Park, R. Kanno, M. Yashima, T. Ida, A. Yama-
da, Adv. Funct. Mater. 2009, 19, 395–403.
[7] M. Wagemaker, D. P. Singh, W. J. H. Borghols et al., J. Am. Chem. Soc. 2011, 133,
10222-10228.
Christian Thomas (Forts.)
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[1] G. Ertl, H. Knözinger, Handbook of heterogeneous catalysis, Wiley-VCH,
Weinheim, 1997.
[2] D. Walter, Z. Anorg. Allg. Chem. 2006, 632, 2165.
[3] A. Neumann, D. Walter, Thermochim. Acta. 2006, 445, 200-204.
[4] E. Füglein, D. Walter, J. Therm. Anal. Calorim. 2012, 110, 199-202.
Dirk Walter (Forts.)
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Carbonate formation in oxidic lanthanum compounds –
Isothermal calorimetry
D. Walter*, E. Haibel
Gefahrstofflaboratorien Chemie und Physik, Institut für Arbeitsmedizin,
Justus-Liebig-Universität, Aulweg 129, D-35392 Gießen
* E-Mail: [email protected]
Lanthanumoxide (La2O3) can be used as
catalysis material for a variety of reactions
[1]. The preparation of La2O3 is usually
performed from lanthanum hydroxide
(La(OH)3) due to a two-step thermal con-
version of lanthanum oxide hydroxide
(LaOOH) [2, 3]. Together with water,
La2O3 again forms the starting product
La(OH)3. Undesirable carbonaceous con-
stituents can arise in a humidified CO2-
containing atmosphere (e.g. air), which
will have influence on the catalytically ac-
tivity [4]. Isothermal calorimetric meas-
urement in a humidified CO2-atmosphere
were performed, to specify the chronologi-
cal development of carbonation for differ-
ent oxidic lanthanum compounds (La2O3,
LaOOH und La(OH)3). The results show,
that the carbonation of La(OH)3, La2O3 as
well as LaOOH is an exothermal reaction
(Fig. 1).
Measurements of La(OH)3 in a humidified
CO2-containing atmosphere result in a
heatflow-maximum after ~3 h (T = 40 °C).
After 20 h the CO2 uptake is finished.
Whereas the measurements of La2O3
reach in a humidified CO2-containing at-
mosphere the heatflow-maximum after
~2 h with considerably greater amounts of
heat compared to La(OH)3. The reason for
this behaviour is two overlapping exo-
thermal reactions: for one La(OH)3 is
formed by an exothermal reaction of
La2O3 with water and, additionally a CO2
incorporation takes place.
Fig. 1: Isothermal calorimetry of La2O3,
La(OH)3, LaOOH and Al2O3
(reference) in a humidified CO2-
containing atmosphere; T = 40 °C
The conversion is finished after 36 h. The
reaction of LaOOH to La(OH)3 and the
incorporation of CO2 happens so quickly
that under the chosen experimental condi-
tions (stable phase = 45 min; T = 40 °C)
the reaction process can not be recorded
completely. The conversion is finished
after 6 h already. Thermogravimetric anal-
ysis confirm that after 40 h at 40 °C in a
humidified CO2-containing atmosphere
La(OH)3 and LaOOH convert completely
into lanthanum carbonate (La2(CO3)3),
whereas La2O3 converts into carbonate
containing La(OH)3
La2O
3+ H
2O + CO
2
La(OH)3
+ H2O + CO
2
LaOOH + H2O + CO
2
Al2O
3+ H
2O + CO
2
Dirk Walter
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig82 / 162 83/ 162
The decomposition of tert.-butyl hydroperoxide studied by
differential scanning calorimetry.
Dr. Thomas Willms*1, Dr. Holger Kryk1, Dr. Jana Oertel², Prof. Dr. Uwe Hampel1
1 Helmholtz-Zentrum Dresden - Rossendorf, Institute of Fluid Dynamics,
Bautzner Landstraße 400, 01328 Dresden, Germany
² Helmholtz-Zentrum Dresden - Rossendorf, Institute of Resource Ecology,
Bautzner Landstraße 400, 01328 Dresden, Germany
* Email-Address of the presenting author: [email protected]
In the frame of the investigation of the
oxidation of isobutane to t-butyl hydroper-
oxide (TBHP), which has been investigat-
ed for the first time as a two-phase pro-
cess in a capillary reactor at high tempera-
tures and pressures, the prevention of
decomposition of TBHP was an important
subject. The observed products di-
tert.butyl peroxide, tert.butanol, acetone,
and methanol are due to the thermal de-
composition of TBHP, which is also influ-
enced by wall effects. Therefore, the de-
composition of TBHP has been studied by
Differential Scanning calorimetry (DSC) at
higher temperatures using for the first time
different DSC conditions (several crucible
types and pressure conditions, heating
rate, substance mass etc.). An aluminium
crucible, a medium pressure and different
high pressure stainless steel crucibles
(steel, gilded, silicon coated) have been
used to show the influence of the crucible
on the DSC curve. The influence of a pro-
tection of the sample against the gilded
copper blowout disk by aluminium foil on
the DSC has been investigated. It has
been found that the blowout-disk has an
important influence on the DSC curve.
The reaction mechanism of the decom-
position of TBHP and its kinetics at differ-
ent conditions has been discussed. It has
been shown mathematically for the first
time that, despite the complex mecha-
nism, a first order kinetics can actually
describe the reaction at low temperature
conditions. Kinetics has been investigated
by evaluation of the DSC curves using an
nth order approach and a model free ki-
netics approach.
Thomas Willms
Solubility Parameters: A Versatile Concept
Emmerich Wilhelm
Institute of Materials Chemistry & Research/Institute of Physical Chemistry,
Universität Wien, Währinger Straße 42, A-1090 Wien, Österreich
E-Mail: [email protected]
The main objectives of this contribution
are (I) providing a brief overview of the
evolution of the solubility parameter ( i )
concept, (II) presentation of the key physi-
cochemical aspects of popular i -related
models in solution chemistry, and (III) a
concise survey of a few selected applica-
tions in physical chemistry and chemical
engineering [1]. Prediction of thermody-
namic properties of liquid nonelectrolyte
solutions from properties of the pure con-
stituents has come a long way since the
classic studies of Scatchard and Hilde-
brand [2,3] leading to regular solution the-
ory for which i is the pivotal property [4]:
r,L, L,, , ,i i iT P U T P V T P ,
where r,L,iU denotes the molar residual
internal energy of pure liquid component i,
and L,iV is its molar volume, i.e. i is the
square root of the cohesive energy
density.
The frequently neglected temperature and
pressure dependence of i will be dis-
cussed, for instance via a generalized
corresponding states theory approach:
0 1 21 2 2c, r, r, r, r, r, r,i i i i i i i i i iP T T T
2 3r, r, r, r, r,
p p p p pi i i i iT a b T c T d T
p = 0, 1 or 2,
where all the symbols have their custom-
ary significance.
Finally, extensions to multi-dimensional
solubility parameter models will be indi-
cated [5], which quantities are used with
mixtures containing strongly polar and/or
hydrogen-bonded substances. The most
widely used three-dimensional solubility
parameter was introduced by Hansen in
1967 [6], and the 50th Anniversary HSP
Conference took place at the University of
York, UK, 5 – 7 April 2017.
[1] E. Wilhelm, Solubility Parameters: A Brief Review, in: Enthalpy and Internal Energy:
Liquids Solutions and Vapours, E. Wilhelm and T. M. Letcher, eds., The Royal
Society of Chemistry/IACT, Cambridge, UK, 2017.
[2] G. Scatchard, Chem. Rev. 8, 321-333 (1931).
[3] J. H. Hildebrand and S. E. Wood, J. Chem. Phys. 1, 817-822 (1933).
[4] J. H. Hildebrand and R. L. Scott, The Solubility of Nonelectrolytes, 3rd edn, Reinhold
Publishing Corporation, New York, USA, 1950.
[5] A. F. M. Barton, CRC Handbook of Solubility Parameters and other Cohesion
Parameters, CRC Press, Boca Raton, Florida, USA, 2nd edn, 1991.
[6] (a) C. M. Hansen, J. Paint. Techn. 39, No. 505, 104-117 (1967);
(b) C. M. Hansen, J. Paint. Techn. 39, No. 511, 505-510 (1967);
(c) C. M. Hansen and K. Skaarup, J. Paint. Techn. 39, No. 511, 511-514 (1967).
Emmerich Wilhelm
KC
L
JT
C
ZW
S
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig84 / 162 85/ 162
Through solution to the gas phase: Evaluation of the enthalpy
of vaporization for thermally unstable ionic compounds with
the help of solution calorimetry
Dzmitry H. Zaitsau, Sergey P. Verevkin
Department of Physical Chemistry, University of Rostock, D-18059 Rostock, Germany
Ionic liquids (ILs) are acknowledged as a
new perspective “green” solvents and re-
action media. The successful application
of ILs in industrial processes can’t be
achieved without recycling of such novel
media. ILs are known as compounds with
extremely low vapor pressures. Determi-
nation of the enthalpy of vaporization for
ILs is a challenging task and even the
most sensitive devices are often not ca-
pable of determining their vapor pressure.
Another approach for evaluation of vapori-
zation enthalpy is going through the ther-
modynamic cycle from liquid or solid state
to gas. Such approach is used not only as
an independent technique but also as a
robust test protocol for experimental en-
thalpies of vaporization. But even in this
case, the complicated chemical composi-
tion is against the precise investigation of
ILs vaporization enthalpy. As a rule, en-
thalpies of formation in the liquid or crystal
phase are determined by using the com-
bustion calorimetry. However, this method
is not well developed for compounds with
a combination of P, B, S, and F elements
yet.
The solution calorimetry opens the door
for determination of liquid phase en-
thalpies of formation for ILs. At the infinite
dilution in water, the close ion pairs of ILs
separates back to solvated cation and
anion. The same way the enthalpy of for-
mation of solvated ILs separates to the
contributions of cation and anion. Thus,
the sum of enthalpies of formation in
aqueous solution for cation and anion to-
gether with experimental dissolution en-
thalpy provides the experimental enthalpy
of formation in the condensed state. The
alternative way is the synthesis of ILs dur-
ing dissolution experiments. The combina-
tion of the enthalpy of synthesis of IL in
water together with the corresponding
solution enthalpy also leads to the liquid
phase enthalpy of formation.
The final part of the thermodynamic cycle
is the high-level quantum-chemical calcu-
lations which provide the enthalpy of for-
mation for isolated ion pairs of ILs in the
ideal gas conditions. We applied this “non-
linear” thermodynamic studies for the
most complicated ILs, when the results of
other techniques were suspicious are oth-
er experimental techniques just failed.
Dzmitry H. Zaitsau
W
Z
T
Can homogenous nucleation be controlled in a
metallic glass?
Bin Yang1,2, Yulai Gao3, Christoph Schick1,2
1 Institute of Physics, University of Rostock, Albert-Einstein Str. 23-24,
18051 Rostock, Germany2 Competence Centre CALOR, Faculty of Interdisciplinary Research,
University of Rostock, Albert-Einstein-Str. 25, 18059 Rostock, Germany.3 State Key Laboratory of Advanced Special Steels, Shanghai University,
149 Yanchang Road, 200072 Shanghai, PR China
Fast scanning chip calorimetry was suc-
cessfully employed to not only suppress
crystallization but also bypass homogene-
ous nucleation of an Au-based bulk metal-
lic glass on controlled fast quenching. A
truly amorphous metallic glass without ho-
mogeneous nucleation was acquired. Fol-
lowing the rapid quenching, annealing at
different temperatures from 0.001 s to
10000 s was realized, in which homoge-
neous nucleation was allowed and various
local-configurations were obtained conse-
quently. Its effect on crystallization was
quantified based on the evolution of en-
thalpy employing nuclei development ap-
proach. Finally, a C-curve illustrating the
homogeneous nucleation kinetics was ob-
tained and added to the conventional TTT
diagram, by which a truly amorphous state
and the kinetics of homogeneous nuclea-
tion can be estimated. The art to control
homogeneous nucleation and the science
to uncover the corresponding mechanism
provide new insights how to tune the
micro- to nano-structure of metallic
glasses, and facilitates the understanding
of solidification and glass forming ability
both in engineering and scientific fields.
Bin Yang
Der optische Weg zur thermischen Analyse
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Guido Lohkamp-SchmitzPerkinElmer GmbH, Rodgau, Germany
In-situ Evolved Gas Analysis During the 3D Printing Procedure (extract)Three-dimensional (3D) printing technology has recei-ved tremendous interests due to its capability of generating complex-shaped structures, unparalleled high effi ciency and zero residual feedstock. Normally, thermoplastic materials are utilized as the raw material of 3D printers, while more advanced and sophisticated solutions uses the precursor of thermoset materials (or a prepreg) as source. Due to the reaction nature of the precursor, various unpleasant gases could emit during the printing procedure which may include regulation prohibited chemicals.PerkinElmer provides effective solutions for in-situ studies separate and characterize the evolved gas. Furthermore it enables a reverse-engineer on target products, regardless if it is already fully cured up to an additive included prepreg.
For the qualitativication of potential unpleasant gas evolved a time/ temperature controlled 100µl portion was further analyzed by GC separation of the multiple evolving compounds for a clear single compound MSD identifi cation.
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Copyright ©2017, PerkinElmer, Inc. All rights reserved. PerkinElmer® is a registered trademark of PerkinElmer, Inc. All other trademarks are the property of their respective owners.
