application of screening methods for the characterisation of ......application of screening methods...

NanoDefine - Final Outreach Event, 19-20 September 2017, Brussels 1 / 14 + x

Application of screening methods for the characterisation

of nanomaterials

NanoDefine

–

Final Outreach EventClassification of nanomaterials

according to the EU

definition

19-20 September 2017, Brussels

Frank Babick, Technische

Universität Dresden (TUD)


A –

Real-world performance test of existing measurement techniques

Real-world performance test


Real-world performance tests

objective•

evaluate measurement techniques for NM identification

programme•

6 quality control materials, 12 representative test materials•

15 measurement techniques•

1815 SOPs, yet: 174 analyses successful/possible•

all measurement reports are accessible to public https://cloudstore.zih.tu-dresden.de/public.php?service=files&t=df134ce4a94b90c4a3da0a16a050ba2b

(password: NanoDefine)

outcome•

knowledge base for NanoDefiner

e-tool•

scientific publication•

report templates, measurement guide, material data


https://cloudstore.zih.tu-dresden.de/public.php?service=files&t=df134ce4a94b90c4a3da0a16a050ba2b



shape TEM SEM ICP PTA DEMA dAC cAC AC-RI AF4 DLS SAXS ALS USSP XRD BET

ID-19 (PSL mono) spherical

ID-17 (FD304) spherical f

ID-16 (nano-Au) spherical

ID-21 (nano-Ag) spherical f

ID-20 (PSL 3mod) spherical

ID-18 (SiO2

3mod) spherical

irmm387 (BaSO4

a) compact f ()

irmm381 (BaSO4

b) compact f

irmm388 (TiO2

) compact

irmm384 (CaCO3

) cigar-like

irmm385 (kaolin) platelets ()

id-12a-1 (pyr. SiO2

) fractals

irmm380 (Y83a) needles f f f

irmm386 (Y83b) needles f f f

irmm389 (BMC) compact ()

irmm383 (n-steel) flakes

irmm382 (CNT) fibrous

BAM-11 (zeolite) µ-porous

measurement performed,

measurement not possible/meaningful, f

failed


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PTA-TUDPTA-MalvernspICP-MS

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ID-12a-1 (fumed SiO2)

Quality control & representative test materialscounting techniques spray-DEMA

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DLS

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F4-L

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DLS-TUDDLS-BAMAF4-LS

ID-16 (nano-Au)

AF4-LS & DLS


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BETBAM-11 (zeolite)

IRMM-385 (kaolin)

VSSA via BET

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AC

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discACcuvACAUC-RI

IRMM-389 (BMC)

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AC techniques static scattering techn.


Conclusions on current state of the art

EM: reliable classification, unless platelets

promising for screening –

“factor 2.5”:•

BET: for powders •

spray-DEMA: good resolution and Q0 determination•

AC techniques: similar good performance by all types•

DLS: surprisingly good performance, data show potential for improvement•

AF4-LS: promising, yet few data on test substances•

spICP-MS: rather limited applicability, yet then accurate, needs validation

remaining MTs•

PTA: low sensitivity for x<100nm needs to and can be increased•

SAXS: no PSD for x>100nm improvement difficult, maybe VSSA measurem.•

ALS: not reliable for submicron particle systems improvement difficult•

USSP: not applicable to <1 vol.-% not assessable



More details in …

Babick, Mielke, Wohlleben, Weigel, Hodoroaba, J. Nanopart. Res., 18:158, 2016; doi:10.1007/s11051-016-3461-7

•

don‘t

miss the

SUPPLEMENTARY MATERIAL i.e. links to measurement

reports, guidance

documents, material data



B –

Application of screening methods



Application within NanoDefine

selected and further potential screening methods

•

spray-DEMA, AC techniques, DLS, BET and spICP-MS, AF4)

application for NM identification

•

rapid decision for majority of particulate materials•

typical drawbacks: intrinsically not number-weighted (AC, DLS, AF4, BET)

mobility-related aggregate size (spray-DEMA, AC, DLS, AF4)

restricted size range (spray-DEMA, AC, DLS, spICP-MS, AF4)

¿how to proceed, if a material is classified as NM?



