Overview of LNE s activities led in aerosol metrology

Transcription

1 Overview of LNE s activities led in aerosol metrology Tatiana Macé Laboratoire National de métrologie et d Essais

2 LNE s STRATEGY FOR NANOPARTICLES Aerosols metrology (generation, characterization,..) Environment Characterization of the aerosolrelated health and environmental risks End-of-life impact (accidental combustion/ incineration) Industry Society Development of tools/methods for the implementation of national or European nanomaterial-related regulations (current or future) Regulation Standardization Biomedical analysis Transfer of measurement protocols in standardization bodies Strategy: To increase the reliability of the measurements 2

3 AEROSOLS METROLOGY (GENERATION, CHARACTERIZATION ) 3

4 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.) Second population DN/dlog d m ( # / cm 3 ) [10 6 ] Nanoaérosol OP Mean diameter d m (nm) First population Averaged mean diameter Averaged mean diameter ± 2 SD Scanning 1 Scanning 2 Stepping DN/dlog d m ( # / cm 3 ) [10 6 ] Diameter (nm) Nanoaérosol DP SMPS1 1 SMPS2 2 SMPS3 3 SMPS4 4 SMPS5 5 6 Laboratory 2 types of SiO 2 stable and reproducible nanoaerosols obtained from 2 colloidal suspensions which contain unagglomerated particles APPLICATIONS: Instrument calibration & Inhalation toxicity studies Diameter (nm) 4

5 EVALUATION OF UNCERTAINTY OF SIZE DISTRIBUTIONS FOR AIRBORNE NPs SMPS = DMA (Differential Mobility Analyser) + CPC (Condensation Particle Counter) f 12 x Aerosol's particles size distribution measurement mean estimate 95 % confidence region original Development of a SMPS raw data processing tool in order to associate a confidence interval with the measured particles size distribution d p Results from L. Coquelin PhD thesis 5

6 MONA PLATFORM (On and off-line NanoAerosol Metrology) GENERATION SYSTEMS Wet process Colloidal suspension, salts, oils Dry process Nanopowders By electrical discharge Metallic and carbonaceous particles Electrospray Atomizer Vortex Shaker Spark generator ON-LINE MEASUREMENT: SIZE DISTRIBUTION/CONCENTRATION OFF-LINE MEASUREMENT Stable aerosol (t > 2min) SMPS 3 nm < d p < 1 µm DMA + CPC Unstable aerosol t < 1 s) DMS 5 nm < d p < 2,5 µm APS 0,6 µm < d p < 20 µm Sample collection methods By electrophoresis: NAS By filtration: Filter and TEM/SEM Grid By Diffusion-Impaction: Nano ID CARMEN platform measurement AFM, SEM, EDS, DLS, BET, XRD, Zetameter 6

7 CARMEN: A PLATFORM FOR THE METROLOGICAL CHARACTERIZATION OF NANOMATERIALS AFM Veeco Size Specific surface area Size distribution Ultra Plus FEG-SEM Shape Metrological AFM (LNE) Micromeritics' ASAP 2020 BET Aggregation/agglomeration state 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 Special interest in: Crystal structure Zeta potential Size distribution - development of deposition methods to obtain well dispersed NPs - development of software tools to obtain particles size distribution from microscopy images PANalytical X'pert PRO XRD Malvern's Zetasizer Nano ZS 7

8 CHARACTERIZATION OF THE AEROSOL- RELATED HEALTH AND ENVIRONMENTAL RISKS - END OF LIFE IMPACT (ACCIDENTAL COMBUSTION/ INCINERATION) - 8

9 RELEASE OF NPs AFTER THERMAL DEGRADATION OF NANOCOMPOSITES Effects of the nanofillers on the aerosols emitted during the thermal degradation of different types of polymers Characterization of the emissions - gas (FTIR) - nanoparticles (AFM Shape SMPS and DMS particles size distribution) depending on the type and content of NPs contained in the plastic polymer matrix Degradation scenarios Accidental combustion (fire): 50 kw/m 2 (ISO ) Incineration (end of life): 75 kw/m 2 (controlled atmosphere) More or less severe degradation conditions 9

10 EFFECTS OF THE PRESENCE OF FLAME RETARDANTS Presence of nano oxides, such as Al₂O₃, in the polymer matrix No significant rise in the number concentration of the emitted fine particles Addition of APP* to the polymer matrix Steep increase in the number concentration of the emitted particles 1 11 PMMA +5 wt.% Al 2 O wt.% of APP 0.8 9PMMA + 15 wt.% Al 2 O 3 1PMMA Number Number concentration concentration (x (x particles/cm particles/cm 3 ) Assistance for the formulation of low environmental impact materials Temps (s) *APP = Ammonium PolyPhosphate Results from NANOFEU project 10

11 BIOMEDICAL ANALYSIS - BIOLOGICAL NANOPARTICLES 11

12 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.) New approach based on the characterization by SMPS of the lipoproteins size distribution ( nm) Low risk Indirect measurement method, not specific to LDLs (measurement bias have been identified) 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 12

13 TRANSFER OF MEASUREMENT PROTOCOLS IN STANDARDIZATION BODIES 13

14 INVOLVEMENT OF LNE IN TERMS OF "NANO" STANDARDIZATION French Committees X457 (Nanotechnologies - nanomaterials) X11L (Particle size analysis and monitoring methods other than screening) Mirror committee of ISO TC 24 SC4 hosted by X457 European Committee TC 352 (Nanotechnologies -nanomaterials) French chairmanship (LNE, J.M Aublant) ISO TC 24 SC4 (Particle Characterization) International Committees ISO TC 229 (Nanotechnologies) JWG2: Measurement and characterization VAMAS (Pre-standardization relating to advanced materials) 14

15 NANOMETROLOGY CLUB (LNE/C'NANO) Created in 2011 More than 300 members / Free membership 3 workgroups 4 thematical meetings in annual conference open to all Website & newsletter 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 Website: To support standardization To disseminate knowledge (guides, technical procedures, website, newsletter, etc.) 15