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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 1 / 10 Applicability of widely available methods to identify nanomaterials in real-life samples NanoDefine 2 nd industry focused workshop Measurement and classification of nanomaterials according to the EU definition 24 October 2017, Frankfurt/Main Frank Babick, Technische Universität Dresden (TUD)

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Page 1: Applicability of widely available methods to identify ... of... · Applicability of widely available methods to ... crystallite size ... Applicability of widely available methods

NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 1 / 10

Applicability of widely available methods to identify nanomaterials in real-life samples

NanoDefine 2nd industry focused workshop Measurement and classification of nanomaterials

according to the EU definition

24 October 2017, Frankfurt/Main

Frank Babick, Technische Universität Dresden (TUD)

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 2 / 10

Metrological challenge

Challenge of NM identification

‘Nanomaterial’ means a natural, incidental or manufactured material containing particles, in an unbound state or as an aggregate or as an agglo-merate and where, for 50 % or more of the particles in the number size distribution, one or more exter-nal dimensions is in the size range 1 nm-100 nm. In specific cases and where warranted by concerns for the environment, health, safety or competitiveness the number size distribution threshold of 50 % may be replaced by a threshold between 1 % and 50 %. By derogation […], fullerenes, graphene flakes and single wall carbon nanotubes with one or more ex-ternal dimensions below 1 nm should be considered as nanomaterials.

keywords • particles: unbound or in aggregates • external dimension • number-weighted median size x50,0

x

q r(x

)

q6(x)

q0(x) q3(x)

impact of type of quantity

∆ equivalent diameter

xZ

q(x Z

) xStokes

xV xh xgyr

xgeo

EC definition

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 3 / 10

NanoDefine project

characterisation method = preparation + size analysis strategy for grouping materials according to the EC definition

• if possible: cheap, rapid screening methods (tier 1) • else confirmatory methods (tier 2)

develop / validate sample preparation talk of Katrin Löschner

develop / validate measurement techniques (MTs) for tier 1 talk of Michael Stintz

develop / validate MTs for tier 2 talk of Frank von der Kammer

test performance of conventional MTs at real-life samples • real-world performance tests with selected MTs & materials

Challenge of NM identification

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 4 / 10

Real-world performance tests (→ Appendix)

objective • evaluate measurement techniques for NM identification

programme • 6 quality control materials,• 12 representative test materials• 15 measurement techniques• 18×15 SOPs, yet: 174 analyses successful/possible

outcome • knowledge base for NanoDefiner e-tool• report templates, measurement guide, material data

Real-world performance test

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 5 / 10

1

10

100

1000

10000

1 10 100 1000 10000SEM-BAM - x50,0, nm

med

ian

size

x50

,0, n

m

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

Results for electron microscopy techniques

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 6 / 10

1

10

100

1000

10000

1 10 100 1000 10000SEM-BAM - x50,0, nm

coun

ting

- x50

,0, n

m

PTA-TUDPTA-MalvernspICP-MS

1

10

100

1000

10000

1 10 100 1000 10000SEM-BAM - x50,0, nm

spra

y-D

EMA

- x 5

0,0,

nmSMPS-TUDSMPS-LNE

ID-12a-1 (fumed SiO2)

Quality control & representative test materials counting techniques spray-DEMA

1

10

100

1000

10000

1 10 100 1000 10000SEM-BAM - x50,0, nm

DLS

& A

F4-L

S - x

50,0

, nm

DLS-TUDDLS-BAMAF4-LS

ID-16 (nano-Au)

AF4-LS & DLS

Results for potential screening techniques

1

10

100

1000

10000

1 10 100 1000 10000SEM-BAM - x50,0, nm

BET

- x B

ET,

min, n

m

BETBAM-11 (zeolite)

IRMM-385 (kaolin)

VSSA via BET

1

10

100

1000

10000

1 10 100 1000 10000SEM-BAM - x50,0, nm

AC

- x 5

0,0,

nm

discACcuvACAUC-RI

IRMM-389 (BMC)

AC techniques

1

10

100

1000

10000

1 10 100 1000 10000SEM-BAM - x50,0, nm

stat

ic s

catte

ring

- x50

,0, n

m

ALS-TUDALS-BAMSAXS

static scattering techn.

