Laboratoire National de métrologie et d’Essais

Overview of LNE’s activities led in aerosol

metrology

Tatiana Macé

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LNE’s STRATEGY FOR NANOPARTICLES

Strategy: To increase the reliability of the measurements

Characterization of the aerosol-related health and

environmental risks

End-of-life impact

(accidental combustion/ incineration)

Aerosols metrology (generation, characterization,..)

Industry

Environment

Society

Standardization Regulation

Biomedical analysis

Development of tools/methods for the implementation of national or

European nanomaterial-related regulations (current or future)

Transfer of measurement protocols

in standardization bodies

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AEROSOLS METROLOGY

(GENERATION, CHARACTERIZATION…)

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AEROSOL GENERATION AND CHARACTERIZATION OF THE NPs SIZE DISTRIBUTION

Development and validation of controlled NPs aerosol's generation protocols

(from powders or colloidal suspensions)

+

Characterization (SMPS, DMS, etc.)

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10 100 1000

Diameter (nm)

DN

/dlo

g d m

( #

/ cm

3 ) [

106 ] Nanoaérosol DP

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Diameter (nm)

DN

/dlo

g d m

( #

/ cm

3 ) [

106 ] Nanoaérosol OP

2 types of SiO2 stable and reproducible nanoaerosols obtained from 2 colloidal suspensions which contain

unagglomerated particles

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Averaged mean diameter

Averaged mean diameter ± 2 SD

First population

Second population

Mea

n di

amet

er d

m (n

m)

Scanning 1Stepping

Scanning 2

LaboratorySMPS1 SMPS2 SMPS3 SMPS4 SMPS5

APPLICATIONS: Instrument calibration & Inhalation toxicity studies

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EVALUATION OF UNCERTAINTY OF SIZE DISTRIBUTIONS FOR AIRBORNE NPs

Results from L. Coquelin PhD thesis

Development of a SMPS raw data processing tool in order to associate a confidence interval with the measured particles size distribution

Aerosol's particles size distribution measurement

SMPS

=

DMA (Differential

Mobility Analyser)

+

CPC (Condensation

Particle Counter)

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10-60

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4

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12 x 1011

dp

f

mean es timate95 % confidence regionorigina l

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MONA PLATFORM (On and off-line NanoAerosol Metrology)

ON-LINE MEASUREMENT: SIZE DISTRIBUTION/CONCENTRATION

GENERATION SYSTEMS

SMPS 3 nm < dp < 1 µm

Unstable aerosol t < 1 s)

APS 5 nm < dp < 2,5 µm

DMS 0,6 µm < dp < 20 µm

By electrophoresis: NAS By filtration: Filter and TEM/SEM Grid By Diffusion-Impaction: Nano ID

Stable aerosol (t > 2min)

Wet process

Electrospray Atomizer Vortex Shaker

Nanopowders Dry process

Sample collection methods

Colloidal suspension, salts, oils

Spark generator

Metallic and carbonaceous particles

By electrical discharge

DMA + CPC

OFF-LINE MEASUREMENT

AFM, SEM, EDS, DLS, BET, XRD, Zetameter

CARMEN platform measurement

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CARMEN: A PLATFORM FOR THE METROLOGICAL CHARACTERIZATION OF NANOMATERIALS

AFM Veeco

PANalytical X'pert PRO XRD

Micromeritics' ASAP 2020 BET

Malvern's Zetasizer Nano ZS

Ultra Plus FEG-SEM

Development of a specific metrology at the nanometer-scale

Creation of a nanomaterial's "ID" with its main describing parameters (ISO TC 229)

For every quantity, ensure the metrological traceability of the measurements and offer optimal uncertainty measurements

Size

Size distribution

Shape

Aggregation/agglomeration state

Crystal structure

Specific surface area

Zeta potential

Size distribution

Special interest in: - development of deposition methods to obtain well dispersed NPs - development of software tools to obtain particles size distribution from microscopy images

Metrological AFM (LNE)

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CHARACTERIZATION OF THE AEROSOL-RELATED HEALTH AND

ENVIRONMENTAL RISKS

- END OF LIFE IMPACT

(ACCIDENTAL COMBUSTION/ INCINERATION) -

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Degradation scenarios

Accidental combustion (fire): 50 kW/m2 (ISO 5660-1)