We need screening methods for monitoring the life-cycle or fade of nanomaterials

release transport & transformatn

exposure

interaction with cells

pre- treatment

primary particles subclusters fractal aggregatesprimary particles subclusters fractal aggregates

weathering

erosion

materials,

products,

applications



Applications beyond NanoDefine

monitoring release, transport, transformation and exposition of NMs

•

requires: volume-weighted size distributions

mobility-related size of particles and aggregates wider size range for monitoring aggregates & agglomerates

quality check of substances and products•

requires: volume-weighted size distributions need of validated and standardised characterisation methods for

NMs

beyond the classification issue•

real-time,

online

or allowing mass-balances

maybe more important than confirmatory

•

further methods appropriate (e.g. ALS or TOF)



C –

People behind NanoDefine



Contributors to real-world performance

tests

BAM: Ralf Bienert, Sigrid Benemann, Kerstin-Brademann-Jock, Marion Gemeinert, Claudia Kästner, Franziska

Lindemann,

Johannes Mielke, Gabriele Steinborn, Andreas Thünemann

BASF: Michael Kaiser, Philipp

Müller, Kai Werle, Thorsten Wieczorek, Wendel

Wohlleben

eawag: Toni Mikael

Uusimaeki

JRC-IHCP: Dora Mehn, Francesca Pianella

LNE: Loic

Coquelin, Charles Motzkus

Nanosight: Phil Vincent

RIKILT: G. van der

Bemmel, Claudia Cascio, F. Gallocchio

TUD: Lars Hillemann, André

Kupka, Christian Ullmann; Frank Babick

UNIVIE: Milica

Velimirovic, Stefan Wagner



www.NanoDefine.eu

This project has received funding from the European Union’s Seventh Programme for research, technological development and demonstration under grant agreement No 604347


A1 –




TEM ICP PTA DEMA dAC- cAC- cAC-RI AF4 DLS SAXS ALS USSP BET

ID-19 (PSL mono)

ID-17 (FD304)

ID-16 (nano-Au)

ID-21 (nano-Ag)

ID-20 (PSL 3mod) ? ? ? ? ?

ID-18 (SiO2

3mod) ?

irmm387 (BaSO4

a) () ? ()

irmm381 (BaSO4

b)

irmm388 (TiO2

) ?irmm384 (CaCO3

)

irmm385 (kaolin) ? ()

id-12a-1 (fumed SiO2

)

irmm380 (Y83a)

irmm386 (Y83b)

irmm389 (BMC) ()

Conformity to NM classification by SEM



SEM ICP PTA DEMA dAC- cAC- cAC-RI AF4 DLS SAXS ALS USSP BET

ID-19 (PSL mono) 1.3% 0.7% 4.0% 5.8%ID-17 (FD304) 3.5% 0.3% 3.0% 17% 6.3%ID-16 (nano-Au) 4.8% 1.9% 0.1% 1.8% 32%ID-21 (nano-Ag) 2.5% 1.8% 7.1% 6.2%ID-20 (PSL 3mod) 1.7% 1.2% 3.8% 3.8% 10%ID-18 (SiO2

3mod) 3.4% 4.0% 0.6% 0.6% 3.0% 0.3%irmm387 (BaSO4

a) 6.7% 0.6% 18% 3.9% 7.0% 3.5% 1.1%irmm381 (BaSO4

b) 5.3% 8% 0.7% 20%irmm388 (TiO2

) 1.6% 1.6% 0.6% 0.5% 1.5% 0.6% 0.7% 2.7%irmm384 (CaCO3

) 1.8% 1.2% 0.4% 1.7%irmm385 (kaolin) 1.9% 0.7% 1.9% 3.1% 0.5% 2.5%id-12a-1 (fumed SiO2

) 7.3% 1.0% 2.5% 16% 4.7% 19%irmm380 (Y83a) 1.1% 14% 1.5% 10% 4.9% 6.9%irmm386 (Y83b) 1.3% 2.0% 56% 0.2% 5.1%irmm389 (BMC) 7.7%

Uncertainty with respect to repeatability


below 5%, between 5% and 20%, above 20%


Summary on real-world performance tests

conformity with SEM classification•

good for most materials and MTs•

problems when Q0,EM

~ 50% (e.g. 3-mod SiO2

: 61%, kaolin: 32%)

material related factors important for agreement with EM-x50,0

:•

polydispersity •

final state of aggregation•

morphology of constituents

MT characteristics•

good performance needs wide range of particle size, at least 10nm…1000nm•

performance: imaging > counting > fractionating > spectroscopic•

yet more important is intrinsic type of quantity:

similar performance of AF4-LS and DLS

similar performance of AC-turbidity and AC-RI for metal & coloured NPs•

practical limits (substances, concentration) should be regarded



Potential screening techniques –

factor 2.5

spray-DEMA, AC and DLS for suspensions (limited use: spICP-MS)

BET for powders

not clear: AF4-LS, USSP, (PTA)

not recommended: ALS, SAXS, (PTA)

spray-DEMA, all AC, DLS, AF4-LS & BET


with factor 2 most data, but not all are covered

factor 2.5 means, if x50,0

< 40 nm nano

> 250nm non-nano otherwise use a second/confirmatory

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DEMAACDLSAF4-LSBET

QCM3 (nano-Au)

parity line with factor 2.5 band


A2 –

Quality of T3.2

Quality of data


Sample preparation -

¡we cannot be satisfied!

considerable discrepancies among dispersion procedures by different labs

preliminary dispersion protocols 16/01/2015 insufficient•

no values on energy density •

incomplete regarding x-EV

or x-t

relationship•

some procedures did not work in practice (e.g. for PY83) individual SOPs

overlap of SOP development and T3.2

two phases •

primary: dispersion ( individualisation of constituents)•

secondary: feed instrument ( avoid re-agglomeration etc.)