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Figure 2: Thermogramm with TG-MSD TIC and SIC overlay
The 3D-printed polymer starts to degrade at 585.2ºC under helium atmosphere. It gives a hint that this po-lymer belongs to the high performance engineering polymer category.The primary pyrolytic products are phenol, biphenyl de-rivative and other aromatic derivatives, this is the cha-racteristic fi ngerprints of aramid group polymers (such as Kevlar or Nomex).The evolved “unpleasant gas” during the 3D printing procedure are mostly azoic compounds as revealed by the TG-GC/MS data, and they are most likely used as the initiator of the chain extension reaction.
Figure 3: TG-GC-MSD evolved gas separation example @315°C azoic compound library identifi cation
N
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Liste der Posterbeiträge
Abdelaziz, Amir (Rostock)
Fast scanning calorimetry - Convenient technic for vaporization study of aprotic and protic ionic liquid(D.H. Zaitsau, A. Abdelaziz, S.P. Verevkin, C. Schick)
Aeby, Christian (Basel, Switzerland)
Ermittlung des Detonationsbereichs von Nitrierungsreaktionsmassen im Mini-Autoklaven nach Whitmore
Anhalt, Klaus (Berlin)
Using a modifi ed laser fl ash apparatus to measure spectral emissivity(K. Anhalt, D. Urban)
Bauerecker, Sigurd (Braunschweig)
Critical Radius of Supercooled Water Droplets: On the Transition toward Dendritic Freezing(T. Buttersack, S. Bauerecker)
Brown, Robert K. (Braunschweig)
Preconditioning electroactive biofi lms to improve substrate turnover and cathode research to improve energetic effi ciency of microbial electrochemical technologies(S. Riedl, R. K. Brown, U. Schröder)
Feja, Steffen (Dresden)
Moderne Fluide der Kältetechnik(S. Feja, C. Hanzelmann)
Feja, Steffen (Dresden)
Methoden der thermischen Analyse an modernen Fluiden der Kältetechnik(S. Feja, C. Hanzelmann)
Heinemann, Robert (Senftenberg)
Thermodynamic analysis of crystal growth of zinc oxide by CVT under addition of group XV elements(R. Heinemann, P. Schmidt)
WIRMESSENGASE
Prozesskalorimeter zur kontinuierlichen Bestimmung des Wobbe-Index von Brenngasen.
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CWD_Thermodynamische Modellierung_148x210_Layout 1 29.05.17 15:18 Seite 1
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig100 / 162 101/ 162
Heinsch, Stefan (Braunschweig)
Energy Metering of Raw Biogas(S. Heinsch, S. Sarge)
Helmig, Simone (Gießen)
Characterization of a precipitate from the reaction between aluminium sulfate and cell culture medium(S. Helmig, N. Haibel, J. Schneider, D. Walter)
Krause, Gerhard (Potsdam)
Self-Ignition caused by Solar Radiation
Lemke, Thomas (Haar)
The Performance and Safety of 20 Ah Secondary Lithium cells; testing with the Accelerating Rate Calorimeter (ARCTM)(T. Lemke, D. Montgomery, I. Hutchins)
Lemke, Thomas (Haar)
Micro Reaction Calorimetry: Newer Applications for the Chemical & Pharmaceutical Industry(S. Stones, M. Ottaway)
Lerchner, Johannes (Freiberg)
Unconventional Calorimetry Using Segmented-Flow Technique. Solid Samples in Flow-Through & Dispersion Free Reaction Calorimetry(J. Lerchner, F. Mertens)
Maskow, Thomas (Leipzig)
Thermodynamic Feasibility Analysis – a Suitable Tool for Systems Biology?(H. Kohrt, C. Held, S. Verevkin, T. Maskow)
Mishina, Karina (St. Petersburg, Russia)
The reference calorimeter system for metrological assurance of combustion energy measurements(E.N. Korchagina, I.V. Kazartsev, D.Yu. Yanovskiy)
Liste der Posterbeiträge
Nopens, Martin (Hamburg)
Water-bonding and sorption enthalpy in nanoporous biopolymer composites(M. Nopens, U. Sazama, M. Fröba, A. Krause)
Pinnau, Sebastian (Dresden)
Untersuchung des Schmelz- und Kristallisationsverhaltens von Phase Change Materials für Latentwärmespeicher(S. Pinnau, C. Breitkopf)
Prozeller, Domenik (Mainz)
Beyond the Protein Corona – Lipids Matter for Biological Response of Nanocarriers(J. Müller, D. Prozeller, A. Ghazaryan, M. Kokkinopoulou, V. Mailänder S. Winzen, . Landfester)
Reschke, Monika (Senftenberg)
Thermochemical modeling and synthesis of elements and compounds of groups 15 and 16 from the element oxides in [C4mim]BF4(M. Reschke, J. Thiesler, P. Schmidt)
Sauter, Waldemar (Braunschweig)
Sustainable electrochemical synthesis of regenerative transportation fuels(W. Sauter, U. Schröder)
Schick, Christoph (Rostock)
Crystallization of polyethylene at large undercooling(E. Zhuravlev, V. Madhavi, A. Lustiger, R. Androsch, C. Schick)
Taubert, Franziska (Freiberg)
Thermodynamic description of the Li-Si-System based on calorimetric and hydrogenation measurements(F. Taubert, R. Hüttl, J. Seidel, F. Mertens)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig102 / 162 103/ 162
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Die 22.Kalorimetrietage
Kurzfassungen der Posterbeiträge
Thomas, Christian (Freiberg)
Isobaric heat capacity data of orthorhombic FePO4 in the temperature range between 223 K to 773 K(C. Thomas, T. Zienert, R. Hüttl, J. Seidel, F. Mertens)
Wels, Martin (Senftenberg)
Evaluation of eutectic mixtures for use as PCM. Thermodynamic modeling and experimental methods(M. Wels, A. Efi mova, P. Schmidt)
Wolf, Adrian (Senftenberg)
Micro reaction calorimetry for investigation of phase formation processes in ionic liquid fl ux systems(A. Wolf, A. Fandrey, P. Schmidt)
Zimmerer, Stefan (Caluire, France)
Recent improvements in the high pressure DSC method applied to the study of gas hydrates(R. André, P. Le Parlouër, L. Marlin, F. Plantier, J.-P. Torre)
Zimmerer, Stefan (Caluire, France)
Combined calorimetric and manometric measurements for the study of sorption properties of porous materials(R. André, J. Francois, P. Le Parlouër)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig104 / 162 105/ 162
Fast scanning calorimetry - Convenient technique for
vaporization study of aprotic and protic ionic liquid
D.H. Zaitsau2,3, A. Abdelaziz1,2, S.P. Verevkin2,3, C. Schick1,2
1 University of Rostock, Institute of Physics, Albert-Einstein-Str. 23-24, 18051 Rostock,
Germany2 University of Rostock, Faculty of Interdisciplinary Research,
Competence Centre CALOR, Albert-Einstein-Str. 25, 18051 Rostock, Germany3 University of Rostock, Institute of Chemistry, Dr.-Lorenz-Weg 2, 18059 Rostock,
Germany
The experimental determination of the
absolute vapor pressure for such extreme-
ly low volatile compounds as ionic liquids
(ILs) is still a challenging task. The con-
ventional methods used to study such
materials have a limited temperature
range since they are limited towards low
temperatures and low vapor pressures by
sensitivity and towards high temperatures
by stability of the compounds. So the de-
termination becomes very time-consuming
and also less reliable due to the possible
decomposition of ILs at elevated tempera-
tures.
The recently developed ultra-fast scanning
calorimetry method was applied to deter-
mine the absolute vapor pressures of ionic
liquids. This technic allows heat capacity
measurements of nanogram samples at
heating rates up to 106 K s-1 giving the
possibility to determine the vaporization
rate even at high temperature range and
to decrease drastically the experimental
time. The DFSC-technique has
shown reliable absolute vapor pressure
data for ionic liquids over a temperature
range from 400 to 780 K.
The study was performed under different
inert atmospheres (N2, He, SF6), which
one needs to distinguish between evapo-
ration and decomposition of the ILs. The
mass loss rates per unit of area were
compared for the different gases since the
decomposition is independent of the am-
bient gas unlike the evaporation process,
and it has been proofed the absence of
decomposition during the evaporation.
The thermodynamic parameters of vapori-
zation of these ILs were also calculated
from the corresponding vapor pressures
data, the agreement of the vapor pressure
and the evaporation enthalpies with the
literature data is remarkably good and
proofs the reliability of the device to de-
termine vapor pressures and evaporation
enthalpies.
Amir Abdelaziz
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig106 / 162 107/ 162
[1] “Investigation of the use of a closed pressure vessel test for estimating condensed phase explosive properties of organic compounds” M.W. Whitmore, G.P. Baker; Journal of Loss Prevention in the Process Industries 12 (1999)
[2] “A closed pressure vessel test (CPVT) screen for explosive properties of energetic organic compounds” A Knorr, H. Koseki, X.-R. Li, M. Tamura, K. D. Wehrstedt, M. W. Whitmore; Journal of Loss Prevention in the Process Industries 20 (2007)
Ermittlung des Detonationsbereichs von Nitrierungsreaktions-massen im Mini-Autoklaven nach Whitmore
Christian Aeby
TÜV SÜD Schweiz AG, Mattenstrasse 24, CH-4002 Basel, Schweiz
Das Explosionsverhalten von Reaktions-gemischen z.B. aus Nitrierungen wird häu-fig mittels Stahlrohr Tests o.ä. untersucht (z.B. BAM 50/60, UN Gap Test, Koenen Test). Diese Tests sind umständlich und können oft nicht in unmittelbarer Nähe des Syntheselabors durchgeführt werden. Bei-spielsweise benötigt der UN Gap Test mehrere hundert Gramm Reaktionsmasse und der Versuch muss auf einem speziel-len Gelände, das für Sprengungen geeig-net ist, durchgeführt werden. Als Alternative bieten sich thermische Prü-fungen im Mini-Autoklaven nach Whitmore an [1]. Bei dieser Prüfung wird nur ein Gramm der Reaktionsmasse kontinuierlich auf ca. 400°C erwärmt. Die Zersetzungs-reaktionen werden hierbei mittels
hochauflösender Druckmessung (im kHz-Bereich) aufgezeichnet. Anhand der maxi-malen Druckanstiegsgeschwindigkeit und der Zersetzungstemperatur kann entschie-den werden ob ein Reaktionsgemisch de-tonationsfähig, deflagrationsfähig oder nicht explosiv ist. Die Entscheidungskrite-rien werden durch Vergleichsmessungen mit Stoffen, welche im Orange book - Ma-nual of Tests and Criteria beschrieben sind, gemäss [2] validiert. Im präsentierten Fall wurden die Detonati-onsgrenzen einer Nitrierungsreaktions-masse in Abhängigkeit des Mischverhält-nisses von organischem Stoff zu Nitrier-säure ermittelt. Diese Werte werden mit Literaturwerten verglichen und diskutiert.
-10000
-5000
0
5000
10000
15000
20000
25000
30000
35000
0
50
100
150
200
250
300
350
400
450
3824 3824.5 3825 3825.5 3826 3826.5 3827 3827.5 3828
Time [s]
Pres
sure
incr
ease
[bar
/s]
Pres
sure
[bar
]
Detonation of a nitration FRM
Pressure [bar] 1kHz Pressure [bar] 2Hz (dp/dt) [bar/s]
Christian Aeby (Forts.)Christian Aeby
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig108 / 162 109/ 162
Critical Radius of Supercooled Water Droplets:
On the Transition toward Dendritic Freezing
Tillmann Buttersack, Sigurd Bauerecker*
Institut für Physikalische und Theoretische Chemie, Technische Universität
Braunschweig, Hans-Sommer-Strasse 10, D-38106 Braunschweig, Germany
E-Mail: [email protected]
The freezing of freely suspended
supercooled water droplets with a
diameter of bigger than a few micrometers
splits into two rather different freezing
stages, because the freezing enthalpy
cannot completely be stored in the droplet
in the first freezing run and has to be
released to the environment during an
about 1000 times longer time span. In the
present work the distribution of the ice
portion in the droplet directly after the
dendritic freezing phase as well as the
evolution of the ice and temperature
distribution has been investigated in
dependence of the most relevant
parameters as droplet diameter, dendritic
freezing velocity (which correlates with the
supercooling) and supercooling
temperature. On the experimental side
acoustically levitated droplets in climate
chambers have been investigated in
combination with high-speed cameras to
study the correlation between
supercooling temperature and freezing
speed. The obtained results have been
used for finite element method (FEM)
simulations of the dendritic freezing phase
under consideration of the beginning
second, much slower heat-transfer
dominated freezing phase. A theoretical
model covering 30 layers and 5 shells of
the droplet has been developed which
allows us to describe the evolution of both
freezing phases at the same time. The
simulated results are in good agreement
with experimental as well as with
calculated results exploiting the heat
balance equation. The most striking result
of this work is the critical radius of the
droplet which describes the transition of
one-stage freezing of the supercooled
water droplet toward the
thermodynamically forced dendritical two-
stage freezing in which the droplet cannot
sufficiently get rid of the formation heat
anymore. Depending on the parameters
named above this critical radius was found
to be in the range of 0.1 to 10 micrometers
by FEM simulations.
