19.02.2016

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How to meet the challenge of the diversity of properties in measuring (nano)materials ?

Dr. Wendel Wohlleben

Dept. Material Physics

NanoDefine – VCI workshop, Frankfurt, 8.2.2016

150 yearsNanotechnology is a cross-sectional enabler for BASF and its customers

Resources, Environment & Climate Food & Nutrition Quality of life

Chemistry as enabler

Health & Nutrition

Consumer GoodsConstructionTransportation Electronics Energy &

ResourcesAgricultureCus

tom

er

ind

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ries

Energy management

Water solutions

Wind energy

Rare earth metals recycling

Heat management Enzymes Plant

biotechnologyBatteries

Leightweight composites

Heat management

Functional crop care

Medical Organic Electronics

Gro

wth

fie

lds*

*including growth fields still under evaluation

Raw material change

Materials, systems & nanotechnology

White biotechnology

Tech

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field

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150 yearsNeed to screen all „particulate“ materials

Indicative ranking of conceptual & metrological challenge

1. Pigments, fillers, anticaking agents are particulate commodities, where product performance is linked to a relatively well-defined morphology

Datasheets often specify size in volume metrics or specific surface area

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Customers pays for particulate properties

No technical relevance of sizein number metrics

Even for this “most intentional” class of particulates, poly-dispersity is 50% to 70%

150 yearsNeed to screen all „particulate“ materials

BiPRO study expects alone in Belgium

about 2,000 – 5,000 substances

80,000 – 160,000 preparations

800,000 – 1,300,000 articles.*

The actual numbers that industry faces are much higher, since BiPRO focused on engineered nanomaterials and excluded non-engineered particulates (such as intermediates)

*A unique article is here a product anywhere along the supply chain, placed on the Belgian market, and that has its own product identifier (e.g. different coloured paints are unique products)

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150 yearsNeed to screen all „particulate“ materialsin the absence of guidance or validated methods.

Indicative ranking of conceptual & metrological challenge

1. Pigments, fillers, anticaking agents are particulate commodities, where product performance is linked to a relatively well-defined morphology

Datasheets often specify size in volume metrics or specific surface area

No technical relevance of size in number metrics

2. Solidified waxes, dried salts, mortars, polymer granulates are particulate, but product performance is after melting or dissolution „intermediates“

Size and shape are not engineered, not specified (µm // mm // cm)

Can be indispersible (soluble, reactive), polydisperse, complex shaped

3. Formulations, liquids with particulate traces, porous materials

Conceptually vague in 2011 definition revise „contain“ to „consist of“

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150 yearsMethods other than counting or EM required:solubles, reactives,

platelet morphologies non-engineered particulates

200 nm 500 nm

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VSSA in recommendations for a revision of the EC nano definition (D7.10)

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• NanoDefine results show very good agreement between EM and VSSA classification for monomodal substances considering known number of nano-scale dimensions (D3.3, D3.5)

• VSSA can be recommended as screening tool to identify both nano and non-nano (with conditional cut-off values)

• Screening strategy and decision scheme for technical guidance provided• Decision-making by VSSA down to 200nm diameter

• Borderline region 50nm to 200nm requires EM …. (always?)

150 years

Sea-sand: large particulatewith adherent debris

200 µm

Screening cut-off VSSA < 6 m²/cm³ resolves paradoxon of„usually not considered a nanomaterial” (JRC report #2)

may „contain“ nanoparticles but do not „consist of“ nanoparticles (JRC #3, D7.10)

BET [m2/g] VSSA [m²/cm³]ULTRAMID B3M6 LS SCHWARZ 23213 <0.01 <0.012ULTRAMID B3S UNGEFÄRBT <0.01 <0.012ULTRAMID B3WG10 SCHWARZ 564 <0.01 <0.012ULTRABATCH 422 <0.01 <0.012

mm-size polymer granulates (which nano-specificphyschem, tox, ecotox testing would be applicable?)

500 nm

Size / µm10 100 1,000 10,000

100%

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150 years

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How to use screening methods within the 50nm to 200nm borderline region?

identify families of same substance, logically relatedmaterials, apply TEM for one lead, screening for all.

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150 yearsTowards a family screening on powders

TEM for one lead, VSSA for all.

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Family of iso-indolines Family of perylenes

Family of di-keto-pyrrolo-pyrroles

150 yearsFamily approach enables nano-identificationthroughout 20th century via VSSA from«historic» pattern cards & publications

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1982 19991967 1969 1985/86 today (online)

80 70 60 50 40 30 20 10 0 years80 70 60 50 40 30 20 10 0 years

~1935

Mainly azo pigments, e.g.:• Hansa Yellows (PY 1-3,

PY 5-6, PO 1)• Permanent Red BB

(PR 48:1, PR 48:2)• Perm. Bord. FRR (PR 12)• Permanent Or. G (PO 13)others:• Indanthren Blue (PB 60) No Physchem data !

CuPc/Diarylide Perylene/Disazo/QA Isoindolinone DPP Introduction of Pigment Class

C.I. substance 1967/69[m2/cm3]

1984/86[m2/cm3]

Today[m2/cm3]

PY 109 Isoindoline 44 44 57

PY 110 transparent Isoindoline 115 85 85

PY 110 opaque Isoindoline 53 46 48

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150 yearsIn strict terms, the three metrics cannot be reconciled… but outside the borderline region, scope is the same… some borderliners can be calibrated… so we do use all metrics

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SEMTEM

VSSA by BET & t-plot

CLS/AC/AUC, spray-DEMA,

DLS

Number metrics

Smallestexternal

dimension

Smallestdispersible

unit

Engineered(nano?)

particulates

surfacemetrics

(nano?)particulate

intermediates

150 yearsIn strict terms, the three metrics cannot be reconciled… but outside the borderline region, scope is the same… some borderliners can be calibrated… so we do use all metrics

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1,000s engineered vs. 10,000s intermediatesmostly commodities:

pigments, fillers, anticaking agents

waxes, polymer granulates, mortars, organics, dried salts, …

EM and VSSA provide same classification on engineeredparticulates (pigment test cases)

VSSA screening reduces by-catch of large particulates, wherenano-specific risk assessmentdoes not work anyway(engineered or intermediates)