edited presentation supramolecular chemistry in fibre...
TRANSCRIPT
Supramolecular chemistry in fibre processing: New
opportunities for functional biomaterials
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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Åbo Akademi University Laboratory of Fibre and Cellulose Technology
Dep of Chemical Engineering
Pedro Fardim, Carl Lange, Beatriz Vega, Thomas Heinze
Edited presentation
Our core competence in Biomass Engineering
Laboratory of Fibre and Cellulose Technology (FCT)
www.abo.fi/fct
Topochemistry
Eco-materials Nanotechnology
Bioenergy
Fibres Sustainable processes
Chemistry in 3D Topology Surface chemistry
Supramolecular chemistry Self-assembly Nanoanalysis
Composites Bioplastics Biochemicals Packaging Paper
Pretreatment Fractionation Functionalisation Shaping
Biofuels Bioconversion
Biomaterials Smart materials Personal care
Supramolecular chemistry
§ Supramolecular Chemistry is all about interactions between molecules: how they can recognise each other, assemble and function on a molecular scale.
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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Lehn, J-M., Nobel Lecture, 1987
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Intramolecular Forces
§ Forces binding atoms in a molecule are due to chemical bonding (intramolecular), e.g.: – Metallic bond (inner electron) – Ionic bond (inner electron) – Covalent bond (outer electron) – Coordination bond (outer electron)
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Intermolecular forces § Forces holding molecules together
(intermolecular) – Dipole-dipole interactions – Hydrogen bonds – Dispersion bonds (also called van der Waals or
London)
The intermolecular forces determines the physical properties of substances and materials, e.g. boiling point (bp), melting point (mp), solubility, surface tension, adhesion, etc.
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Bond energies
Chemical forces Bond energy (kJ/mol) Metallic bonds 2100 Ionic bonds 630 Covalent bonds 460 Coordination bonds 210 Hydrogen bonds 21 Dipole-Dipole 4 Dispersion 4
Supramolecular assemblies in fibre processing
1. Cellulose assembly in pulping
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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AGGREGATION OF NANOFIBRILS DURING PULPING
§ Cellulose nanofibrils (2-4 nm) form aggregates of 16-30 nm during pulping (Wickholm, 2001; Hult 2001)
§ Co-crystallization or coalescence of cellulose crystals during pulping (Newman, 1994; Ioelovich, 1989)
Other effects Temperature as dominating factor
for increase of cellulose crystallinity (Attala, 1978; Isogai et al 1991)
CHEMICAL DEGRADATION IN PULPING
12 14 16 18 20 22 2410
12
14
16
18
20
22
24
26
28
30
32
34
36
38
40
Active alkali in pulping (% Na2O)
Iso Brightness (% ISO)
Lignin content x10 (%)
Kappa number
Lignin
12 14 16 18 20 22 240
10
20
30
40
1000
1200
1400
1600
1800
Active alkali in pulping (% Na2O)
Cellulose retention (%)
Degree of Polymerization
Cellulose
XYLAN DEGRADATION
12 14 16 18 20 22 240
2
6
8
10
Active alkali (% Na2O)
Xylan retention (%)
Uronic acid retention (%)
X-ray Diffraction
0 10 12 14 16 18 20 22 2456
70
72
74
76
78
80
Active alkali in pulping (% Na2O)
Wood
Cristallinity index (Cr)
? 17
16
0 10 20 30 40 50
0
200
400
600
800
1000
1200
1400
1600
1800
2000
Line
ar in
tens
ity (c
ount
s pe
r sec
)
Diffraction angle 2θ (degrees)
(101)
(002)(020)
(110)
CPMAS 13C NMR
10 12 14 16 18 20 22 24 2644
46
48
50
52
54
56Xc
Cel
lulo
se c
rista
llini
ty (
%)
Active alkali (% Na2O)
Transition point
NIR and PCA
PC1 (93,3%)
PC2
(3
,70
%)
HF12A
HF14A
HF15A
HF16A
HF17A
HF18AHF20A
HF22A
HF24A
-0.08
-0.06
-0.04
-0.02
0
0.02
0.04
0.06
0.08
-0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4
Transition point detected by PC1
PC1 H2O
Ph-OH
Work of adhesion
15 20 25 30
20
40
60
80
100
120
140
Wap-AB
Wap-LW
Wap
mJm
-2
Active alkali in pulping (% NaOH)
Fardim, Durán (2005), J. Braz. Chem. Soc. 16 (5) 915
More H-bonds
Surface Energy
15 20 25 30 35
22
24
26
28
30
32
34
36S
urfa
ce e
nerg
y (m
Jm-2)
Active alkali in pulping (% NaOH)
Lignin removal increases γ