Further, in our presentation we adopt the
hypercooling temperature as a concept
which is common in the materials
sciences to water ice research. The
hypercooling temperature is defined by
the highest temperature at which the
freezing enthalpy can completely be
stored within the freezing system. This
means that the liquid droplet can
completely freeze in one run without heat
release to the environment. We
emphasize that the heat capacity of the
supercooled water strongly depends on
the temperature, and also the freezing
enthalpy is temperature dependent. This
leads to a considerably higher hyper-
cooling temperature compared to the
value found in the literature.
Using a modified laser flash apparatus to measure spectral emissivity
K. Anhalt, D. Urban
Physikalisch-Technische Bundesanstalt (PTB), Abbestraße 2-12, D-10587 Berlin, Germany
The precise knowledge of the spectral emissivity is essential for industrial radia-tion thermometry and the design of high temperature applications and the model-ling of radiative heat transfer. It becomes increasingly important at elevated temper-atures above 1000 K where the heat transfer is dominated by radiation. In recent years, the PTB developed a new measurement technique for the spectral emissivity, the so called dynamic emissiv-ity measurement (AdεM) [1]. The meas-urement is based on a laser flash set-up – a well-established method for determining the thermal diffusivity [2]. The setup is modified to measure in situ the absolute
laser energy, used to pulse heat the sam-ple, and the absolute temperature rise of the rear side of the sample. Recently, the conventional tube furnace was replaced with an inductive heating system, which allows for the sample to be heated in a cold environment. Any interre-flections between hot furnace walls and sample are therefore minimized, which al-lows to reduce the measurement uncer-tainty especially for samples with a reflect-ing surface (i.e. smaller emissivity). In this set-up, a characterised array spec-trometer allows for a spectral emissivity measurement in the spectral range be-tween 550 nm to 1100 nm.
[1] Krenek, S., Gilbers, D., Anhalt, K., Taubert, D. R., Hollandt, J. (2015). A Dynamic Method to Measure Emissivity at High Temperatures. International Journal of Thermo-physics,36(8), 1713-1725.
[2] Parker, W. J., Jenkins, R. J., Butler, C. P., Abbott, G. L. (1961). Flash method of deter-mining thermal diffusivity, heat capacity, and thermal conductivity. Journal of applied physics, 32(9), 1679-1684.
Sigurd BauereckerKlaus Anhalt
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig110 / 162 111/ 162
Moderne Fluide der Kältetechnik
Steffen Feja, Christian Hanzelmann
ILK Dresden gGmbH, Bertolt-Brecht-Allee 20, 01309 Dresden
Tel.: 0351-4081767, E-Mail: [email protected]
Für die Kälteerzeugung werden heutzu-
tage zum Großteil Kompressionskältema-
schinen eingesetzt. Der Kältetechniker be-
dient sich dabei je nach Anwendungsfall
bei den natürlichen Kältemitteln oder syn-
thetisch hergestellten Kältemitteln. Seit
Einführung der Sicherheitskältemittel, je-
doch spätestens seit Inkrafttreten des
Montreal Protokolls, steht ihm dabei ein
umfangreiches Potpourri von derzeit mehr
als 300 als Refrigerant (Abkürzung: R) ge-
listeten Chemikalien und deren Mischun-
gen zur Verfügung (Tabelle 1).
Alternativ zur beschriebenen Kompressi-
onskälte kann Kälte auch aus Wärme
durch den Absorptionskälteprozess er-
zeugt werden. Auch hierfür sind eine
beliebige Kombination aus Kältemitteln
und Absorptionsmitteln denkbar. Neuer-
dings halten Nanofluide und Ionische
Flüssigkeiten in der Kältetechnik Einzug.
Für die obengenannte Kompressionskälte
kommen zudem noch Kältemaschinenöle
zur Schmierung der bewegten Teile hinzu.
Auch hier steht dem Anwender eine Reihe
von speziellen Schmierstoffen zur Verfü-
gung.
Im Rahmen der Präsentation wird auf die
Neuentwicklungen im Sektor der Kälteer-
zeugung und Wärmeübertragung einge-
gangen, wobei auf umweltpolitische und
energetische Fragestellungen eingegan-
gen wird.
Tabelle 1 Entwicklung von Kältemitteln
(Zeitstrahl und verbesserte Umwelteigenschaften)
Vor 1900 1930‘s 1950‘s 1990‘s 2011 Trend
Natürliche KM;andere
CFCs HCFCs HFCs HFOsNatürlicheKM
Eis, CO2, SO2,NH3, Ether
R11, R12,R13
R22R134a; R404A(Gemisch)
R1234yfKWs, CO2,
NH3, H2O
Chlor-methan
CCl3F,CCl2F2,CClF3
CHClF2 CF3CH2F CF3CF=CH2
Chlorgehalt Hoch Gering - „-“ -
ODP Hoch Gering - „-“ -
GWP Hoch Hoch Hoch (>1000) Gering (< 50) ~ 1
Montreal Protokoll Phase Out Kyoto Protokoll + F-Gase VO Phase Out
Verbesserte Umwelteigenschaften
Preconditioning electroactive biofilms to improve substrate
turnover and cathode research to improve energetic
efficiency of microbial electrochemical technologies
Sebastian Riedl, Robert Keith Brown, Uwe Schröder*
Institute for Environmental and Sustainable Chemistry,
Technical University of Braunschweig, Hagenring 30, 38106 Braunschweig
* Author of correspondence; E-Mail: [email protected], Tel.: +49 531 391 8425
Microbial fuel cells and microbial electroly-
sis cells (MEC) are part of a developing
and widely diversified microbial electro-
chemical technology platform [1]. All of these
technologies utilize electrochemically active
microorganisms (EAM) to catalyze one or
both of the reduction as well as oxidation
half-reactions at the anode and/or cath-
ode. MECs use EAMs at the anode to
convert e.g. organic carbon in a
wastewater stream into a current flow to
the cathode, at which an inorganic mole-
cule e.g. hydrogen gas, is formed.
This study mainly focuses on two aims:
Firstly, on approaches for sophisticated
biofilm growth or preconditioning proce-
dures, which lead to enhanced and sus-
tained electrocatalytic biofilm turnover
rate [2] at an improved efficiency, in a
complex artificial wastewater. Secondly,
on the dimensioning of a MEC by balanc-
ing the required amount – surface area of
the – cathode, based on its electrocatalytic
properties, against the current flow from
the EAMs at the anode. This study also
addresses the transfer of these laboratory
results to real wastewater applications
both in terms of the possible increase in
effective treatment capacity [3] as well as
the associated energetic considerations.
[1] Schröder, U., Harnisch, F., Angenent, L.T. Microbial electrochemistry and technology:
terminology and classification. Energy Environ. Sci. 2015, 8, 513–519. DOI:
10.1039/C4EE03359K.
[2] Baudler, A., Riedl, S., Schröder, U. Long-Term Performance of Primary and
Secondary Electroactive Biofilms Using Layered Corrugated Carbon Electrodes.
Front. Energy Res. 2014, 2. (30). DOI: 10.3389/fenrg.2014.00030.
[3] Brown, R.K., Harnisch, F., Wirth, S., Wahlandt, H., Dockhorn, T., Dichtl, N., Schröder,
U. Evaluating the effects of scaling up on the performance of bioelectrochemical systems
using a technical scale microbial electrolysis cell. Bioresour. Technol. 2014, 163,
206 – 213. DOI: 10.1016/j.biortech.2014.04.044.
Steffen FejaRobert K. Brown
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig112 / 162 113/ 162
Thermodynamic analysis of crystal growth of zinc oxide
by CVT under addition of group XV elements
R. Heinemann*, P. Schmidt
BTU Cottbus – Senftenberg, Universitätsplatz 1, 01968 Senftenberg, Germany
* E-Mail: [email protected]
Beside its possible use as TCO or sub-
strate for crystal growth of GaN, applica-
tion of ZnO in optoelectronics is highly
discussed. Therefore, one of the key as-
pects is the growth of p-doped single crys-
tal phases. Group XV elements such as
phosphorus, arsenic and antimony are
currently discussed as promising dopants.
Chemical vapor transport (CVT [1]) using
CO(g) as transport agent proved its worth
as a well suited method for growth of ZnO
single crystals. Thermodynamic modelling
with TRAGMIN software package [2] (see
figure 1) revealed that addition of P, As
and Sb do not impair the transport equilib-
rium between ZnO and CO(g) in the tem-
perature range in which CVT is performed.
Furthermore, it is shown that the gaseous
species Sb4, Sb2 and As4, respectively,
are involved as transport agent as well.
First attempts of chemical vapor transport
with zinc oxalate, graphite and the regard-
ed group XV element as transport additive
provided ZnO crystals up to 700 µm in
length. The choice of the used group XV
element affects the morphology of the
grown crystals significantly. Transport
attempts with P and As more likely pro-
duced crooked crystals with inclusions.
Whereas addition of Sb to the initial mix-
ture results rather in growth of well-formed
hexagonal columns. Further optimization
of transport conditions, especially the use
of temperature profiles containing two
deposition zones, results into an im-
provement of the crystals’ morphology and
size (more than 1 mm in length) as well as
the yield of single crystals.
Fig. 1: Composition of the gas phase, calculated by TRAGMIN and ZnO crystals grown
by CVT for initial mixtures of zinc oxide, zinc oxalate, graphite, and addition of: A)
phosphorus, B) arsenic, C) antimony
Methoden der thermischen Analyse an modernen
Fluiden der Kältetechnik
Steffen Feja, Christian Hanzelmann
ILK Dresden gGmbH, Bertolt-Brecht-Allee 20, 01309 Dresden
Tel.: 0351-4081767, E-Mail: [email protected]
In der Kältetechnik und Energietechnik
werden derzeitig in jedem Sektor Spezial-
fluide zur Kälte- und Energieerzeugung,
Wärmeübertragung oder als Hilfswerk-
stoffe, wie zum Beispiel als Schmierstoffe
entwickelt. Diese spezialisierten Hochleis-
tungsfluide sind in der jeweiligen Anwen-
dung in direkten Kontakt mit den Dicht-
und Prozesswerkstoffen. Als Beispiel für
die Werkstoffe seien hier genannt: Elasto-
mere für Dichtungen, Metalle als Kon-
struktionswerkstoffe, Glas für Schauglä-
ser, aber auch Klebwerkstoffe, Isolations-
werkstoffe und Schlauchmaterialien kom-
men in der Kältetechnik zum Einsatz.
Zum einen bietet die thermische Analyse
eine Vielzahl von Möglichkeiten zur Beur-
teilung der Flüssigkeiten selbst und der
Wechselwirkungen der Fluide mit den ge-
nannten Werkstoffen. Die Bestimmung der
Wärmeleitfähigkeit und der Wärmekapazi-
tät der Fluide ist beispielsweise eine
Grundvoraussetzung für die
Auslegungsberechnung kältetechnischer
Anlagen. Schmelztemperaturen und Pha-
sendiagramme von Flüssig-Flüssig- oder
Flüssig-Feststoff-Gemischen bilden die
Grundlage zum Verständnis des physikali-
schen Verhaltens von Kühl- und Absorpti-
onssolen. Die Veränderung der Werkstof-
feigenschaften von Kunststoffen unter
dem Einfluss der Fluide kann durch ther-
mische Analyse, zum Beispiel durch die
Glasübergangstemperatur oder Schmelz-
und Zersetzungstemperaturen gut be-
schrieben werden.
Der Beitrag beschäftigt sich mit der Mes-
sung der thermischen Eigenschaften
durch Erweiterung handelsüblicher Appa-
raturen oder neuentwickelten Apparaturen
und Prozeduren (Abb. 1) zu speziell auf
die Kältetechnik zugeschnittenen Hoch-
druckmessmöglichkeiten. Ergebnisse zur
Messung bis zu 160 bar und bei Tempera-
turen von -90 °C bis 140 °C werden ge-
zeigt.
Abb. 1 Apparatur und Prozedur zur Befüllung von Hochdrucktiegeln für die DSC Q200
Robert HeinemannSteffen Feja
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig114 / 162 115/ 162
Energy Metering of Raw Biogas
Stefan Heinsch, Stefan M. Sarge
Physikalisch-Technische Bundesanstalt (PTB), Bundesallee 100, 38116 Braunschweig,
Germany
Biogas is regarded as one possible re-
newable energy carrier for solar energy. It
is produced from organic waste, manure
or energy crops. The resulting biogas is
used either on-side to produce electricity
and heat or upgraded and fed into the
natural gas grid. Although the efficiency of
the conversion of solar radiation into or-
ganic material by plants is rather low
(0.5 % … 2 %) and the conversion into
biogas (mostly methane, carbon dioxide
and water vapour) costs another 50 % in
efficiency, the big advantage compared to
most other so-called renewable energies
is its possibility for disconnecting produc-
tion from use by storage of the gas either
in dedicated biogas storage facilities or –
after upgrading to pipeline quality – in nat-
ural gas storage facilities.
Biogas production offers a number of ad-
vantages which makes it promotion attrac-
tive:
reduction of the use of fossil fuels
reduction of greenhouse gas emissions
(CO2, CH4, N2O)
closing the nutrient cycle (digestate as
bio-fertiliser)
reduction of nitrification of soil and
water
reduction of health risks connected to
inhalating high amounts of ammonia
avoidance of unpleasant odour
creation of added value in rural areas
offering farmers new income opportuni-
ties
Traditionally, the energy content of natural
gas is determined by measuring the vol-
ume flow of the gas under metering condi-
tions, converting this volume to standard
conditions, subtracting the amount of wa-
ter and multiplying the result with the su-
perior calorific value of the gas. However,
our current research in energy metering
aims at qualifying an instrument for relia-
ble, cost-effective, robust and accurate
measurement of the energy content of raw
biogas.
