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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)
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
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
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
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
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.
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
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
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
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
NanoDefine - 2nd Industry focused workshop, 24 October 2017, Frankfurt/Main 11 / 10
Appendix – Real-world performance tests
Application of screening methods
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−
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
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%)
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
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
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