A Hypothesis is put forward
§ Different molecular self-assemblies are formed during kraft pulping of eucalyptus
§ The self-assembly mechanism is driven by H-bonds and increase in γ due to removal of lignin
§ The adhesion forces during cocrystallisation cause increase of order in nanofibrills
0 10 12 14 16 18 20 22 2456
70
72
74
76
78
80
Active alkali in pulping (% Na2O)
Wood
Cristallinity index (Cr)
M1
M2
Aggregation of nanofibrils ΔGagg= -T[ΔSagg] : entropy driven
Molecular self-assembly (ΔGinteraction dominates the process, not ΔSagg)
New insigths in Pulping
§ Control of fibre-water interactions § Tailoring of crystallinity of fibres § Effects on fibre wall compressibility/
mechanical properties § New route to obtain nanocellulose
Supramolecular assemblies in fibre processing
2. Xylan assembly in oxygen bleaching
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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Notice
§ This part has unpublished data which was removed
§ Data will be available after publication
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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Contact angle and surface energy
Contact angles (CA) of a ethylene glycol droplet on a oxygen bleached pine fibre with 2 % hot water extracted xylan added. sample: QX-1-47-T)
Bleached pine fibre γSV γSVLW γSVAB γSVA γSVB
QX-1-47-T (GM) 47.4 29.9 17.5
QX-1-47-T (vOCG) 36.0 29.9 6.11 0.3 28.5
Cooperation with Tampere
Supramolecular assemblies in fibre processing
3. Extractives assembly in low-consistency refining
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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Surface coverage by XPS
Carbohydrates
Lignin
Extractives
R
R
R
Modification of fibre surfaces during LC-refining
New Insights in Refining
§ Modification of fibre surfaces § Release of xylan and fatty acid salts
from fibre wall to fibre surfaces § Strategies to benefit of this mechanism:
– Encapsulation of chemical to promote bonding/interactions with paperchemicals
– Removal of paperchemicals (defoamers/biocides) in papermachine
Supramolecular assemblies in fibre processing
4. Xylan polyelectrolytes assembly in wet-end
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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Xylan
• Raw material: birch chips
• Extraction conditions: 160°C, 10 min, static pressurized hot water
extraction mode
• Sugar composition: 73% xylose, 3% methyl glucuronic acid
• Mw = 10728 g/mol
• DSac = 0.39
• Soluble in: Water DMSO, and DMF/LiCl
Xylan derivatives (XDs)
CMX-
XS-
XN+
§ Chemical characterization using: § NMR, SEC, HPLC
Characterization of XDs
CMX-
XS-
XN+
Weight average molar mass (Mw), degree of polymerization (DP) and polydispersity (PDI) of pressurized hot water extracted xylan and xylan derivatives determined by size exclusion chromatography Sample Structure DS MRU
*
[g/mol]
Mw [g/mol] DP DPI
Xylan
0.39 (acetate) 148 10728 72 2.1
XS-‐
0.16 148 16314 110 1.5
CMX-‐
0.50 172 16153 94 2.0
XN+
0.32
200 -‐-‐-‐-‐-‐-‐-‐-‐ 276* 1.7
*MRU, Molar mass of repeating unit
O
OOR
R O
C H 3
OR = H ,
O
OOR
R O
R = H , S O 3Na
O
OOR
R O
R = H , C H2 COO Na
R = H, ,
N(C H3 )3 C l
O
O
OOR
R O
C H 3
O
Weight average molar mass (Mw), degree of polymerization (DP) and polydispersity (PDI) of pressurized hot water extracted xylan and xylan derivatives determined by size exclusion chromatography Sample Structure DS MRU
*
[g/mol]
Mw [g/mol] DP DPI
Xylan
0.39 (acetate) 148 10728 72 2.1
XS-‐
0.16 148 16314 110 1.5
CMX-‐
0.50 172 16153 94 2.0
XN+
0.32
200 -‐-‐-‐-‐-‐-‐-‐-‐ 276* 1.7
*MRU, Molar mass of repeating unit
O
OOR
R O
C H 3
OR = H ,
O
OOR
R O
R = H , S O 3Na
O
OOR
R O
R = H , C H2 COO Na
R = H, ,
N(C H3 )3 C l
O
O
OOR
R O
C H 3
O
Weight average molar mass (Mw), degree of polymerization (DP) and polydispersity (PDI) of pressurized hot water extracted xylan and xylan derivatives determined by size exclusion chromatography Sample Structure DS MRU
*
[g/mol]
Mw [g/mol] DP DPI
Xylan
0.39 (acetate) 148 10728 72 2.1
XS-‐
0.16 148 16314 110 1.5
CMX-‐
0.50 172 16153 94 2.0
XN+
0.32
200 -‐-‐-‐-‐-‐-‐-‐-‐ 276* 1.7
*MRU, Molar mass of repeating unit