The biggest challenge here is the water
content of the raw biogas (up to 100 %
relative humidity at 40 °C, about 6 % ab-
solute humidity) which makes traditional
measurement techniques for calorific val-
ue like gas chromatography or infrared
spectroscopy unreliable. Calorimetry, on
the other hand, is in principle not influ-
enced by any component of the biogas as
long as it is in the gaseous phase, there-
fore, this technique is employed here.
Many modern calorimeter on the market
employ instead of an open flame with dif-
ferential temperature measurement a
catalytic combustion chamber with deter-
mination of the residual oxygen concentra-
tion in combination with metering of the
fuel gas by pressure controlled nozzles.
Both technologies add additional complex-
ity to the calorimeter, because now an
assumption is made about the stochiome-
try of the combustion process and the
metered volume depends on the density
of the fuel gas.
In our research it is shown that with the
calorimeter employed here, the stochiom-
etry of the combustion can be taken into
[1] M. Binnewies, R. Glaum, M. Schmidt, P. Schmidt, Chemical Vapor Transport Reac-
tions, De Gruyter, Berlin (2012), ISBN 978-3-11-025465-5.
[2] G. Krabbes, W. Bieger, K.-H. Sommer, T. Söhnel, U. Steiner GMIN Version 5.0b,
package TRAGMIN for calculations of thermodynamic equilibrium, Dresden (2008)
Stefan HeinschRobert Heinemann (Forts.)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig116 / 162 117/ 162
Characterization of a precipitate from the reaction
between aluminium sulfate and cell culture medium
Simone Helmig, Natalia Haibel, Joachim Schneider, Dirk Walter
Institut für Arbeitsmedizin, Justus-Liebig-Universität, Aulweg 129, D-35392 Gießen
E-Mail: [email protected]
Background: In vitro analyses make it
possible to investigate complex biochemi-
cal processes and toxicological effects on
cellular level. Cell culture experiments,
besides epidemiological and animal stud-
ies, are an important source of information
in particular for risk assessments of haz-
ardous substances. Nevertheless an ac-
curate interpretation of the results can be
hampered by chemical interactions be-
tween non bio-persistent metal-containing
dusts and the ingredients of the cell cul-
ture medium. Therefore it is necessary to
gain knowledge about these reactions and
to define their resulting products. Espe-
cially soluble metal ions can change their
substance specific properties completely
by such undesirable reactions. As an
example we describe and characterise the
resulting product of a reaction with soluble
aluminium containing dusts and the cell
culture medium RPMI.
Method: Aqueous stock solution (5 mg/ml)
of aluminium sulphate (Al2SO4∙nH2O) was
dissolved in 10 ml RPMI cell culture medi-
um (final concentrations from 1 µg/ml to
100 µg/ml). Then the solutions were fil-
trated. The initial as well as the final sub-
stance products were analysed by elec-
tron microscopy (REM, EDX) and thermal
analysis (TG, DSC).
Results: Soluble Al3+-Ions of non bio-
persistent aluminium-containing dusts and
RPMI cell culture medium form aluminium
phosphate concentration dependently.
The solubility of aluminium phosphate
depends on the number of water mole-
cules integrated into the structure. TG and
DSC analysis show the content of crystal
water and provide the transformation en-
thalpy for the dehydration reaction There-
fore these results provide knowledge on
the solubility of the formed aluminium
phosphate and contribute to correct inter-
pretation of further “in vitro” results.
account by computation and the metering
issue by using adequate calibration gases.
This results in an instrument for the de-
termination of the energy content of raw
biogas fulfilling the requirements of legal
metrology worldwide as laid down in OIML
Recommendation R140 “Measuring Sys-
tems for Gaseous Fuels”.
Simone HelmigStefan Heinsch (Forts.)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig118 / 162 119/ 162
Self-Ignition caused by Solar Radiation
Dr. G. Krause
Dr. Krause GmbH, Ahornstr. 28-32 Haus 55, D-14482 Potsdam
A palette loaded with hard coal dust is stored outside and exposed to solar radiation
Auto-Ignition caused by Solar Radiation
Neglecting Solar Radiation
Dr. Krause GmbHE-Mail: [email protected]: www.selbstentzuendung.com
The Performance and Safety of 20Ah Secondary Lithium cells;
testing with the Accelerating Rate Calorimeter (ARCTM)
Thomas Lemke1, Danny Montgomery2, Ian Hutchins2
1 C3-Analysentechnik2 Thermal Hazard Technology
1. Introduction
The Accelerating Rate Calorimeter (ARC)
gives adiabatic data on electrochemical
cells. These tests fall under two main cate-
gories: Performance (non-destructive) test-
ing and safety testing.
The advantage of the ARC is in its adapta-
bility. An EV or EV+ ARC system with ap-
propriate options can evaluate cells for both
performance and safety.
This poster covers a range of tests carried
out on two cells from different manufactur-
ers using differing chemistries. Although
both cells have the same amp-hour capaci-
ty, total stored energy (watt-hours) between
the cells varies due to the difference in volt-
age resulting from the particular chemis-
tries.
The two cells investigated here are both
20 Ah. One cell is a 20 Ah lithium NMC type
manufactured by EIG while the other is a
20 Ah lithium iron phosphate type produced
by A123. The general industry consensus
regarding these two cells is that iron phos-
phate is a “safer” chemistry than NMC,
however the trade-off is a reduction in cell
cycling performance.
2. Heat capacity
Specific heat capacity is applicable to a ho-
mogenous material, however the heat ca-
pacity of composites can also be measured.
In this case the result is a combination of
the specific heat of the materials making up
the composite sample. The sample in ques-
tion is an electrochemical cell. Heat capacity
measurements on soft-case pouch cells,
used in automotive applications, are simple
to carry out in the ARC. Two cells are
placed either side of a thin kapton-insulated
heating element. The shape of the heater is
rectangular and should approximately
match the cell dimensions. The test protocol
is straight forward – the ARC electronics will
control the power supply, giving an appro-
priate power level in order to heat the cells
at the specified temperature rate.
Thomas LemkeGerhard Krause
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig120 / 162 121/ 162
3. Performance (cycling) tests
With knowledge of the cell average heat
capacity, cycling tests carried out in the
ARC become more useful because the heat
generation of the cell during charging or
discharging can be quantified. For real
world applications, lower heat generation is
generally preferred. This means a more
efficient cell and a reduction in the cooling
requirements for the battery system. Cycling
tests in the ARC are carried out on a single
cell. The cell terminals are secured with
large aluminium clamps to ensure effective
current transfer while the cell is held secure-
ly within a metal frame inside the calorime-
ter chamber. Cables enter the chamber via
a special collar or through current connect-
ors built into the calorimeter. In this case, a
simple C/5 (4 A) charge (CCCV), 1C (20 A)
and C/3 ( 6.7A) discharge (CC) for both
cells was compared. Larger currents can be
applied using appropriate cables. Integrated
cyclers may be provided with the
The calorimeter chamber matches the cell
temperature, so all heat from the element
heats the cells, and no heat is lost from the
cells to the environment. The temperature
rise is therefore approximately linear:
Heat capacity data from the ARC is shown
above. Simple visual inspection of the tem-
perature graph is not useful for analyzing
the results because the mass of the cells
and the input power to the heating element
varies. Taking these two parameters into
consideration gives results of heat capacity
against temperature. The graph then gives
a discrete Cp value for data averaged for
every 2 °C temperature increase. At 35 °C
the Cp values of the cells are:
LiFePO4: 1.03 J/gK; Li NMC: 1.04 J/gK
Graphical Cp values versus temperature are
shown below:
Thomas Lemke (Forts.)Thomas Lemke (Forts.)
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Each cell is heated then held at the starting
temperature for around 45 minutes to check
for self heating. If self-heating exceeds the
sensitivity threshold, the ARC tracks the
reaction. If it does not, the temperature is
increased again and the process is repeat-
ed. The starting temperature was 50 °C, the
temperature step was 50 °C and the ex-
otherm sensitivity was 0.02 °C/min. The cell
was held in a steel frame suspended from
the calorimeter lid with small diameter wires
connected to the cell terminals to monitor
the voltage during the test. The test finishes
when the decomposition reaction is com-
plete. Below – Iron phosphate cell on the
left, NMC in the middle. Comparative data is
shown on the right:
There was a considerable difference be-
tween the response of the two cells in these
tests. Above right is the ARC temperature
data of each test plotted together. The
LiFePO4 cell is in blue and the Li NMC cell
is in red.
The height of the peak is proportional to the
energy released in decomposition. There-
fore the NMC cell decomposition is more
energetic. Although somewhat difficult to
see on the above graph, the NMC cell ex-
ceeded the 0.02 °C/min sensitivity threshold
at 90 °C, however slower self-heating
(0.002 °C/min) was seen from temperatures
as low as 65 °C. In contrast the Iron
Phosphate cell exhibited no self heating
until the very rapid decomposition reaction
at 135 °C. Self-heating rate versus tempera-
ture for the NMC cell is plotted to the right.
5. Further Work – 18650 comparison
Comparison between cell chemistries is a
particular area of study where the ARC can
work as a useful evaluation tool, the instru-
ment’s sensitivity and accuracy allows the
detection of subtle difference between cells.
For example, the effect of repeated cycles
on a cell’s thermal stability may be analysed
using the heat-wait- seek protocol to evalu-
ate how stability changes with the age of the
cell. Examining the effect of cell scale-up is
also possible. Will an 18650 cell have the
same thermal profile as a much larger au-
tomotive-size cell? Below is the heat capaci-
calorimeter system. Any stand-alone cycler
can be used in conjunction with ARC but
data from the two instruments must be
manually synchronized in time. Below is the
charging and discharging data from both
cells plotted together for comparison. In all
cases the lithium iron phosphate cell from
A123 produced more heat (greater tempera-
ture rise) during the electrical process. The
difference in results is examined in greater
detail in the tables below.
4. Cell Safety Testing
The next stage is to use the ARC to carry
out safety tests on both cells. These tests
can simulate conditions that may occur in
real world use if there is a failure in the con-
trol systems of the battery pack, or if there is
major physical damage to the pack. Heat
generated from one cell cannot pass to ad-
jacent cells as there is a uniform tempera-
ture throughout the pack. Data obtained is
in adiabatic conditions. The most fundamen-
tal ARC safety test is a heat-wait-seek test
which establishes the onset of self- heating
in the cell by increasing the cell temperature
in uniform steps. The various components
that make up the cell may begin to react at
different temperatures. Different chemistries
can have different onset temperatures and
“safer” chemistries should have higher on-
set temperatures, as well as giving out less
energy during decomposition. Differences in
speed of reaction (kinetics) are also im-
portant when evaluating safety.
The testing carried out on these two cells
used a standard heat-wait-seek methodolo-
gy. Both cells are charged to 100 % SoC.
Thomas Lemke (Forts.)Thomas Lemke (Forts.)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig124 / 162 125/ 162
Micro Reaction Calorimetry: Newer Applications for the
Chemical & Pharmaceutical Industry
Steve Stones, Martyn Ottaway
Thermal Hazard Technology, 1 North House • Bond Avenue • Bletchley MK1 1SW •UK
Tel.: +44 1908 646700, E-Mail: [email protected]
Introduction
All chemical, physical and biological reac-
tions are accompanied by heat change.
These reactions, though sometimes sub-
tle, can be measured using calorimetry.
This poster aims to show capabilities of
the THT µRC [micro Reaction Calorime-
ter].
The calorimeter consists of a sample and
reference cell designed to accomodate
2ml disposible HPCL glass vials. Optional
pressure cells rated to 10 bar are also
available.
Titration measurements can be made us-
ing the automated syringe tower delivering
µL injections to the magnetically stirred
sample vial.
The in-built peltier allows for experimental
temperatures in the range -5°C to 150°C.
Scan rates up to 2°C/min are also feasi-
ble.
Heat Capacity Measurement
Measurement of heat cpacity is an inte-
grated function of the µRC. Cp is deter-
mined by directly measuring the amount of
heat required to shift the sample tempera-
ture.
A small temperature step (usually in the
order of 0.5-1°C) is applied to the system
and the heat is measured. The experiment
is then repeated in reverse to verify the
measurement. The results from each shift
direction are averaged to give the final re-
sult. Measurement with empty vials was
conducted first to ensure that any differ-
ences between the heat capacity of the vi-
als is accounted for.
ty result for metal-oxide 18650 cells. The
results from this test and others carried out
in the ARC indicate these cells have a 10-
20 % lower heat capacity value over their
operational temperature range compared to
pouch cells of the same chemistry. The test
on both sizes of cells were carried out in the
same calorimeter.
The graph below is a comparison of ARC
thermal runaway data from a commercially
available high-capacity 18650 cell and the
EIG 20 Ah pouch cell detailed earlier.
There are several key differences resulting
from the variations in cell design. The pouch
cell shows a more pronounced internal short
when the separator layer melts, however
cell decomposition occurs at a higher tem-
perature for the pouch cell. The 18650 de-
composition is linked to the cell venting
which is designed to occur through the burst
disk when significant pressure builds up
inside the cell. The pouch cell has no dedi-
cated vent so the entire cell is blown apart
by the decomposition. The graph below is a
comparison of ARC thermal runaway data
from a commercially available high- capacity
18650 cell and the EIG 20 Ah pouch cell
detailed earlier.