Incineration (end of life): 75 kW/m2 (controlled atmosphere)

RELEASE OF NPs AFTER THERMAL DEGRADATION OF NANOCOMPOSITES

Characterization of the emissions

- gas (FTIR)

- nanoparticles

(AFM Shape

SMPS and DMS particles size distribution)

More or less severe degradation conditions

depending on the type and content of NPs contained

in the plastic polymer matrix

Effects of the nanofillers on the aerosols emitted during the thermal degradation of different types of polymers

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EFFECTS OF THE PRESENCE OF FLAME RETARDANTS

Presence of nano oxides, such as Al₂O₃, in the polymer matrix

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Temps (s)

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ber

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atio

n (x

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part

icle

s/cm

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icle

s/cm

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1PMMA1PMMA

9PMMA + 15 wt.% Al2O39PMMA + 15 wt.% Al2O3

11PMMA +5 wt.% Al2O3 + 10 wt.% of APP11PMMA +5 wt.% Al2O3 + 10 wt.% of APP

Results from NANOFEU project

Assistance for the formulation of low environmental impact

materials

*APP = Ammonium PolyPhosphate

No significant rise in the number concentration of the emitted fine particles

Steep increase in the number concentration of the emitted particles

Addition of APP* to the polymer matrix

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BIOMEDICAL ANALYSIS

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BIOLOGICAL NANOPARTICLES

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ENUMERATION OF LIPOPROTEINS USING THE SMPS TECHNIQUE

So far, the diagnosis of cardiovascular diseases was

based on the measurement of the Total Cholesterol and on a

lipidic profile (different Lipoproteins types and densities:

LDL, HDL, etc.)

Indirect measurement method, not specific to LDLs (measurement bias have been identified)

New approach based on the characterization by SMPS of the lipoproteins size distribution

(10-100 nm)

Low risk

High risk

(Caufield et al., Clinical Chemistry, 54, 2008)

Development of a metrologically traceable method of enumeration of lipoproteins using the SMPS technique + assessment of the uncertainty relating to the particles size distributions

GOAL: To improve the diagnosis reliability

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TRANSFER OF MEASUREMENT PROTOCOLS IN

STANDARDIZATION BODIES

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INVOLVEMENT OF LNE IN TERMS OF "NANO" STANDARDIZATION

European Committee

French Committees

International Committees

TC 352 (Nanotechnologies -nanomaterials) French chairmanship (LNE, J.M Aublant)

ISO TC 24 SC4 (Particle Characterization) ISO TC 229 (Nanotechnologies) JWG2: Measurement and characterization

VAMAS (Pre-standardization relating to advanced materials)

X457 (Nanotechnologies - nanomaterials) X11L (Particle size – analysis and monitoring methods other than screening) Mirror committee of ISO TC 24 SC4 hosted by X457

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NANOMETROLOGY CLUB (LNE/C'NANO)

Created in 2011 More than 300 members / Free membership 3 workgroups 4 thematical meetings in 2013 1 annual conference open to all Website & newsletter

Website: www.club-nanometrologie.fr

GOALS

To create a network bringing together the academic and industrial worlds

To gauge industrial requirements

To define R&D programmes (response to calls for proposals, etc.)

To offer solutions in terms of toxicity and ecotoxicity assessment

To support standardization

To disseminate knowledge (guides, technical procedures, website, newsletter, etc.)

Slide Number 1LNE’s STRATEGY FOR NANOPARTICLESSlide Number 3AEROSOL GENERATION AND CHARACTERIZATION OF THE NPs SIZE DISTRIBUTIONEVALUATION OF UNCERTAINTY OF SIZE DISTRIBUTIONS FOR AIRBORNE NPsMONA PLATFORM (On and off-line NanoAerosol Metrology)CARMEN: A PLATFORM FOR THE METROLOGICAL CHARACTERIZATION OF NANOMATERIALSSlide Number 8RELEASE OF NPs AFTER THERMAL DEGRADATION OF NANOCOMPOSITES Slide Number 10Slide Number 11ENUMERATION OF LIPOPROTEINS USING THE SMPS TECHNIQUESlide Number 13INVOLVEMENT OF LNE IN TERMS OF "NANO" STANDARDIZATIONNANOMETROLOGY CLUB (LNE/C'NANO)