O
OOR
R O
C H 3
OR = H ,
O
OOR
R O
R = H , S O 3Na
O
OOR
R O
R = H , C H2 COO Na
R = H, ,
N(C H3 )3 C l
O
O
OOR
R O
C H 3
O
vacuum filtration
through glassmicrofibre
filter
polyelectrolyte titration
surface characterization
of pulp
Initial concentration of
XD
Final concentration of
XD
Sorption of XDs on fibre surfaces*
*bleached pine kraft pulp
Sorption of XS- on fibre surfaces
0.000
0.002
0.004
0.006
0.008
0.010
0.000 0.005 0.010 0.015 0.020 0.025 0.030
meqsorbed/100 mg dry pulp
meq free
XS- sorption isotherm
Sorption isotherm showing the amount of XS- per 100 mg of bleached pine Kraft pulp versus “meq free” representing the amount of XS- still in solution after sorption.
Sorption of CMX- on fibre surfaces
0.000
0.002
0.004
0.006
0.008
0.010
0.00 0.01 0.02 0.03 0.04 0.05
meqsorbed/100 mg dry pulp
meq free
CMX- sorption isotherm
Sorption isotherm showing the amount of CMX- per 100 mg of bleached pine Kraft pulp versus “meq free” representing the amount of CMX- still in solution after sorption.
Sorption of XN+ on fibre surfaces
0.000
0.002
0.004
0.006
0.008
0.010
0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035
meqsorbed/100 mg dry pulp
meq free
XN+ sorption isotherm
70 µmol of XN+ / g pulp
Sorption isotherm showing the amount of XN+ per 100 mg of bleached pine Kraft pulp versus “meq free” representing the amount of XN+ still in solution after sorption.
Sorption of XN+ on fibre surfaces
70 µmol XN+/ g pulp
73 µmol SAGs/ g pulp
Surface anionic groups (SAGs) value was determined by using X-ray photoelectron spectroscopy (XPS)
The amount of sorbed XN+ was estimated from the sorption isotherm
Vega et al, Carb. Pol. 89, 3, 1 July 2012, Pages 768–776
Åbo Akademi University - Domkyrkotorget 3 - 20500 Åbo 37
Total ion Peaks 58 + 146 0.5 mg/ml XTMAB The surface distribution of the XTMAB polymers on the fibres was quite
homogeneous and the polymer is covering evenly the surface
Sorption experiments using XTMAB, ToF-SIMS imaging
100 µm 100 µm
Supramolecular assemblies in fibre processing
5. Polysaccharide-nanohybrids assembly
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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The concept in general
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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From colloidal particles… …and pulp fibres…
…to functionalized fibres…
…to product ideas.
flame retardant insulation
composites rethinking pulp
The colloidal particles
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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§ Layered Double Hydroxides (LDH) • Are formed from divalent and trivalent mixed
metal hydroxides (Mg2+, Zn2+,Al3+, Cu2+, Fe2+/3+ etc) ü They are versatile!
• Occurs in nature with a chemical composition of Mg6Al2(CO3)(OH)16 • 4(H2O) and is called the Hydrotalcite ü Can be synthesized from non toxic chemicals!
• One of the rare cationic minerals therefore behaving as an anion exchanger ü Favourable charge with respect to pulp fibres!
The colloidal particles
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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http://webmineral.com/data/Hydrotalcite.shtml
Rethinking pulp
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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0,000 0,005 0,010 0,015 0,020 0,025-0,2
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
1,6 OBA-pulp LDH/OBA pulp
ΨOBAO.D.
A
Leaching of OBA into pulp filtrate• Optical brightening agents (OBA) are anionic and require retention aids to incorporate them into pulp fibre matrix.
• LDHs are white particles and they capture anions easily from aqueous solution.
• Prevents leaching of OBA into effluent thus reducing chemical dosage and effluent contamination
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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Rethinking pulp
under natural light
under UV-light
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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Rethinking pulp
0 3 6 9 12
0
20
40
60
80
100
120
140
dθap
p/dt
SDS (%)
• Surfactants can be bound to pulp fibre matrix.