Thomas LemkeThomas Lemke (Forts.)
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Heat of reaction under controlled gas
flow
The Gas Flow Option (GFO) gives added
versatility to the instrument making meas-
urement of the heat of reaction at different
flow rates and gas pressures possible.
The option has been used to good effect
to study Carbon Capture involving the ex-
othermic reaction that occurs when CO2
gas is absorbed by an amine solution. The
GFO consists of a flow controller to regu-
late the flow rate of CO2 into the cell con-
taining the amine solution. Weighing the
vial before and after the test is used to cal-
culate the rate of CO2 update.
Methylethanolamine (MEA) was added to
water in 30 % concentration by weight
CO2 absorption was monitored at three
different flow rates.
The new Gas Flow option accurately con-
trols CO2 dosing and allows direct calcula-
tion of CO2 loading in the solvent. The
ability of the µRC Micro Reaction Calorim-
eter to quickly carry out heat of absorption
and heat capacity measurements using
micro litre volumes of reagents makes it
ideal for routine carbon capture studies.
Results
The data in the table below show the re-
sults from Cp measurement of pure materi-
als. The values all agree well with the liter-
ature data which was obtained from NIST.
The largest error was 1.2% which shows
the accuracy of the instrument using sam-
ple quantity 1g or less.
This very simple approach makes the
THTµRC ideal for rapid (less than 1 hour)
measurement of heat capacity of liquids,
solids or mixtures.
Cp / J/gK
(Measured)
Cp / J/gK
(Lit.)
Error /
%
Acetone 2.157 2.130 1.2
Toluene 1.722 1.704 1.1
Soya Oil 1.970 1.970 0.0
NaCl (s) 0.864 0.854 1.2
Heat Production from Microbes
The sensitivity of the µRC is such that mi-
crobial activity can be accurately moni-
tored. Rate of heat production of rumen
microbes was successfully studied at
39°C in the calorimeter. Rumen fluid was
collected from Jersey cows and the cell
suspension (1 mL) added to the sample
vial against a reference cell filled with wa-
ter (1 mL).
The titration syringe was used to deliver
250 µL of 5 mM glucose.
Heat production measured at 1 second in-
tervals. Data courtesy of Timothy J. Hack-
mann, The Ohio State University. USA.
Thomas Lemke (Forts.)Thomas Lemke (Forts.)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig128 / 162 129/ 162
Unconventional Calorimetry Using Segmented-Flow
TechniqueSolid Samples in Flow-Through & Dispersion Free Reaction
Calorimetry
Johannes Lerchner, Florian Mertens
TU Bergakademie Freiberg, Institute Physical Chemistry, Freiberg, Germany
The adaptation of the segmented-flow
technology (SFT) to chip calorimetry ex-
tends its application range considerably, in
particular for the study of
(micro-)biological materials. Primarily, the
SFT was developed to handle samples of
picoliters or nanoliters in microfluidic sys-
tems. Samples dissolved or suspended in
aqueous droplets are forced through the
fluidic channels by a water-immiscible
carrier liquid. Due to the interface tension,
plug flow characteristic is achieved which
is the precondition for an increased
throughput. Moreover, the formation of
spatially limited plugs enables the defined
transport of solid or aggregated samples
through the measuring device. As an ef-
fect of the viscous entrainment of the car-
rier liquid and the capillary pressure inside
the droplets, a thin lubricant film is present
between the droplets and the walls. The
thin film protects the walls against contam-
ination by the sample
(e. g. biofilm formation) and prevents
cross-talking.
In the presented work, we demonstrate
the capability of a segmented flow chip
calorimeter to analyze drug effects on
cancer tissues in real-time. Samples of 1
mm3 of colorectal cancer tissue were
treated with 5-Fluorouracil or staurospor-
ine and subsequently analyzed by seg-
mented flow chip calorimetry. The
observed dynamics of the drug effects is
characterized by defined inflection points
in the heat rate curves.
The investigation of the effect of adrenalin
and noradrenalin on the metabolism of
daphnia demonstrated the excellent real-
time capabilities of the used segmented
flow chip calorimeter. The small thermal
time constant of the calorimeter of only
25 s enabled the detection of drug caused
changes in the motility of the daphnia in a
frequency band-width of 0.02 Hz.
The growth of biofilms at the specifically
prepared surface of small aluminum cylin-
ders which were transported in segments
containing nutrient medium was studied.
The influence of the properties of the nu-
trient medium on the growth rate could be
analyzed.
The controlled fusion of segments inside
the measuring chamber offers opportuni-
ties for the design of new procedures for
high-throughput reaction calorimetry. In
case of an appropriate parameterization of
the segmented flow regarding segment
size and carrier flow rate, separate seg-
ments containing the reactants can be
sequentially transported to the measuring
chamber and merged therein at a defined
position. First application examples will be
presented.
Enthalpy calculated by:
ݐݎݏܣ��ݕℎݐܧ =ݐܪ
ݎݏଶ�ܥ��ݏ��ݎݑ௦ܪ∆ =
ܬ�222.4
ቀ0.12
44.01ቁ
= ଵܬ81.55�
Sample Flow rate of
CO2 feed
(ml/min)
CO2
Absorbed
(g)
CO2
Absorbed
(mmol)
Energy
released
(J)
Enthalpy
(kJ/mol)
MEA 0.3 (wt) 0.98 0.12 2.7 222.4 81.55
1.11 0.12 2.7 226.0 82.87
0.56 0.11 2.5 209.0 83.60
0.26 0.12 2.7 224.0 81.13
Average 0.73 0.12 2.7 220.4 81.54
Adsorption: CO2 and N2 Gas Flow
Through Zeolite
The Micro Reaction Calorimeter from THT
can perform isothermal enthalpy measure-
ments on the exothermic reactions that
occur when gas is absorbed by Zeolites or
other adsorbents.
A comparison of the adsorption capacity
of an adsorbent with saturated or unsatu-
rated active sites can be made. Using the
Zeolite without prior preparation means
that it will already have adsorbed atmos-
pheric species and thus its adsorption ca-
pacity will be lower than that of regener-
ated Zeolite. This is demonstrated in the
following graph.
In the two tests shown, 100 mg of regen-
erated Zeolite was measured for heat of
adsorption in the µRC with a constant CO2
flow. The test was then repeated with 100
mg of unprepared Zeolite. As expected,
the unprepared Zeolite with partially-occu-
pied active sites had a measurably lower
adsorption capacity than the regenerated
Zeolite.
Johannes LerchnerThomas Lemke (Forts.)
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Fig. 1: Research Areas
[1] Maskow, T.; von Stockar, U. Biotechnol. Bioeng. 2005, 92, 223-230.
[2] von Stockar, U.; Maskow, T.; Vojinovic, V. Thermodynamic Analysis of Metabolic
Pathways; EPFL Press Distributed by CRC Press., 2013.
Thermodynamic Feasibility Analysis – a Suitable Tool for
Systems Biology?
H. Kohrt1, C. Held2, S. Verevkin3, T. Maskow1*
1 Department of Environmental Microbiology, WG Biocalorimetry/Ecothermodynamics,
Helmholtz Centre for Environmental Research-UFZ, 04318 Leipzig, Germany2 Laboratory of Thermodynamics, Department of Biochemical and Chemical Engineering,
Technische Universität Dortmund, 44227 Dortmund, Germany3 Institute of Chemistry, Department of Physical Chemistry, University of Rostock,
18051 Rostock, Germany
* E-Mail: [email protected]
Metabolic Flux Analysis (MFA) is a power-
ful tool of systems biology in describing
the functioning of an entire biological cell.
MFA by applying mass balances as well
as kinetic relations results unfortunately in
huge undetermined equation systems.
Thermodynamics might help in reducing
solution space by eliminating solutions
that fulfill mass balances but violate sec-
ond law of thermodynamics. For this rea-
son an algorithm called Thermodynamic
Feasibility Analysis (TFA) has already
been tested on well-known glycolysis
pathway [1]. Unfortunately, even glycoly-
sis pathway has been estimated thermo-
dynamically unfeasible. Neglecting activity
coefficients, poor thermodynamic basic
data as well as neglecting the influence of
special conditions in the cytosol of the cell
(e.g. macromolecular crowding, ionic
strength etc.) have been detected as pos-
sible reasons of the unexpected outcome
[2].
Within the algorithm of TFA, ΔRg is calcu-
lated for each single reaction of a certain
metabolic pathway as well as for combina-
tions of consecutive reactions using the
measured concentration range of the
metabolites. Reactions that will reveal a
positive value of ΔRg will be considered as
thermodynamically unfeasible and desig-
nated as localized bottlenecks. Combina-
tions of consecutive reactions with a posi-
tive value of ΔRg for the total reaction re-
sult in so called distributed bottlenecks.
Both, the occurrence of localized and dis-
tributed bottlenecks, will make a given
metabolic pathway unfeasible.
In the current work, the applicability of
TFA on glycolysis will be explored using
state of the art thermodynamic data and
models. Three areas will be researched
(Fig. 1). First, physical and thermochemi-
cal basic data of selected pure metabo-
lites will be determined. Second, the reac-
tion equilibria of these metabolites under
real cytoplasmic conditions (e.g. ionic
strength, molecular crowing) are deter-
mined and modelled with e-PC-SAFT. Fi-
nally, the pure component data as well as
the reaction data are applied to a dynamic
metabolic network. This project will help to
clarify the potential role of thermodynam-
ics to enlighten complex intra-cellular
metabolic networks.
Thomas Maskow (Forts.)Thomas Maskow
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig132 / 162 133/ 162
Diesen Vortrag bitte unter dem Autor Karina Mishina
«KATET» – heat pipe based calorimeter, the «В-06АК» – calorimeter-comparator. Obtained measurement results confirm the declared accuracy (see table 1). Accu-racy of the CAPG has also been re-searched by means of testing various imi-tators of APG (see table 2), and estimated by a limit of 0,3%. Accuracy of the CLPG is currently being researched and approx-imately estimated at 0,5%. The technical task to implement the pos-sibility of burning various gases in a range of (3 – 90) MJ/m3 with a relative accuracy
of less than 0,5% has been successfully completed. Now the priority is to create the certified standards of gas mixtures with different calorific values. That will be used for cali-bration and verification of industrial gas calorimeters. The production of the reference calorime-ter system is being carried out by the do-mestic scientific enterprise – JSC «Teplofizicheskie pribory (Thermo-physical equipment)» (Russia, Saint-Petersburg).
Fig. 1: The Reference Calorimeter Sys-
tem (CAPG / CLCG) Fig. 2: Scheme of CAPG / CLCG:
1 – control and regulation unit (em-bedded computer); 2 – PID-regulation unit; 3 – electronic communication line; 4 – comparative cell (with electric heater inside); 5 – thermal unit with air thermostat; 6 – heat flow sensor; 7 – measuring cell (with gas burner inside); 8 – pressure sensor system (absolute and gauge); 9 – gas pipe-line; 10, 11 – cylinders, forcers; 12 – step engines; 13 – gas bottle
Diesen Vortrag bitte unter dem Autor Karina Mishina
The Reference Calorimeter System for Metrological Assurance of Combustion Energy Measurements
E.N. Korchagina1, I.V.Kazartsev1, D.Yu. Yanovskiy2
1 Russian Federation, St. Petersburg, D.I. Mendeleyev Institute for Metrology (VNIIM) 2 Russian Federation, St. Petersburg, JSC «Teplofizicheskie pribory»
Recently the Calorimetric Laboratory of D.I. Mendeleyev Institute for Metrology (VNIIM) has been focusing on improving the national system of metrological assur-ance of combustion energy measure-ments of gaseous fuels (gas calorimetry), solid and liquid fuels (bomb calorimetry). The State Primary Standard of the units of combustion energy, specific combustion energy and volumetric combustion energy «GET 16-2010» makes the basis for en-suring the uniformity of measurements and providing traceability in the most im-portant industrial fields of the country – fuel and energy complex, petrochemical, coal, metal and chemical industries. D.I. Mendeleyev Institute for Metrology has been improving the State Primary Standard in the area of combustion calo-rimetry «GET 16-2010» since 2015 (last time it was improved in 2010). This work is performed in accordance with the State Government Assignment and is directed to expand the measurement range from 50 to up to 90 MJ/m3 and decrease the lower range from 10 to 3 MJ/m3. Finally it will allow to develop the metro-logical assurance for precision measure-ments of calorific value of associated pe-troleum gas (APG), natural gas (NG), low-calorific gases (LCG): coke gas, blast-furnace gas, biogas and its mixes using modern calorimeters and chromatographs. The reference calorimeter system (fig. 1) has been assembled, launched and re-
searched by specialists of the Calorimetric Laboratory of VNIIM. The calorimeter sys-tem includes 2 reference calorimeters, which implement a direct calorimetric method of measurements of inferior heat of combustion: in the range of 25 to 90 MJ/m3 – typical for the different types of NG and APG (the calorimeter for APG – CAPG), in the range of 3 to 25 MJ/m3 – typical for the different types of LCG (the calorimeter for LCG – CLCG). The calorimeter system is intended for long-term continuous measurement. Scheme and work principles (fig. 2) are based on a comparison of the gas calorific value with the velocity of its feed rate. The calorimeter contains a gas burner and an electrical heater inside the thermal unit. Heat balance between these parts is con-stantly maintained during combustion pro-cess (compensation method). The CLCG contains additional gas mixing system for combustion of gases with low calorific value: gases in the range of (3 − 10) MJ/m3) are diluted by pure methane in a volume ratio of 3/1 (60% of LCG and 30% of methane) for continuous and steady burning. Calibration of the calorimeters is per-formed using high-purity gases – me-thane, ethane and propane, hydrogen, hydrogen-helium mix. Interlaboratory comparisons have been performed using a NG imitator and 2 other types of reference gas calorimeters: the
Karina Mishina (Forts.)Karina Mishina
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Water-bonding and sorption enthalpy in nanoporous
biopolymer composites
Martin Nopens, Uta Sazama, Michael Fröba, Andreas Krause
Universität Hamburg, Fakultät für Mathematik, Informatik und Naturwissenschaften,
Fachbereich Biologie, Zentrum Holzwirtschaft Holzphysik,
Leuschnerstr. 91 c, 21031 Hamburg
Transport phenomena and material be-
havior of porous biopolymer composites
like wood are mainly influenced by the
water sorption and the chemical structure
of the material. Information in this field
provides possibilities for a better usage of
lignocellulosic materials in classical con-
struction, actual modification and high
advanced products.