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 7 / 10

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

Summary

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 8 / 10

More details in …

Babick et al., J. Nanopart. Res., 18:158, 2016; doi:10.1007/s11051-016-3461-7 • supplementary material: measurement reports, guidance documents, material data

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

Reference

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 9 / 10

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

People behind NanoDefine

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 10 / 10

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

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 11 / 10

Appendix – Real-world performance tests

Application of screening methods

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 12 / 10

imaging • TEM & SEM constituents, Q0

counting + spray-DEMA • PTA, spICP-MS & DEMA Q0

fractionating • AF4-LS, AC (cuv/disc, τ/RI) highly resolved Qint/ext/3

spectroscopic • DLS low resolved Qint , yet 10nm…10µm • SAXS constituents, low resolved Q2 • ALS & USSP low resolved Q3 , yet …1000µm

integral • BET specific surface area • XRD crystallite size

Considered measurement techniques

Measurement techniques

imaging • TEM & SEM constituents, Q0 potentially confirmatory

counting + spray-DEMA • PTA, spICP-MS & DEMA Q0 potentially screening

fractionating • AF4-LS, AC (cuv/disc, τ/RI) highly resolved Qint/ext/3 screening?

spectroscopic • DLS low resolved Qint , yet 10nm…10µm screening? • SAXS constituents, low resolved Q2 screening?? • ALS & USSP low resolved Q3 , yet …1000µm ???

integral • BET specific surface area approximate of constituents • XRD crystallite size – forget about it

e−

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 13 / 10

Quality control materials (QCMs)

monomodal particle systems • ID-19 (PSL spheres, organic, 45 nm, x99,0/x1,0 = 1.7) • ID-17 (SiO2 spheres, oxide, 20 nm, x99,0/x1,0 = 3.0) • ID-16 (Au grains, metal, 20 nm x99,0/x1,0 = 1.7) • ID-21 (Ag grains, metal, 5 nm, x99,0/x1,0 = 3.8)

trimodal particle systems

• ID-20 (PSL spheres, organic, 45+100+350nm, x99,0/x1,0 = 12)

• ID-18 (SiO2 spheres, oxide, 25+75+105nm, x99,0/x1,0 = 10)

Test materials

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 14 / 10

Representative test materials (RTM)

Test materials

inorganic • IRMM-387 (BaSO4, compact, Q0(100nm)=99%) • IRMM-381 (BaSO4, compact, Q0(100nm)=7%) • IRMM-388 (coated TiO2, compact, Q0(100nm)=5%) • IRMM-384 (CaCO3, cigar-like, Q0(100nm)=22%) • IRMM-385 (kaolin, platelets, Q0(100nm)=32%) • BAM-12a-1 (pyrogenic SiO2, fractals, Q0(100nm)=100%)

organic • IRMM-380 (pigment Y83, needles, Q0(100nm)=100%) • IRMM-386 (pigment Y83, needles, Q0(100nm)=10%) • IRMM-389 (BMA, compact, Q0(100nm)=14%)

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 15 / 10

Real-world performance test

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 (BaSO4a) compact f () irmm381 (BaSO4b) 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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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 16 / 10

TEM ICP PTA DEMA dAC-τ cAC-τ 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 (BaSO4a) () ? () irmm381 (BaSO4b) irmm388 (TiO2) ? irmm384 (CaCO3) irmm385 (kaolin) ? () id-12a-1 (fumed SiO2) irmm380 (Y83a) irmm386 (Y83b) irmm389 (BMC) ()

Conformity to NM classification by SEM

Real-world performance test

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NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 17 / 10

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

Real-world performance test

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 method 1

10

100

1000

10000

1 10 100 1000 10000SEM - x50,0, nm

x 50,

0 or x

BE

T,m

in, n

m

DEMAACDLSAF4-LSBET

QCM3 (nano-Au)

parity line with factor 2.5 band