• LDHs are can be used as a platform to impart hydrophobic character to pulp fibres.
• High contact angles can be achieved!
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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Rethinking pulp
Water is unable to penetrate the fibre matrix
• Injection moulded to match ISO 527-2 1BA test specimen • Atactic polypropylene matrix
• Chosen because it is cheap, widely applicable and hydrophobic.
• Working temp.: 190 °C (200 rpm, 2 min) • Injection pressure: 4 bar (40 °C) • Pulp to matrix ratio: 0.2
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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Composites
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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A B C D E F
A) PP matrix B) PP + fibres C) PP + fibres with 10 mM LDH, D) PP + fibres with 100 mM LDH E) PP + fibres with 100 mM LDH + 3% SDS F) PP + fibres with 100 mM LDH + 6% SDS
Composites
BKraft BTMP
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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BTMP E (MPa) σ(YS) (MPa) ε(max) (%)
50 mm /min 5 mm /min 50 mm/min 5 mm/min 50 mm/min 5 mm/min
PP 5.46 24.9 > 300
PP + BTMP 11.3 7.48 39.5 29.6 9.32 20.6
PP-BTMP-LDH (100) 11.8 8.20 35.2 30.5 14.4 15.6
PP-BTMP-LDH (100) + 3% SDS 10.7 7.85 30.8 28.3 17.5 20.3
Composites
Standard deviations are approximately 10% in each value
Under a relatively fast (50 mm/min) and slow (5 mm/min) deformation rate showing the elastic and viscous behaviour of the composite respectively
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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BKraft E (MPa) σ(YS) (MPa) ε(max) (%)
PP 5.46 24.9 > 300
PP-Bkraft 7.66 35.2 17.8
PP-BKraft-LDH (10) 7.01 30.1 27.1
PP-BKraft-LDH (100) 6.52 27.3 28.7
PP-BKraft-LDH (100) + 3% SDS 7.77 30.1 18.9
Standard deviations are approximately 10% in each value
Composites Relatively slow (5 mm/min) deformation rate showing the viscous behaviour of the composite
§ Supramolecular chemistry in fibre processing: – Hydrogen bonds – Hydrophobic interactions – Electrostatic forces – New multifunctionalisation strategies for fibres
§ Supramolecular assemblies: – New pulp fibres – Functional polysaccharides in fibre lines (O
bleaching) and wet end – Bionanohybrids as functional agents for biofibres – New bioproducts for different value chains 10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5,
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Conclusions
References § Hybrid Clay Functionalized Biofibres for Composite Applications. C Lange, F Touaiti, P
Fardim - Composites Part B: Engineering, 2012http://dx.doi.org/10.1016/j.compositesb.2012.10.032
§ Hydrophobisation of mechanical pulp fibres with sodium dodecyl sulphate functionalised layered double hydroxide particles. C Lange, T Lundin, P Fardim - Holzforschung, 2012 DOI: 10.1515/hf.2011.168
§ Studies on the fibre surfaces modified with xylan polyelectrolytes. B Vega, K Petzold-Welcke, P Fardim, T Heinze - Carbohydrate Polymers, 2012http://dx.doi.org/10.1016/j.carbpol.2012.04.006
§ Molecular assembly in kraft pulping of Eucalyptus. P. Fardim, N. Duran. O Papel 2007, 68, 8, 98-108 . http://www.revistaopapel.org.br/noticia-anexos1311965922_9fed06c715ac8765dcec040e4da8bed6_781788484.pdf
§ Modification of fibre surfaces during pulping and refining as analysed by SEM, XPS and ToF-SIMS. P Fardim, N Durán - Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2003 http://dx.doi.org/10.1016/S0927-7757(03)00149-3
§ Extractives on fiber surfaces investigated by XPS, ToF-SIMS and AFM P Fardim, J Gustafsson, S von Schoultz, J Peltonen… - Colloids and Surfaces A: Physicochemical and …, 2005http://dx.doi.org/10.1016/j.colsurfa.2004.12.027
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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Acknowledgements
§ Prof. Philip Turner and Zurine Hernandez § Tekes § Academy of Finland § Metsafiber, UPM, StoraEnso, Kemira,
Danisco, ViscoTeepack § Friedrich Schiller University of Jena,
Germany § University of Sao Paulo (USP), Brazil
10.12.2012 Laboratory of Fiber and Cellulose Technology, Porthansgatan 3-5, 20500 Åbo, FINLAND
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