The structure of such biopolymer compo-
sites like wood is not understood com-
pletely yet. Circumstances in different ana-
lytical fields are caused by the absence or
the presence of water. Especially bound
water which does not freeze but is rea-
sonable for the swelling and shrinking of
the material is one main problem.
Actual theories indicate a tightly bound
interaction of the water to the OH-groups
of the material as main reason for the be-
havior of this water type.
The Poster will focus on past and actual
research results regarding the under-
standing of the porous structures of wood
and bound water as well as own actual
research in this field. These investigations
are going on to explain the relationship
between the change of mechanical prop-
erties at different moisture contents and
the chemical structure of the materials.
This is done by studying the thermody-
namically behavior and the porosity of the
materials with different experimental
methods.
Diesen Vortrag bitte unter dem Autor Karina Mishina
Table 1: Interlaboratory comparison results
CAPG / CLCG «KATET» heat pipe based calorimeter
«В-06АК» calorimeter-comparator
Developed / approved as a standard at:
by the end of 2017 2010 2010
Measurement range, MJ/m3
3 ÷ 90 10 ÷ 50 25 ÷ 50
Expanded relative uncertainty, %
0,30 ÷ 0,50 0,14 0,20
Measuring results of NG imitator (Hinf
ref = 32,05 MJ/m3, according to ISO 6976:1995)
32,06 (CAPG) 32,06 32,08
Table 2: Measurement results in APG range (calibrated within ethane & propane)
Hinfref,
MJ/m3 Hinf
measured, MJ/m3
(Hinfmeasured-Hinf
ref) / Hinf
ref, %
APG imitator № 1 (methane – 46,37, ethane – 40,35, propane – 10,13,
n–butane – 2,55, n–pentane – 0,6 mol. %)
51,97 51,91 -0,12
APG imitator № 2 (methane – 25,55, ethane – 54,57, propane – 10,13,
n–butane – 3,96 mol. %) 59,28 59,34 0,10
APG imitator № 3 (methane – 1,57, ethane – 75,00, propane – 18,72,
butane – 4,69 mol. %) 66,82 66,84 0,02
APG imitator № 4 (methane – 11,43, ethane – 55,0, propane – 20,0, butane – 8,0, pentane – 4,05, hexane – 1,5, nitrogen – 0,01, carbon dioxide – 0,01 mol. %)
71,03 70,98 -0,08
Note: calculation results are obtained according to ISO 6976:1995. All of the gases are prepared by a gravimetric method. Its component composition is exactly known
Martin NopensKarina Mishina (Forts.)
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Beyond the Protein Corona – Lipids Matter for Biological
Response of Nanocarriers
Julius Müller1,2, Domenik Prozeller1, Artur Ghazaryan1, Maria Kokkinopoulou1,
Volker Mailänder1,2, Svenja Winzen1, Katharina Landfester1
1 Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany2 Dermatology Clinic, University Medical Center Mainz, Langenbeckstraße 1,
55131 Mainz, Germany
In order to use nanomaterials for biomedi-
cal applications in a predictable manner
(e.g. as systems for targeted drug delivery
in the blood stream), their interactions with
the different components of the organism
need to be understood and controlled.
While adsorption processes of different
proteins of the human blood onto nanocar-
rier systems have been investigated thor-
oughly in the past [1-2], the interactions of
lipids and lipid-like molecules in the blood
with nanocarriers are still widely unknown.
Usually, phospholipids, cholesterol, tri-
glycerides and cholesteryl esters are dis-
tributed in the body though the blood
stream in the form of lipoprotein clusters
with a concentration depending on food
intake and physical constitution. These
micelle-like lipoproteins are held together
by protein components, the so called
apolipoproteins. If interaction occurs, the
question arises whether the lipoproteins
will disintegrate upon contact with the na-
nomaterial's surface or if complete lipopro-
tein cluster will interact with the nanoparti-
cles [3]. Following this, we examined in-
teractions of different lipoproteins and
their components with polystyrene nano-
particles as model systems for nanocarri-
ers via isothermal titration calorimetry
(ITC) in order to determine the thermody-
namic adsorption parameters of the inter-
action process and to address the mode
and consequences of their interaction.
Our data indicate that lipoproteins will dis-
integrate upon direct contact with polysty-
rene nanoparticles and that all compo-
nents including the hydrophobic molecules
adsorb on the surface, while excessive
lipoproteins remain intact after surface
saturation of the nanoparticles is reached.
This can most dominantly be observed in
the large change of enthalpy (relative to
complete lipoprotein clusters) during inter-
actions between all lipoprotein classes
and the nanoparticles via ITC. Additional-
ly, this could be imaged by using trans-
mission electron microscopy. As a result
of the lipoprotein adsorption, cell uptake
into macrophages was significantly re-
duced, which means that the biological
behavior of nanocarriers could be greatly
influenced by external factors such as
nutrition.
Untersuchung des Schmelz- und Kristallisationsverhaltens
von Phase Change Materials für Latentwärmespeicher
Sebastian Pinnau, Cornelia Breitkopf
Technische Universität Dresden, Professur für Technische Thermodynamik
Der Wärme- und Kältebedarf von Gebäu-
den und die Verfügbarkeit regenerativer
Energien weisen starke Lastschwankun-
gen auf. Der Einsatz von thermischen
Energiespeichern bietet ein großes Po-
tential zur Erhöhung der Effizienz von
Energieversorgungsanlagen sowie zur
Integration von erneuerbaren Energien.
Latentwärme- und Kältespeicher ermögli-
chen dabei durch die Nutzung von fest-
flüssig Phasenumwandlungen hohe
Speicherdichten. Da aber für jeden An-
wendungsfall ein Phase Change Material
(PCM) mit angepasster Schmelztempera-
tur zur Verfügung stehen muss, besteht
hier ein großer Forschungs- und Entwick-
lungsbedarf.
Häufige Probleme bei der Entwicklung
von PCM sind die bei der Kristallisation
auftretende Unterkühlung sowie
Phasenseparationen bei inkongruent
schmelzenden Gemischen. Diese Effekte
können durch die Zugabe geeigneter
Keimbildner und Verdickungsmittel redu-
ziert oder beseitigt werden.
In der vorgestellten Arbeit wird das
Schmelz- und Kristallisationsverhalten
potentieller PCM charakterisiert. Dazu
werden experimentelle Untersuchungen
mittels simultaner kalorimetrischer und
optischer Analyse mit DSC und Lichtmik-
roskopie durchgeführt. Schwerpunkte
sind die Untersuchung des Einflusses
verschiedener Keimbildner auf die Unter-
kühlung sowie die Kristallisation von
Mehrkomponentengemischen. Der me-
thodische Ansatz und Ergebnisse für
ausgewählte Systeme werden präsen-
tiert.
DSC-Messung mit verschiedenen Heizraten und Mikroskopaufnahme für ein Paraffin
Domenik ProzellerSebastian Pinnau
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig138 / 162 139/ 162
Thermochemical modeling and synthesis of elements and
compounds of groups15 and 16 from the element oxides in
[C4mim]BF4
Monika Reschke*, Johnny Thiesler, Peer Schmidt**
Institute of Applied Chemistry, BTU Cottbus-Senftenberg, 01968 Senftenberg, Germany
* E-Mail: [email protected], ** E-Mail: [email protected]
Innovative synthesis strategies for the
formation of elements of group 15
(phosphorus, arsenic, antimony, bismuth)
and group 16 (selenium, tellurium) or
chalcogenides of group 15 metals for
example Bi2Te3 can be realized by use of
ionic liquids. This can be achieved both
with and without using of an additional
reducing agent.
Using complex CalPhaD modeling [1] and
the resulting electromotive series of oxides
according to SCHMIDT [2], rational synthesis
planning can be carried out before the actual
material synthesis. The electromotive series
allows the clear representation of existence
ranges (pi, Ei)T of present compounds i
and the assessment and prediction of the
course of redox reactions (Fig. 1). In order
to verify this theoretical approach,
experiments with group 15 and 16 element
oxides dissolved in the ionic liquid 1-butyl-3-
methylimidazolium tetrafluoroborate
([C4mim]BF4) were carried out by means
of differential scanning calorimetry (DSC)
with and without a reducing agent in a
temperature range from −30 °C to 300 °C.
The values of the thermochemical stability
(decomposition temperatures) of
[C4mim]BF4 vary widely in the literature:
from 360 °C [3] to 424 °C [4]. However,
since the knowledge of thermal stability is
essential for synthesis planning, the
calculation of the maximum operation
temperature (MOT) (Fig. 2) based on a
kinetic model using non-isothermal TG-
measurements has been performed
before synthesis of investigated systems
[5, 6].
Fig. 1: Electromotive series of solid oxides
for the elements of groups 15 and 16,
calculated at T = 400 K
Fig. 2: Calculation of the maximum operation
temperature (MOT) of [C4mim]BF4
depending on the operating time
[1] S. Winzen, et al., Complementary analysis of the hard and soft protein corona:sample preparation critically effects corona composition, Nanoscale 2015, 7,
2992-3001.
[2] E. Vogler, Protein adsorption in three dimensions, Biomaterials 2012, 33, 1201-1237.
[3] E. Hellstrand, et al., Complete high-density lipoproteins in nanoparticle corona, FEBS
Journal 2009, 276, 3372 – 3381.
Monika ReschkeDomenik Prozeller (Forts.)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig140 / 162 141/ 162
Sustainable electrochemical synthesis of regenerative
transportation fuels
Waldemar Sauter, Uwe Schröder*
Institute for Environmental and Sustainable Chemistry, Technical University of
Braunschweig, Hagenring 30, 38106 Braunschweig
* Author of correspondence; E-Mail: [email protected], Tel.: +49 531 391 8425
In times of declining fossil fuel resources,
new pathways to sustainable transporta-
tion fuels are more important than ever.
Research on methods like Power-to-liquid
are a necessity for the establishment of a
new generation of liquid fuels. Electro or-
ganic synthesis is one possible way to
produce these new fuels, but to fully utilize
the potential of the method, it is most im-
portant that precursor molecules and the
energy used for the process, are renewa-
ble sources.
Photovoltaic and wind energy are weather
depended sources of energy. The fluctua-
tion of electricity is difficult to compensate
in conventional methods of fuel genera-
tion. A fully electrified one-pot process is a
lot more flexible and simplifies mainte-
nance as well as leads to easier scalabil-
ity.
We have demonstrated the principal fea-
sibility of the ElectroFuels approach by
means of the electrochemical conversion
of levulinic acid to octane, the electrocata-
lytic hydrogenation of 5-HMF and furfural
to dimethylfuran and methylfuran, re-
spectively, and the conversion of fatty
acids and oils to alkanes/alkenes [1-4].
[1] Nilges, P.; dos Santos, T.; Harnisch, F.; Schröder, U.: Electrochemistry for biofuel
generation: Electrochemical conversion of levulinic acid to octane. Energy and Envi-
ronmental Science 2012, 5 5231-5235
[2] Nilges, P., Schröder, U.: Electrochemistry for biofuel generation: Production of fu-
rans by electrocatalytic hydrogenation of furfurals. Energy and Environmental Sci-
ence. 2013, 6, 2925-293
[3] Harnisch, F.; Blei, I.; dos Santos, T.R.; Möller, M.; Nilges, P.; Eilts, P.; Schröder, U.:
From the test-tube to the testengine: Assessing the suitability of prospective liquid
biofuel compounds. RCS Advances 2013, 3, 9594-9605
[4] dos Santos, T.; Nilges, P.; Schröder, U.: Electrochemistry for biofuel generation: Trans-
formation of fatty acids and triglycerides to "diesel -like" olefin/ether mixture and ole-
fins. ChemSusChem, 2015, 8 886-893
[1] GMIN Version 5.0b, package TRAGMIN for calculation of thermodynamic equilibrium, G.
Krabbes, W. Bieger, K.-H. Sommer, T. Söhnel, U. Steiner, Dresden, 2008.
[2] P. Schmidt: Thermodynamische Analyse der Existenzbereiche fester Phasen -
Prinzipien der Syntheseplanung in der anorganischen Festkörperchemie, Habilitation,
Technische Universität Dresden, 2007.