“real-world”: •

¿how to ensure adequate dispersion for each substance and product?

Quality of data


Impact of material properties

refractive index

•

for ALS, DLS, AC-turbidity•

depends on wavelength•

imaginary part: important for extinction•

absolute value: important if close to that of dispersion medium

density

•

for spICP-MS, AC, USSP•

Important, if value close to that of dispersion medium

Quality of data


Impact of data analysis

inversion of spectroscopic signals

•

for ALS, DLS, SAXS, USSP•

data analyses requires bias on shape of q(x)•

algorithms are not standardised and may be customised

analysis of cuvette-AC data

•

via time curve, concentration profile, total data set

manual data treatment

•

necessary: spray-DEMA, AF4-LS•

may be meaningful: disc-AC, cuvette-AC, DLS

conversion into Q0

Quality of data


A3 –

Details on the real-world-performance tests

Details


NanoDefine

materials

reference and quality control materials

•

PSL mono: monomodal polystyrene latex (45 nm)

•

PSL 3-mod:

trimodal polystyrene latex (45+100+350 nm)•

ERM-FD304:

colloidal silica, monomodal (20 nm)•

SiO2 3-mod:

colloidal silica, trimodal (25+75+105 nm)•

BAM-nano-Au:

colloidal gold sol (20 nm)•

BAM-nano-Ag:

colloidal silver sol (5 nm)


NanoDefine

materials

representative test materials –

substances:•

IRMM-384: CaCO3(calcite)

(fine grade)•

IRMM-387: BaSO4

(ultra-fine grade)•

RMM-381:

BaSO4

(fine grade)•

IRMM-388: TiO2(rutile

, coated with alumina and a silicon compound (coating <4nm)

•

IRMM-385: kaolin

•

IRMM-383: nano

steel

•

IRMM-382: multi-walled carbon-nanotubes

(MWCNT)

•

IRMM-380: organic pigment Yellow 83 (nano

grade)

•

IRMM-380: organic pigment Yellow 83 (coarse grade)•

IRMM-389: basic methacrylate

copolymer (BMC)

•

BAM-11:

zeolite

(SiO2

: Al2

O3

= 23

:

1)


NanoDefine

materials

representative test materials –

products:•

BAM-12a:

tomato soup with SiO2

(nanolyse

10)•

BAM-13a:

complex sunscreen (emulsion with nano-TiO2and Fe2

O3

pigments)•

BAM-14:

HDPE pellets containing Fe2

O3

pigments•

BAM-15:

toothpaste containing Al2

O3

“bonus”

materials•

BAM-12a-1: commercial suspension of fumed SiO2

(200 m²/g)•

BAM-12b:

pancake mix with SiO2

as flowing agent•

BAM-13b:

“simple”

sunscreen (emulsion with nano-TiO2

)•

BAM-14-1:

HDPE pellets (base material of BAM-14)•

BAM-14-2:

Fe2

O3

pigments Red 101 (incorporated in BAM-14)


Critical remarks on real-world performance tests

MTs

and instrumentation employed:•

not fully comprehensive •

e.g. for ALS more variations in instrumentation•

e.g. for USSP instrumentation based on resonator cells ignored•

maybe reflecting current state-of-the-art

particle systems tested•

max. polydispersity x99,0

/x1,0

in Q0,SEM

: 24 (kaolin), 14 (BMC), 12 (3-mod-PSL)•

mostly clear distinction between “nano”

and “non-nano”•

most systems dispersible to constituent or small, non-fractal aggregates •

¿representative for real-world?

procedures (sample preparation, data analysis)•

not perfect, yet probably much better than outside NanoDefine



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TEM - eawagTEM - BASF

IRMM-383(n-steel)

Agreement among EM results

deviation among EM techniques•

is < factor 2 for most materials (even < factor 1.5)•

applies also for 1% and 99% quantiles

median size x50,0

parity line plus factor 2

band



A4 –

Brief comment on new developments

Quality of data


Brief comment on new developments

PTA•

main problem is insensitivity for x <50..70 nm for quite a lot of materials, difficult to improve considerably

spICP-MS•

main problem is limited applicability, since only heavy elements

have lower size limit in nano-range [ Ruud

Peters ]

sub-10nm-DEMA•

no benefit for NM classification

analytical centrifugation remember real-world performance

examine further candidates future

application of screening methods for the characterisation of ......application of screening methods...

Documents