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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 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)


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


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


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


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


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.


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


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

http://dx.doi.org/10.1007/s11051-016-3461-7

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


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


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


Appendix – Real-world performance tests

Application of screening methods


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−


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


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%)



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


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



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 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

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