[3] J. D. Holbrey, K. R. Seddon, J. Chem. Soc., Dalton Trans. , 1999, 2133–2139.
[4] M. E. Van Valkenburg, R. L. Vaughn, M. Williams, J. S. Wilkes, Thermochim. Acta, 2005,
425, 181–188.
[5] A. Seeberger, A.-K. Andresen, A. Jess, Phys. Chem. Chem. Phys, 2009, 11,
9375–9381.
[6] A. Efimova, L. Pfützner, P. Schmidt, Thermochim. Acta, 2015, 604, 129–136.
Waldemar SauterMonika Reschke (Forts.)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig142 / 162 143/ 162
Thermodynamic description of the Li-Si-System based on calorimetric and hydrogenation measurements
Franziska Taubert, Regina Hüttl, Jürgen Seidel, Florian Mertens
TU Bergakademie Freiberg, Institute of Physical Chemistry, Leipziger Str. 29, 09599 Freiberg
Key words: lithiumsilicides, heat capacity, entropy, enthalpy of formation, hydrogenation
The dominating anode material in Lithium-Ion-Batteries (LIB) is graphite with a spe-cific capacity of 372 mAh g-1. An attractive alternative in few of costs and capacity is silicon. The formation of Li17Si4 leads to a theoretical specific capacity of 4054 mAh gSi
-1 [1]. A basic understanding of the un-derlying phase and electrochemical equi-libria based on reliable thermodynamic data in the Li-Si-system is essential for the battery development. For this reason, our group performed extensive experimental studies on lithium silicides using calorime-try and hydrogenation equilibrium meas-urements in the ternary system Li-Si-H. Currently, five stable phases Li17Si4, Li16.42Si4, Li13Si4, Li7Si3 und Li12Si7 are dis-cussed in literature, as well as the so-called high-pressure phase LiSi and the metastable phase Li15Si4. The heat capac-ities of the five stable phases [2,3] and the enthalpies of formation of Li7Si3 and Li12Si7 based on hydrogen sorption investigations have already been reported by our group [4].
The focus of this contribution is directed to the experimental determination of the heat capacities and entropies of LiSi and Li15Si4 and the determination of the enthalpies of formation of the stable phases by combin-ing the heat capacity and entropy results with the hydrogenation equilibrium pres-sure data determined by recording pres-sure-composition-isotherms in a Sieverts type apparatus at 450°C, 475°C and 500°C. The heat capacities were meas-ured using two different calorimeters: a Physical Properties Measurement System (Quantum Design) in the temperature range from 2 K to 300 K and a DSC111 (Setaram) in the temperature region from 300 K to 600 K. The measurements at low temperatures allow the calculation of the standard entropy of the lithium silicides. Applying the resulting new thermodynamic data set, completely based on experi-mental data, the phase diagram of the Li-Si-system has been calculated with excel-lent quality by the CALPHAD method.
[1] M. Zeilinger, D. Benson, U. Häussermann, T. F. Fässler, Chem. Mater. 2013, 25, 1960–1967.
[2] D. Thomas, M. Abdel-Hafiez, T. Gruber, R. Hüttl, J. Seidel, A. U. B. Wolter, B. Büch-ner, J. Kortus, F. Mertens, J. Chem. Thermodyn. 2013, 64, 205–225.
[3] D. Thomas, M. Zeilinger, D. Gruner, R. Hüttl, J. Seidel, A. U. Wolter, T. F. Fässler, F. Mertens, J Chem Thermodyn 2015, 85, 178–190.
[4] D. Thomas, N. Bette, F. Taubert, R. Hüttl, J. Seidel, F. Mertens, Journal of Alloys and Compounds 2017, 704, 398–405.
Crystallization of polyethylene at large undercooling
Evgeny Zhuravlev1, Vadlamudi Madhavi2, Arnold Lustiger2, René Androsch3,
Christoph Schick1
1 University of Rostock, Institute of Physics, Wismarsche Str. 43-45, 18051 Rostock,
Germany2 ExxonMobil Research & Engineering Company, 1545 Route 22 East,
LD 152, Annandale, New Jersey 08801, USA3 Martin-Luther-University Halle-Wittenberg, Center for Engineering Sciences,
06099 Halle/S., Germany
Extremely fast crystallization of high-den-
sity polyethylene and random copolymers
of ethylene with up to 16 mol% 1-octene
was observed for the first time by ultra-fast
scanning calorimetry. In order to account
for the inherently high crystallization rate
of polyethylenes, in non-isothermal and
isothermal crystallization experiments
cooling rates up to 1,000,000 K/s and
crystallization times as short as 10 µs, re-
spectively, were employed. It was possible
to supercool the melt of high-density poly-
ethylene down to 57 °C, and the melt of a
random ethylene/1-octene copolymer with
16 mol% 1-octene down to -33 °C, without
prior crystallization. At these tempera-
tures, the characteristic time of the
primary crystallization process is of the or-
der of magnitude of 100 µs. Complete vit-
rification of the liquid would require cooling
even faster than 1,000,000 K/s. Compared
to the homopolymer, the cooling-rate de-
pendence of the crystallization tempera-
tures and the temperature dependence of
the characteristic time of primary crystalli-
zation of random ethylene/1-octene copol-
ymers both are nearly parallel shifted to
lower temperatures. Fast crystallization
under condition of reduced linear crystal
growth rate is possibly caused by boosting
homogeneous nuclei density up to
1027 m-3 and urgently requires further in-
vestigation.
Franziska TaubertChristoph Schick
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig144 / 162 145/ 162
Evaluation of eutectic mixtures for use as PCM.
Thermodynamic modeling and experimental methods
Martin Wels*, Anastasia Efimova, Peer Schmidt**
Institute of Applied Chemistry, BTU Cottbus-Senftenberg, 01968 Senftenberg, Germany
* E-Mail: [email protected], ** E-Mail: [email protected]
The investigation and optimization of the
thermochemical properties of phase
change materials (PCM) is very complex.
Since there are currently no suitable con-
cepts for the rational planning of PCM sys-
tems, procedures for the efficient screen-
ing of these systems have to be estab-
lished.
With the help of thermochemical calcula-
tion methods (CalPhaD method) [1] on the
one hand, extended insights into the
phase equilibria of eutectic systems are
obtained, on the other hand,
time-consuming calorimetric measure-
ments can be specified and a ‘trail-and-er-
ror’ procedure avoided.
Within the eutectic system of the salt hy-
drates Mn(NO3)2·4H2O and
Zn(NO3)2·6H2O a large number of DSC
measurements have already been carried
out for the determination of characteristic
temperatures and latent heats [2]. The
modeling of the phase diagram is intended
to support these measurements as well as
other measurements used to clarify the
system.
Fig. 1: a) Designation of the eutectic point based on the enthalpy contributions of the mix-
tures (TAMMAN-Plot) and b) predicted phase diagram of the salt hydrates
Isobaric heat capacity data of orthorhombic FePO4 in the
temperature range between 223 K to 773 K
C. Thomas1, T. Zienert2, R. Hüttl1, J. Seidel1, F. Mertens1
1 Institute of Physical Chemistry, TU Bergakademie Freiberg, Leipziger Str. 29,
D-09599 Freiberg2 Institute of Materials Science, TU Bergakademie Freiberg, Gustav-Zeuner-Str. 5,
D-09599 Freiberg
The orthorhombic iron(III)-phosphate
(FePO4) with the space group Pmna re-
versibly intercalates lithium ions under re-
ducing conditions. Hence, FePO4 raised a
lot of attention since 1997 [1] because of
its potential application as cathode mate-
rial in lithium ion batteries (LIB). Despite
its huge relevance to industry and re-
search the availability of reliable thermo-
dynamic data of FePO4 is presently limited
to the low temperature range of 2K to
300 K.
This contribution focuses on the experi-
mental determination of precise isobaric
heat capacity values cp between 223 K
and 773 K using two different types of cal-
orimeters. A power compensation twin-
type calorimeter DSC 8000 from Perkin-
Elmer equipped with the external cooling
unit IntraCooler II was applied in the tem-
perature range from 223 K to 553 K. The
sample was pressed manually to a flat pel-
let in order to gain a good thermal conduc-
tivity inside the sample. The measurement
was continuously performed in intervals of
100 K each. In the temperature range be-
tween 298 K and 773 K the heat flux calo-
rimeter Sensys DSC from Setaram was
utilised and the sample was densely
packed into a stainless steel crucible,
which was tightly crimped with a nickel
sealing ring. In contrast to the measure-
ment with the DSC 8000, the heat capac-
ity was determined via the cp-by-step ap-
proach with temperature steps ΔT of 10 K.
Prior to the measurements, both calorime-
ters were calibrated with a sapphire stand-
ard.
The resulting cp-data of both calorimeters
are identical within the experimental error
of 1 % to 2 % and fit perfectly to the low
temperature heat capacity data of Wood-
field et al. [2]. Consequently, the pre-
sented results for cp of orthorhombic
FePO4 are very reliable and can improve
the quality of further CALPHAD calcula-
tions in the temperature interval from
300 K to 773 K.
[1] A. K. Padhi, K. S. Nanjundaswamy, J. B. Goodenough, J. Electrochem. Soc. 1997,
144, 1188–1194.
[2] Q. Shi, L. Zhang, M. E. Schlesinger, J. Boerio-Goates, B. F. Woodfield, J. Chem.
Thermdynamics 2013, 62, 35-42.
Martin WelsChristian Thomas
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig146 / 162 147/ 162
Micro reaction calorimetry for investigation of phase formation
processes in ionic liquid flux systems
Adrian Wolf*, Andrea Fandrey, Peer Schmidt**
Institute of Applied Chemistry, BTU Cottbus-Senftenberg, 01968 Senftenberg, Germany
* E-Mail: [email protected], ** E-Mail: [email protected]
The formation of Te4[AlCl4]2 from tellurium,
TeCl4, AlCl3 [1] has been used as a model
system for the establishment of a new
measurement method in ionic liquids (IL)
using a micro reaction calorimeter (µRC,
Thermal Hazard Technology).
With the IL flux system 1-butyl-3-
methylimidazolium chloride / aluminium
chloride as a source material, different
compositions and amounts of solid reac-
tants have been added. Thus various sub-
reactions could be analyzed, such as dis-
solution processes, oxidation, and phase
formation reaction. Applying the solid addi-
tion system the reaction can be analyzed,
even if the reaction starts immediately at
ambient temperature. Using the micro
reaction calorimeter isothermal, time de-
pendent measurements can be realized
with distinction of the quantity of different
sub-reactions. Finally, the reaction course
of various isothermal runs can be evaluat-
ed.
As assistant method Raman spectroscopy
was applied to identify the reactive spe-
cies in the system and to get a better in-
sight of the reaction [2-4].
Fig. 1: setup and principle of µRC Fig. 2: measurement of heat of reaction
with µRC
[1] E. Ahmed et al., Z. Anorg. Allg. Chem. 2010, 636, 2602–2606.
[2] C. J. Dymek et al., Polyhedron 1988, 7, 13, 1139–1145.
[3] W. Brockner et al., Z. Anorg. Allg. Chem. 1980, 461, 205–210.
[4] P. J. Hendra et al., J. Chem. Soc. (A) 1968, 600–602.
[1] C. W. Bale, E. Bélisle, P. Chartrand, S. A. Decterov, G. Eriksson, K. Hack, I. H. Jung,
Y. B. Kang, J. Melançon, A. D. Pelton, C. Robelin and S. Petersen, FactSage Ther-
mochemical Software and Databases - Recent Developments, Calphad, vol. 33
(2009) 295-31.
[2] S. Pinnau, A. Efimova, P. Schmidt, M. Mischke, Identifikation technischer Salze als
Latentspeichermaterialien im Temperaturbereich von 4 bis 15 °C und deren Verkap-
selung. BMWi-Forschungsbericht, Bundesministerium für Wirtschaft und Technologie
(2013) 1-92, DOI: 10.2314/GBV:786966173.
Adrian WolfMartin Wels (Forts.)
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig148 / 162 149/ 162
Autor hier: Stefan Zimmerer
Combined calorimetric and manometric measurements for the study of sorption properties of porous materials
Rémi Andre1, Julien Francois, Pierre Le Parlouër1
1 SETARAM Instrumentation, 7 rue de l’Oratoire, Caluire 69300, France
The gas sorption Sievert’s technique has proven to have many advantages for the evaluation of the ad- or ab-sorbed amount of gas by porous materials in a wide range of temperature and pressure. In addition, there is a total freedom in the size and shape of the sample holder in the volu-metric technique, enabling the coupling of techniques and in-situ measurements of various chemical and physical parame-ters. X-rays and neutrons diffractomers, gas chromatographs or mass spectrome-ters have already been successfully tested and allow having simultaneous PCT iso-therms and kinetic measurement with structural or gas composition data. The thermodynamics of the adsorption are essential for the practical application and among all the heat of adsorption (or de-sorption) is a key parameter. Practically there are two ways to determine it. The first one is an indirect method, where it is derived from adsorption isotherms at dif-ferent temperatures. The second one is a
direct method, where the enthalpy is measured via calorimetric techniques. When used on its own, the biggest disad-vantage of calorimetry is that it gives a heat output per mole of solid sample and not per mole of gas. The combination of manometric technique (to quantify the amount of hydrogen absorbed/released) and calorimetry was successfully applied to overcome this issue and the direct measurement of enthalpy of formation per mole of gas was reported [1-3]. The presentation will give some new re-sults on combinations of calorimetric and volumetric technique, especially on MOF-5, selected as an example of Metal Organ-ic Framework that is available commer-cially. But also on different other porous materials such as amine modified meso-porous silica and hydrotalcite based cata-lysts. It will give an overview of the state-of-the art possibility of combined calori-metric analysis together with the Sievert’s technique.
[1] M. R. Mello, D. Phanon, G. Q. Silveira, P. L. Llewellyn, C. M. Ronconi, Microporous and Mesoporous Materials 143 (2011) 174–179
[2] A. Auroux et al, “Calorimetry and Thermal Methods in Catalysis”, Springer Series in Materials Science (2013), Vol. 154
[3] R. Bulanek, K. Frolich, E. Frydova, P. Cicmanec, Top Catal 53 (2010) 1349–1360
Autor hier: Stefan Zimmerer
Recent improvements in the high pressure differential calorimetry method applied to the study of gas hydrates
Rémi Andre1, Pierre Le Parlouër1, Laurent Marlin2, Frédéric Plantier2, Jean-Philippe Torre2
1 SETARAM Instrumentation, 7 rue de l’Oratoire, Caluire 69300, France 2 Univ. Pau & Pays Adour, CNRS, TOTAL – UMR 5150 – LFC-R – Laboratoire des
Fluides Complexes et leurs Réservoirs, Avenue de l'Université, BP 1155 – PAU, F-64013, France
Calorimetry and especially High Pressure Differential Scanning Calorimetry (HP-DSC) applied to the study of gas hydrates has originally been developed and patent-ed (US6571604) by a collaborative work lead by the French Institute of Petroleum – New Energies. It was found to be a rele-vant tool for investigating the thermody-namics of formation and dissociation of gas hydrates as it is able to simulate the temperature and pressure conditions of their formation. Originally applied to fields related to oil and gas production and flow assurance [1], then extended to the study of oil-water-gas systems and the emulsion sta-bility of oils with hydrate [2], it has now been involved in several new studies. In-deed, carbon dioxide sequestration by CO2/CH4 exchange in natural gas hy-drates present in marine sediments, car-bon dioxide hydrates reversible for-mation/dissociation for refrigeration loops, hydrogen storage system through the for-mation of hydrogen hydrates [3], and many other studies involve the use of HP-DSC.
However, the technique still has some lim-itations which are linked to the fact that the gas hydrate formation in the calorimet-ric cell occurs at the gas-liquids interface. It leads to problems such as inefficient gas dissolution, long induction times, formation of a hydrate crust covering the gas/liquid interface, low hydrate to water conversion, etc. Thus it makes for example difficult or impossible the accurate determination of heat capacities or of kinetics of for-mation/dissociation (except when water-in-oil emulsions are involved). The presented work will cover these new fields of application of the technique and will include the description of a new high pressure, mechanically stirred calorimetric cell which overcomes the existing limita-tions. This cell has been developed by the Laboratory of Complex Fluids and their Reservoirs of the University of Pau and Pays de l’Adour (patent #FR/2012/57319 UPPA-CNRS) and has been industrialized and commercialized by SETARAM Instrumentation.
[1] L. Ma, Z. Chen, J. Therm. Anal. Calorim., 87 (2009) 1567. [2] A. Ionescu, V. Alecu, “Thermal properties of solids”, Expert Publishing House, (2008)
1356–1364. [3] W. Weselowski, A. Kartuj, F. Laam, J. Therm. Anal. Calorim., 81 (2008) 1237.
Stefan ZimmererStefan Zimmerer
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig 151/ 162
Abdelaziz, AmirUniversität RostockAlbert-Einstein-Straße 23-2418059 [email protected]
Aeby, ChristianTÜV SÜD Schweiz AGMattenstrasse 244002 [email protected]
André, RémiSETARAM Instrumentation7 rue de l’Oratoire69300 Caluire [email protected]
Anhalt, KlausPhysikalisch-Technische Bundesanstalt (PTB) - AG 7.31Abbestr. 2-1210587 [email protected]
Barros, NievesUniversity of Santiago de Compostela Dept. Applied Physics, Faculty of Physics15782 Santiago de [email protected]
Bartl, GuidoPhysikalisch-Technische Bundesanstalt (PTB)Bundesallee 10038116 [email protected]
Bauerecker, SigurdInstitut für Physikalische und Theoretische Chemie - TU BraunschweigGaußstraße 1738106 [email protected]
Autorenliste
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig152 / 162 153/ 162
Feja, SteffenInstitut für Luft- und Kältetechnik Dresden gGmbHBertolt-Brecht-Allee 201309 [email protected]
Gödde, MarkusBASF SE GCP/RS-L511 SicherheitstechnikCarl-Bosch-Straße 3867056 [email protected]
Gorodylova, NataliiaUniversity of PardubiceStudentska 9553210 [email protected]
Haug, TorstenUNION Instruments GmbHMaria-Goeppert-Straße 2223562 Lü[email protected]
Heerklotz, HeikoUniversität FreiburgHermann-Herder Str. 979104 [email protected]
Heinemann, RobertBrandenburgische Technische Universität Cottbus - SenftenbergUniversitätsplatz 101968 [email protected]
Heinsch, StefanPhysikalisch-Technische Bundesanstalt (PTB)Bundesallee 10038116 [email protected]
Autorenliste
Becattini, ViolaETH ZurichSonneggstrasse 38092 [email protected]
Bläker, ChristianThermische Verfahrenstechnik - Universität Duisburg-EssenLotharstraße 147057 [email protected]
Braissant, OlivierUniversity of Basel - Center for Biomechanics and BiocalorimetryGewerbestarsse 14-16CH-4123 [email protected]
Brown, Robert K.Technische Universität Braunschweig - Institut für Ökologische und Nachhaltige ChemieHagenring 338106 [email protected]
Bunjes, HeikeTU Braunschweig - Institut für Pharmazeutische TechnologieMendelssohnstr. 138106 [email protected]
Cammenga, Heiko K.Universitätsplatz 2Johanniterstraße 7A38106 [email protected]
Dumas, PhilippeInstitut de génétique et de biologie moléculaire et cellulaire (IGBMC)1 Rue Laurent Fries67400 [email protected]
Autorenliste
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig154 / 162 155/ 162
Krause, GerhardDr. Krause GmbH - Sicherheitstechnisches Prüfl abor PotsdamAhornstr. 28-3214482 [email protected]
Leithner, ReinhardTU Braunschweig – Institute of Energy and Process Systems EngineeringFranz-Liszt-Straße 3538106 [email protected]
Lemke, ThomasC3 Prozess- und Analysentechnik GmbHPeter-Henlein-Str. 285540 [email protected]
Lerchner, JohannesTU Bergakademie Freiberg - Inst. Physikalische ChemieLeipziger Str. 2909599 [email protected]
Marenchino, MarcoMalvern Instruments GmbHRigipsstr. 1971083 [email protected]
Maskow, ThomasHelmholtz-Zentrum für Umweltforschung (UFZ)Permoserstr. 1504318 [email protected]
Mishina, KarinaD.I. Mendeleyev All-Russian Scientifi c and Research Institute for Metrology (VNIIM)Moskovskiy pr-t, 19190005 Saint [email protected]
Autorenliste
Helmig, SimoneInstitut für Arbeits- und Sozialmedizin - Justus-Liebig-UniversitätAulweg 12935392 Gieß[email protected]
Hempel, ElkeMettler-Toledo GmbH - Business Unit AnalyticalSonnenbergstrasse 7408603 [email protected]
Hess, UweProsense GmbHAretinstraße 2481545 Mü[email protected]
Husemann, TobiasAnton Paar OptoTec GmbHLise-Meitner-Str. 630926 [email protected]
Kaiser, GabrieleNETZSCH-Gerätebau GmbHWittelsbacherstraße 4295100 [email protected]
Kazartsev, IaroslavD.I. Mendeleyev All-Russian Scientifi c and Research Institute for Metrology (VNIIM)Moskovskiy pr-t, 19190005 Saint Petersburg [email protected]
Knorr, AnnettBundesanstalt für Materialforschung und -prüfung (BAM) - FB 2.2Unter den Eichen 8712205 [email protected]
Autorenliste
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Prozeller, DomenikMax-Planck-Institut für PolymerforschungAckermannweg 155128 [email protected]
Reschke, MonikaBrandenburgische Technische Universität Cottbus – SenftenbergUniversitätsplatz 101968 [email protected]
Sauter, WaldemarInstitut für Ökologische und Nachhaltige Chemie - TU BraunschweigHagenring 338106 [email protected]
Schick, ChristophUniversität Rostock - Institut für PhysikAlbert-Einstein-Str. 23-2418051 [email protected]
Schmidt, PeerBTU Cottbus-Senftenberg - Institut für Angewandte ChemieUniversitätsplatz 101968 [email protected]
Schröder, UweTU Braunschweig - Institute for Environmental and Sustainable ChemistryHagenring 338106 [email protected]
Span, RolandRuhr-Universität Bochum - Fakultät für MaschinenbauUniversitätsstraße 15044801 [email protected]
Autorenliste
Nicolaus, ArnoldPhysikalisch-Technische Bundesanstalt (PTB)Bundesallee 10038116 [email protected]
Nopens, MartinUniversität Hamburg - Fakultät für Mathematik, Informatik und Naturwissenschaften - Fachbereich Biologie - Zentrum Holzwirtschaft HolzphysikLeuschnerstr. 91 c21031 [email protected]
Omelcenko, AlexanderClausthal University of Technology - Institute of Energy Research and Physical Technologies (IEPT)Am Stollen 19 B38640 [email protected]
Orava, JiriUniversity of CambridgeCharles Babbage RoadCB3 0FS [email protected]
Ortmann, ChristianTA InstrumentsHelfmann-Park 165760 [email protected]
Pérez-Sanz, Fernando J.Physikalisch-Technische Bundesanstalt (PTB)Bundesallee 10038116 [email protected]
Pinnau, SebastianTechnische Universität Dresden - Institut für Energietechnik - Professur für Technische ThermodynamikHelmholtzstraße 1401062 [email protected]
Autorenliste
Die 22. Kalorimetrietage | 7. – 9. Juni 2017 | Braunschweig158 / 162
Stones, Stevethermal hazard technology1 North House, Bond AvenueMK1 1 SW [email protected]
Taubert, FranziskaTU Bergakademie Freiberg - Institut für Physikalische ChemieLeipzigerstraße 2909599 [email protected]
Thomas, ChristianInstitute of Physical Chemistry - TU Bergakademie FreibergLeipziger Straße 2909599 [email protected]
Vidi, StephanBavarian Center for Applied Energy Research (ZAE Bayern)Magdalene-Schoch-Straße 397074 Wü[email protected]
Walter, DirkGefahrstoffl aboratorien Chemie und Physik-Institut für Arbeitsmedizin - Justus-Liebig-UniversitätAulweg 12935392 Gieß[email protected]
Wels, MartinBrandenburgische Technische Universität Cottbus – Senftenberg - Fakultät 2 - Umwelt und Naturwissenschaften - Institut für Angewandte ChemieUniversitätsplatz 101968 [email protected]
Wilhelm, EmmerichInstitute of Materials Chemistry & Research-Institute of Physical Chemistry - Universität WienWähringer Straße 42A-1090 [email protected]
Autorenliste Autorenliste
Willms, ThomasHelmholtz-Zentrum Dresden Rossendorf - Institut für experimentelle Fluiddynamik.Bautzner Landstraße 4001328 [email protected]
Wolf, AdrianBrandenburgische Technische Universität Cottbus - Senftenberg - Fakultät 2 - Umwelt und Naturwissenschaften - Institut für Angewandte ChemieUniversitätsplatz 101968 [email protected]
Yang, BinUniversity of Rostock - Institute of PhysicsAlbert-Einstein-Str. 23-2418051 [email protected]
Zaitsau, DzmitryUniversität Rostock - Institut für ChemieAlbert-Einstein-Str. 2518059 [email protected]
Zimmerer, StefanSETARAM Instrumentation7, rue de l'Oratoire69300 [email protected]
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Ankündigung
Die 23.KalorimetrietageBraunschweig12. – 14. Juni 2019(vorbehaltlich des CeBIT-Termins)
NETZSCH-Gerätebau GmbHWittelsbacherstraße 42 95100 [email protected]/n21479
Perkin Elmer LAS (Germany) GmbHFerdinand-Porsche-Ring 1763110 RodgauTelefon: 06106 610-0www.perkinelmer.com/hyphenation
PROSENSE GMBHAretinstraße 2481545 MünchenTelefon: +49 (0)89 210 258 52Telefax: +49 (0)89 210 258 51www.prosense.net
SETARAM Instrumentation7 rue de l‘Oratoire69300 CaluireFrancewww.setaram.com
TA Instrumentsein Unternehmensbereich der Waters GmbHHelfmann-Park 1065760 EschbornTelefon: 06196/400-7060Telefax: 06196/[email protected]
THASS GmbHThermal Analysis & Surface Solutions GmbHPfi ngstweide 2161169 FriedbergTelefon: +49-6031-16223-1Telefax: [email protected]
UNION Instruments GmbHZeppelinstraße 4276185 KarlsruheTelefon: +49 (0) 721-68 03 81 20Telefax: +49 (0) 721-68 03 81 [email protected]
Die 22. Kalorimetrietage werden unterstützt von: