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Measurements at the nanometric scale

Latest update : March 2014

What is needed : reinforcement of the reliability, competitiveness and safety of nanotechnologies and nanomaterials

State-of-the-art processors involve a 32 nm technology, which means that the smallest object or pattern that could be designed presents a 32 nm CD (Critical Dimension).
Objective : change to a 16 nm technological node, whereas manufacturers are currently not able to monitor nanometer uncertainties which are associated with these CDs.

What is reported : the absence of reliable measurements slows down the development of nanotechnologies and nanomaterials risk analyses

Applications of nanotechnologies constitute a source of disruptive technologies and concern all sectors, from health to energy, food, computer science or transports. According to an inventory which was carried out in 2011 as part of the American initiative “Project on Emerging Nanotechnologies”, nanoparticles and nanomaterials can thus already be found in more than 1,300 commercial products.

Although nanotechnologies represent a potential market estimate of 500 to 3,500 billion euros on a global level by 2015 (Lux Research Inc, 2009, Nanomaterials State of the Market Q1 2009), the people involved in this emerging sector agree on the fact that the development of these technologies is slowed down by the absence of any metrology and instruments adapted to the nanometric field (1-100 nm).

As a result, nanometrology is provoking increasing interest from industries which are expecting accurate and reliable tools in order to better monitor manufacturing processes and to improve quality systems.

Besides, several studies have shown that toxicity of nanomaterials and in particular nanoparticles actually differs from that of bulk materials, which leads to the need of assessing the risks linked with these new materials. Yet numerous reports issued by agencies, whether governmental, for the surveillance or regulation of consumer products, have highlighted the lack of tools or methods adapted to the measurement of nano-objects by emphasizing the absence of reliable and reproducible measurements that has sometimes led to conflicting results which slowed those studies.

LNE’s answer : references at nanometric scale

Pyramid of traceability to the meter

Pyramid of traceability to the meter

Given these reports and in order to meet these needs, LNE has been implementing R&D actions for several years as part of its public service mission: these actions are related to the development, setting up and validation of instruments that are specific to nanomaterials characterization. Since metrology at the nanometric scale involves multiple quantities and various skills, LNE has chosen to favour three aspects of development: physical and chemical measurements of nanoparticles in aerosols, dimensional measurements of structured objects and measurement of the local properties of materials at nanometer scale.

These three aspects have led to projects that focus on the following fields :

This work will enable manufacturers to get traceability to SI units for their measurements. The processes used for instance in electronics or cosmetics will then benefit from more reliable measurements in order to ensure monitoring and follow-up, which would thus improve production processes control. The effects of nanoparticles on human health will also be better evaluated.

Contact : Georges Favre

Development of instruments

CARMEN platform

CARMEN platform :
click on the image to see the whole diagram

>> CARMEN platform dedicated to the MEtrological ChARacterization of Nanomaterials

LNE has been developing a platform for the MEtrological ChARacterization of Nanomaterials (CARMEN) since 2010 with the aim of offering industries and the academic sector a thorough solution for the measurement of the main parameters which characterize nano-objects (size, shape, polydispersity, chemical composition, aggregation/agglomeration state, surface charge, specific surface area, …).

This platform, unique in France, provides a national metrological reference for characterizing objects at nanometric scale. It gathers in a clean room and controlled environment (temperature, humidity, vibration, etc.) all the measuring devices required for a complete characterization of nano-objects (AFM, SEM, DLS, zeta potentiometry, BET, XRD), as well as several devices dedicated to sample preparation (optical microscope, ultrasonicator, vortex, titrator, centrifuge, scale, spin-coater). In addition to CARMEN, and as part of its particularity, a metrological AFM provides a direct metrological traceability to the meter for dimensional measurements (see section dedicated to the metrological AFM). Furthermore, these devices being available within the same clean room enable to avoid any risk of contamination of samples when they are handled and moved from one instrument to the other.

The ongoing work consists in determining the appropriate traceability chains and developing metrologically validated measurement protocols and sampling methods: thus each measurement will be associated with an uncertainty, and will provide platform users with an optimum confidence level for their characterizations. This will also enable to support the ongoing toxicological and ecotoxicological studies on the assessment of risks related to the use of nanomaterials.

Besides, thanks to this platform, LNE will be able to help manufacturers and laboratories meet the government’s demands regarding the reporting of nanoparticle substances, in conformity with decree n°2012-232 dated February 17th, 2012 (JORF n°043 dated February 19th, 2012) and with the August 6th, 2012 order (JORF n°185 dated August 10th, 2012).

Contact : Nicolas Feltin

AFM : atomic force microscope

Atomic Force Microscope

>> Dimensional measurements by Atomic Force Microscopy: Metrological AFM

LNE is in charge of developing national expertise in the field of dimensional nanometrology.

In France, numerous industries, laboratories and research institutes commonly use scanning probe microscopes which need to be periodically calibrated. This traceability to the SI unit of length (the meter) is obtained through the use of reference samples –1D or 2D grids – whose dimensional characteristics are assessed by an NMI (National Metrology Institute). However, at the moment nobody in France is able to calibrate these secondary references. As a result, users have to turn towards foreign NMI.

LNE thus decided in 2007 to start developing a metrological AFM whose measurements are traceable to the meter. This instrument was thoroughly developed by LNE in order to control all the design choices and thus reduce the influence of major sources of errors of the uncertainty budget (Abbe error, thermal effects, position monitoring by interferometry in the ambient air…). Ranges amount to about 60 µm for XY-axes and 15 µm for Z-axis, with an uncertainty on the measurement of the tip’s relative position compared to the sample of about a nanometer. The first images were obtained in 2010.

This primary reference instrument is now able to calibrate all the French stock of Atomic Force Microscopes and of Scanning Electron Microscopes which belong to industries or academic laboratories.

Contact : Sébastien Ducourtieux

 

 

 

 

 

 

Development of reference protocols

The RIP-oN2 project (REACH Implementation Projects on Nanomaterials, October 2011), which is supported by the European Commission, emphasizes the obvious lack of standards and validated methods for nanomaterials sampling and characterization. This lack of harmonization of the measurement protocols used to characterize nano-objects sometimes leads to conflicting results in toxicity studies related to nanoparticles. Besides, it curbs the implementation of ad hoc regulations.

>> Characterization of airborne nanoparticles: VAMAS project

Producing nanostructured particles intended for industrial use has existed for a few years, and the range of industries involved implies that occupational exposure to airborne nanoparticles might lead to a major public health issue in the near future.

Such rapid expansion of nanotechnologies thus raises a new prevention-related issue. Indeed, nanoparticles can penetrate the human body by respiratory route and their small size enables them to get through biological barriers and then migrate to the whole body. The effects of inhaled particles on human health depend on their toxicity potential, which is unique to them and varies according to their chemical composition, size, surface, shape, structure, solubility and the surface treatments they might have undergone. Nevertheless, one of the main physical factors is their size, since it determines the place where they will deposit within the respiratory tract as well as their interactions with the biological system. However the lack of standardized methods and sampling strategies in order to measure reference parameters (number, mass, surface, size, shape, …) of airborne nanoparticles does slow down occupational exposure measurements.

Results of SMPS comparison for the mean diameter of a SiO2 double-populated aerosol

Results of SMPS comparison for the mean diameter of a SiO2 double-populated aerosol

As a result, this project aims to validate reference methods regarding generation, sampling and characterization of several types of nanometric aerosols in terms of size and shape through inter-laboratory comparisons. The whole measurement chain (sampling, analysis, data processing, …) is at stake, in order to be able to provide traceable protocols that are easy to implement and whose measurement uncertainties will have been estimated. The first comparison aimed to use a direct technique (SMPS) to characterize repeatability and reproducibility of the aerosol generation from colloidal suspensions as well as of the measurement of the particle number size distribution. The second comparison focused on an indirect approach, with the sampling of nanoparticles on appropriate supports (filters, grids, mica) and their analysis with microscopy techniques (TEM, SEM and AFM). SiO2 particles are sensitive materials, thus they remained a priority for characterization, which in term shall provide harmonized methods that can be used by the standards bodies.

This study is part of the VAMAS (Versailles project on Advanced Materials And Standards), which is one of the 18 cooperative projects resulting from the G7 meeting that was held during the Versailles Summit (France, June 1982), when its members decided to enhance exchanges in advanced technologies. The VAMAS was set up as an international collaboration mechanism on pre-standard research dedicated to advanced materials. It spontaneously contributes to an upstream transfer of its results to international, regional and national standards bodies. The project was launched in May 2009 and involved the following laboratories: BAM (Germany), UNIGE (Italy), KRISS (South Korea), NPLI (India), CENAM (Mexico), INPL (Israel), DFM (Denmark), NMIJ-AIST (Japan), NMISA (South Africa), NMIA-QUT (Australia), LISA (France) and IRSN (France). The results have been proposed within the ISO’s Technical Committee in charge of nanotechnologies (ISO/TC 229) as raw material for the preparation of a potential future normative document.

Contact : François GAIE LEVREL

European research project NANoREG

European research project NANoREG

>> A common European approach to the regulatory testing of nanomaterials : NANoREG

The NANoREG project mainly aims to provide European regulations with harmonized tools that can quickly determine the hazard potential of new nanomaterials that are placed on the market. The project is funded thanks to the 7th European Framework Programme on technological research and development (FP7/NMP) and coordinated by the Dutch Ministry of Infrastructures and Environment. It will involve a consortium of 57 participants from 15 countries over a period of four years (from 2013 to 2017).

LNE is directly involved in this project given its participation in nanomaterials characterization. The laboratory is currently working on nanoparticles in aerosol phase and contributes to the development and validation of protocols for the generation of a reference aerosol with stable and reproducible concentrations of nanoparticles, that is intended for future inhalation toxicology studies. Methods to characterize the nanoparticles generated will also be implemented.

Nanoparticles sampling protocols shall be developed and validated (selection of supports, deposit conditions, ...) in order to make this critical stage reliable while characterizing dimensional parameters of nanoparticles through microscopy techniques (SEM, TEM, AFM).

This project will enable LNE to provide both a metrological framework and an assessment of the uncertainties of the measurements carried out for studies on exposure to nanoparticle aerosols.

Website : www.nanoreg.eu

Contact : Georges Favre

NanoDefine

NanoDefine

>> Defining a nanomaterial (NanoDefine)

Over the last few years, several definitions have been proposed at international level in order to describe what is a nanomaterial. These definitions are based either on the dimensional aspect or on the fact that new properties appear at this scale. For now, none of these definitions has been drawn up with general agreement, even though most of the time the sizes considered tend to be in the range of 1 to 100 nm. On October 18th 2011, the European Commission published a Recommendation for a definition, that would provide a basis for all regulatory documents to be drawn up regarding nanomaterials (cosmetic sector, food, environment, …). According to this Recommendation, a nanomaterial shall consist at least of 50 % of primary particles in the range of 1 nm to 100 nm. Once a definition is adopted, the appropriate means of characterization have still to be implemented in order to enable verification of that criterion and to provide reliable answer to the question "what is a nanomaterial?". Only then, regulatory texts resulting from this definition will be applicable.

This is what the European project NanoDefine intends to do, by providing by late 2017 the tools and ad hoc methodology so as to characterize nanoparticles size distribution in every type of matrices. The ability of the available methods to characterize the size of nanoparticles will be assessed and harmonized measurement methods will be developed to ensure that the application of the definition leads to consistent results at any moment and for all materials.

The consortium responsible for this 4-years project is led by RIKILT representatives (Netherlands) and gathers 29 partners, among which three are French representatives (LNE, CEA, L’Oréal).

LNE will assess the ability of SMPS (Scanning Mobility Particle Sizer) technique to meet the requirements of the definition of a nanomaterial, as provided by the European Commission, in order to outline the case (type of matrices, of nanoparticles, …) where this technique may be implemented as a priority. It will also be assessed the possibility to generate, from nanostructured powders, non-agglomerated nanoparticles in aerosol phase. Indeed, this condition is essential for the direct measurement of size distribution. This innovative approach would allow to simplify and accelerate the analysis procedure by making a characterization of the size distribution of a nanoparticles population through microscopy (SEM, TEM and/or AFM) and the preliminary sampling unnecessary.

Since this project is aimed at proposing a clear, validated and harmonized analytical strategy in order to reach reliable conclusions on the nano nature of a given material and/or product (within the meaning of the definition of October 2011), regular exchanges with the European (CEN) and the international (ISO) standardization bodies are scheduled. Because of its close links with standardization activities, LNE is directly involved by the validation of results obtained through transfer to CEN and ISO.

Website : www.nanodefine.eu

Contact : Georges Favre

Enhancing the industrial feasability of nanomaterials production: SMEs get access to methodological tools for the metrological characterization of nano-objects (NANOMET)

It is agreed that nanotechnologies act as a major lever of innovation for several industrial sectors. However, moving from R&D to industrialization of nanomaterials is still considered as a technical challenge. About 100 SMEs said they ceased their activity in nanomaterials because they were not able to recover the functional properties highlighted in laboratory. (D&Consultats study, "Les réalités industrielles dans le domaine des nanomatériaux en France"- Industrial realities in the field on nanomaterials in France, 2011).

>> Complementarity of SEM and AFM measurements: towards hybrid metrology

Study of the AFM/SEM complementarity for dimensional measurements

Study of the AFM/SEM complementarity for dimensional measurements

A SEM (Scanning Electronic Microscope) is a truly multi-purpose characterization tool which performs scanning at a very high rate and with a wide measurement range. The progress made in the field of sources and the control of electron beams now make lateral resolutions inferior to the nanometer possible with state-of-the-art SEM, which makes them competitive for nanoparticle measurement. However, the information provided on Z-axis is limited by the deflection of secondary electrons that are recovered by lateral detectors.

The AFM (Atomic Force Microscope) is the most widely used instrument in the industrial and academic worlds as well as in NMIs, because of its high resolving power due to its ability to put the sample to be pictured in interaction with a thin tip whose end has a radius of curvature of about 10 nm. The AFM is able to recreate a three-dimensional image of the surface by scanning the tip on the sample, whether it be in the ambient air, under vacuum or within a liquid environment. The resolution obtained on Z-axis is better than the nanometer but is degraded in the XY plane because it then depends on the tip’s size and geometry.

Thus the current SEM provide a very good lateral resolution (XY) and the AFM can reach subnanometric resolutions on the measurement of a nano-object’s height (Z): the two instruments then seem to be complementary.

Such complementarity of these techniques is ideal for the development of hybrid metrology at the laboratory. This concept was originally imagined in the field of micro-electronics and considers that the measurement of a given measurand is no longer only carried out with a unique instrument, but results from a data fusion from instruments of a different nature. The project aims to apply the concept to the concrete case of measurements that come from an AFM and an SEM.

Thus, developments are ongoing on the most appropriate deposit methods to be implemented (selection of substrates, deposit protocols, ...) so as to carry out measurements through both AFM and SEM. This also requires developing sample repositioning devices that allow to recover the exact same particles on both instruments, which is necessary to permit metrologically traceable characterization of a nanoparticle in the three dimensions. In this regard, the software nanoFocus was developed so as to quickly access the particle size distribution of a spherical nanoparticles population from AFM or SEM images (see the section dedicated to the development of data processing software). The measurement uncertainties must be estimated on both instruments and the traceability to the meter will be ensured by calibration thanks to the metrological AFM.

Contact : Nicolas Feltin

Enhancing the industrial feasability of nanomaterials production: SMEs get access to methodological tools for the metrological characterization of nano-objects (NANOMET)

Nanoparticles characterization using SME

Nanoparticles characterization using SEM

It is agreed that nanotechnologies act as a major lever of innovation for several industrial sectors. However, moving from R&D to industrialization of nanomaterials is still considered as a technical challenge. About 100 SMEs said they ceased their activity in nanomaterials because they were not able to recover the functional properties highlighted in laboratory. (D&Consultats study, "Les réalités industrielles dans le domaine des nanomatériaux en France"- Industrial realities in the field on nanomaterials in France, 2011).

The major impediment to the development of a nanomaterials industrial system in France is the lack of metrological tools and standardized procedures. This lack hinders the implementation of reliable controls of industrial processes and of efficient responses to the risk assessment studies associated with their use. Laying the foundation of a reliable and robust characterization of nanomaterials will have an effect on the competitiveness of the sector’s SMEs.

This 3-years project (2014-2017), funded by the French Direction Générale de la compétitivité, de l’industrie et des service (DGCIS – General Directorate for Competitiveness, Industry and Services), is aimed at enhancing the industrial feasability of processes involving nanomaterials by providing French companies (about 900) with reliable and reproductible protocols for measuring the main parameters which characterize a nano-object. On the one hand, the aim is to provide industry, in particular SMEs, with characterization tools and the associated methods required for enhancing their processes which generate or involve nano-objects and, on the other hand, to support them in their regulatory obligation (French decree no. 2012-232 dated February 17th 2012) to declare every year their nanoparticulate substances. The research of solutions aimed at harmonizing the methods of characterization of materials shall also contribute to the French proposition in the pre-normative framework at international level on the subject.

A survey phase of SMEs will precede R&D activities in order to identify precisely the measurement equipment available and their associated metrological requirements. This will allow to identify developments to be carried out during this project led by LNE which also involves CEA, ARMINES and the companies NanoThinking and Nanoceram. Two levels of nanomaterials characterization will be developed. The first one involves inexpensive and relatively simple implementation measurement techniques (DLS, BET, SMPS, ...) whereas the second focuses on the microscopy techniques that require more expertise and time, but whose advantage is to be directly traceable to the Internation System units, and thus to provide reference techniques. A website shall be created and updated all along the project in order to clearly present the developed methodologies and tools in the form of worksheets, freely available to SMEs.

Website : www.nanomet.fr

Contact : Nicolas Feltin

Better understanding and control of heat transfers at nanoscale (QUANTIHEAT)

Nanoparticles characterization using SME

Controlling heat transfers is of crucial importance in modern technologies which include nanocomponents or nanostructured materials. This challenge affects particularly industrial professionals in the field of micro-electronics, manufacturers of micro and nanosystems (MEMS/NEMS) or new energy recovery or conversion devices manufacturers, who need to have new tools and more reliable and reproducible measurement methods to support their future developments.

The European project QUANTIHEAT, implemented by a consortium of over 20 partners from 9 European countries, and led by CETHIL (Center for Thermal Sciences of Lyon, CNRS, France), is aimed at improving the understanding of these thermal phenomena at nanometric scale and at establishing a “thermal nanometrology” with a sustained experimental effort and a theorical contribution in the field of physics of thermal transfers during the next four years (2013-2017). In this regard, QUANTIHEAT partners plan to identify a common terminology for the different devices used and to create reference materials and devices for their calibrations activities. The project will also allow to develop new instruments for studying thermal transfers at ultra-local scale, building in particular on local probe thermal microscopy, derived from atomic force microscopy. Thermal models connecting the atomic scale to the macroscopic scale will be developed in order to interpret the observed phenomena. The new metrology tools will be applied to representative industrial materials so as to suggest ways to improve their properties or their manufacturing processes. The project QUANTIHEAT should result in a greater control of nanoscale thermal phenomena and should also promote the transfer of new thermal characterization methods towards industry. LNE is part of the project’s seven French partners and will provide its expertise in metrology for assessing and quantifying measurement uncertainties obtained through local probe thermal microscopy.

It should be noted that this project is unique as it brings together academic partners – physicists, experts in materials science and in modelling, experimenters and microscopists, industrial partners, including SMEs and characterization equipment manufacturers, as well as metrology institutes and microfabrication and nanofabrication platforms.

Website : www.quantiheat.eu

Contact : Bruno Hay

Development of data processing software

Particle size distribution and 95% confidence interval associated for a colloidal suspension of SiO2

Particle size distribution and 95% confidence interval associated for a colloidal suspension of SiO2

>> Airborne nanoparticles measurements: NANOAEROSOLS

Measuring airborne nanoparticles (of a 10-100 nm diameter) is a public health issue. However until today, the means used for measurements and the metrology associated have not always been adapted to ultrafine particles (<100 nm). It is thus necessary to develop a new metrology.

Within this context, LNE has been working on improving a measurement system based on the use of a SMPS (Scanning Mobility Particle Sizer) dedicated to the characterization of ultrafine particles in aerosol phase. This commercial instrument is commonly used to measure the size of ultrafine particles. It associates a DMA (Differential Mobility Analyzer), which enables the selection of particles in suspension in the air according to their electrical mobility, with a CNC (Condensation Nuclei Counter) placed downstream and whose role is to detect and count the selected particles. The particle size distribution of the aerosol sampled is finally obtained according to the number of particles detected by the CNC and to the DMA’s transfer function thanks to a technique of data inversion. To this day, although SMPSs are often considered as reference instruments for this type of measurement, the uncertainty associated with a particle size measurement is never assessed.

Within the framework of this project, carried out in collaboration with the IRSN (Institute for Radioprotection and Nuclear Safety) and Supélec (Electricity College), LNE has developed a software for processing SMPS raw data which allow to associate a confidence interval with the particule size distributions obtained. The different components of uncertainty of the measurement of a particle size distribution obtained with a SMPS (influence of the particles charge law, counts registered by the CNC and presence of particles bearing multiple charges, ...) have been identified and quantified. It is now possible to associate an uncertainty to the values measured for the main parameters of interest (median diameter and geometric standard deviation).

Contact : Tatiana Macé

>> Nanoparticles characterization by microscopy : nanoFocus

AFM or SEM image processing software nanoFocus for the characterization of nanoparticles size distribution

AFM or SEM image processing software nanoFocus for the characterization of nanoparticles size distribution

The number size distribution of particles may be characterized using different measurement techniques depending on the type of nanoparticles considered (chemical composition, size, monodispersity or polydispersity of the population, ...) and the matrix.

Scanning probe microscopy (SEM) or local probe microscopy (AFM) have the advantage of allowing a metrological traceability to the meter, through the calibration of a transfer structure using a metrological AFM, but are also the last resort solution where simpler and cheaper techniques (DLS, PTA, CLS, SMPS, ...) cannot be used. However, the main shortcoming is the number of particles than can be considered in order to calculate the particles size distributions.

This limitation may be avoided by using image processing software tools. In this regard, LNE developed the nanoFocus software, which allows to identify all the objects that are present in a AFM or SEM picture, and gives users the choice whether to incorporate in the distribution under construction or not each particle which has been identified in a dedicated window. This semi-automatic approach allows to avoid taking into account aggregates/agglomerates which could bias the the particle size distribution obtained. A particle size distribution of several hundreds of nanoparticles considered as spherical may be obtained within a few minutes from a SEM or AFM picture.

Contact : Nicolas Feltin

Nanomaterials and life cycle

>> Study of the reproducibility of manufacturing processes : NANOSES

AFM (a) and SEM (b) images of commercial gold nanoparticles (60 nm) deposited on a mica substrate

AFM (a) and SEM (b) images of commercial gold nanoparticles
(60 nm) deposited on a mica substrate

Primary nanoparticles are industrially manufactured in accordance with determined protocols that for the most part are monitored according to quality assurance procedures. When they are placed on the market, the manufactured batches’ specific properties thus do meet manufacturers’ requirements. However, it remains legitimate to wonder whether the intrinsic variability of manufactured batches, although it is in conformity with the aimed industrial applications, have an impact on people’s exposure.

Thus this study, which is funded by ANSES (French Agency for Food, Environmental and Occupational Health and Safety), aims to assess the impact of manufactured batches’ variability on the physical and chemical properties of interest of nanoparticles by the estimation of uncertainties. The parameters considered in this project are the particle size, the number concentration, the specific surface area, the crystalline structure, the size of primary particles and the chemical composition. Besides, the two materials focused on are titanium dioxide (TiO2) and silica (SiO2) for which France bears the status of “sponsor” in the OECD working group on manufactured nanomaterials launched in November 2007.

It will then be possible to take into account the variability that will have been highlighted within toxicological studies in order to better understand nanoparticles behaviour towards human health.

Contact : Tatiana Macé

>> Behaviour of nanostructured materials to incineration: INNANODEP

The growing development of polymer matrix nanocomposites raises the issue of end-of-life management of these materials, especially since no adapted recycling solutions are available yet and since studies on particles emissions and on potential impact on human health are rare. The nanoparticles included within these nanocomposites cannot be detected by the identification and sorting methods traditionally used for plastic materials at the moment. Besides, the absence of any specific marking of these nanocomposites usually leads to them being processed with polymer materials of a similar nature. They may thus be incinerated, in particular for their calorific potential, which increases the quantity of ultra-fine particles released in the air. This question might thus constitute a major public health issue within the years to come.

This project is funded by ADEME (French Environment and Energy Management Agency) and led by LNE in partnership with joint centre ARMINES (CMGD - a research center for Materials / Ecoles des Mines d’Alès) and with the collaboration of manufacturers such as ARKEMA, NANOLEDGE and PLASTICSEUROPE. It is meant to assess the efficiency of incineration industries (degradation conditions are much harder than in the NANOFEU project) in order to process waste that contains manufactured nanomaterials whose production is superior to 100 tons per year (silica, alumina, carbon black, TiO2, CNTs, modified clay) and for which ANSES (French Agency for Food, Environmental and Occupational Health and Safety) considers it is currently impossible to dismiss risks on both humans and the environment.

The work done will consist in determining the impact of incinerating polymer matrix nanocomposites on the composition and microstructure of ultra-fine particles that can be found in the released aerosols in order to determine whether the current methods used by incinerators for smoke processing are still adapted to this new types of waste.

Contact : Carine Chivas-Joly

Nanoparticles

Nanoparticles

Besides, still within the same theme of the study on nanomaterials end-of-life, namely thanks to the characterization of smoke and aerosols produced during their combustion or incineration, LNE is also involved in the COST Action MP1105 FLARETEX, which aims at gathering the main European actors that focus on flame retardants.

>> Fire behaviour of nanostructured materials : NANOFEU

The materials used to meet performance criteria regarding protection against fire (namely domestic fires) involve the use of additives which improve their behaviour. New systems based on the introduction of nanoloads may thus provide an alternative to traditional ways. As part of this evolution, the environmental impact of the alternative offered by nanoloads shall however be assessed and confronted to traditional systems.

The NANOFEU project consisted in studying fire behaviour of polymers containing nanoparticles (in presence or not of conventional flame retardant components). The parameters that determine the emission of nanoparticles and the modifications in the composition of gas products emitted in comparison with polymers only or with polymers containing conventional flame retardant systems were assessed. It was also possible to evaluate the morphological transformations undergone by nanoparticles during combustion.

Contact : Carine Chivas-Joly

>> Study for the assessment of dispersed composite fibre risk during fire: DACOFEU

Choosing composite materials for naval and aeronautical design is now widespread. These materials offer several advantages, including the ability to significantly reduce the mass of these devices (and thus their fuel consumption)and the improvement of some of their characteristics (mechanical strength, stealth,…) thanks to specific properties. Besides, the inexorable spread of composite materials in transports should also reduce transports ecological impact by reducing the CO2 emissions per passenger.

Given their nature and specific composition (fibres/matrix), studying the behaviour of these materials in case of fire is essential. Indeed the organic matrix of composites decomposes at high temperatures and releases gas species and aerosols whose toxic effects and environmental impact are still unclear. As a result, the environmental impact of a composite materials fire (for example following an aircraft crash) and the effects on health (acute and chronic) generated by the dispersion of solid degradation products (fibres/particles) and gaseous ones need to be better known.

This three-year project gathers DGA-TA, Eurocopter and DCNS Research around the same theme and aims to provide answers to this issue. Aerosols and gases resulting from the combustion of composite materials will be characterized by using several instrumental techniques (cone calorimeter, FTIR, impactor, SMPS, CNC, AFM, SEM). Besides, using digital simulation will help modelling fire behaviour of these materials as well as the atmospheric dispersion of degradation products.

Contact : Carine Chivas-Joly

>> Study of emissions linked with the incineration of nanostructured materials and possible impact on industrial processes : NANOEMI

Several categories of new materials (technical thermoplastics, thermosetting plastics, elastomers, paint) are developing, while there is currently no approved recycling and processing industry. However, the presence of nano-objects in materials is likely to modify the emissions produced. It is thus essential on the one hand to identify whether certain types of nanomaterials can generate a significantly high particle rate in specific scenarios and, on the other hand, to evaluate whether smoke processing systems that equip incineration installations are adapted to these new types of products.

This study aims to study the behaviour when incinerated of industrial or consumer goods based on nanocomposites for which there exists no recycling industry, and whose end-of-life is dealt with by incineration. The matrices studied will be technical thermoplastics and thermosetting plastics (epoxy resin, polyamides 6, polycarbonates) containing reinforcing particles (carbon nanotubes, nanotubes silicate (halloysite), fibres silicate (sepiolite)). Mechanisms for thermal degradation of nanostructured materials will be determined and the possible emission of nano-objects during incineration will be characterized with a wide range of instrumental techniques. This work will enable the development of a tool for decision support based on the classification of product categories (matrix, nanoloads) as well as the implementation of a process to reduce risks linked with the emission of nano-objects.

This three-year project is half funded by ADEME (French Environment and Energy Management Agency) and results from a collaboration between INERIS (French National Institute for Industrial Environment and Risks), LNE and ARMINES. It is included in preoccupations 46 and 50 of PNSE2 (National Plan for Health and Environment 2) and should provide answers to the lack of reliable metrological tools to characterize nanoparticle emissions (in particular in the air) by products that contain nanomaterials throughout their life cycle.

Scientific and technical supervision of this work is ensured by TREDI (Subsidiary of the Séché Environnement Group specialized in processing hazardous industrial waste by thermal and physico-chemical techniques), one of the major actors in the field of waste processing in France. This collaboration will enable the confrontation of laboratory’s approach with the changes in scale.

Contact : Carine Chivas-Joly

Support to manufacturers and to public authorities

>> Club nanoMétrologie

Club nanoMétrologie

LNE and the competence centre in nanosciences C’Nano set up the Club nanoMétrologie, in 2011. The club is open to all manufacturers and bodies that are interested in nanoscience and nanotechnologies. It aims at helping experts and companies meet in order to detect innovation lines and suppress technological limitations.

The Club currently gathers more than 280 members, including almost 35% of people coming from industry, and is composed of three working groups which each deal with specific topics :

  • - the needs for measurements in the field of health and environment (WG1) ;
  • - traceability of measurements at the nanometric scale : needs in reference materials, standards, traceability chains, methodology, uncertainties budget (WG2) ;
  • - instruments : needs in measuring instruments that are specific to nanotechnologies (WG3) ;

The aim is to build a bridge between the industrial and academic worlds by pooling metrological issues in all the fields covered by nanoscience and nanotechnologies. Exchanges within the club will lead to the setting up of strategic documents as well as research programmes.

The « 3èmes Rencontres annuelles en Nanométrologie » (3rd annual nanometrology meeting) took place on December 11th, 2013 in Paris and helped assess the work done throughout the year.

Website : www.club-nanometrologie.fr

Contact : Georges Favre

>> DGPR

Decree n° 2012-232 dated February 17th, 2012 sets the procedures for the annual mandatory reporting of production, distribution or importation of nanoparticle substances. Reporting is mandatory once a minimum quantity of 100 grams of a substance is produced, imported or distributed whether within the industrial or research sectors and shall be made each year before May 1st.

LNE was appointed by the DGPR (French government’s General body for Risk Prevention) to get involved in setting up the decree which will set the reporting and information obligations for nanoparticle substances by providing its skills in metrology and technical expertise in measurement and characterization methods.

This joint order of the French Ministers for Environment, Agriculture, Health, Labour and Industry came into force in 2012. Moreover, by the end of 2013, ANSES (French Agency for Food, Environmental and Occupational Health and Safety) was able to assess the situation in France (report available here).

Contact : Tatiana Macé

>> Standardization

Standardization committees in nanotechnologies and nanomaterials

LNE’s representation in standardization committees in nanotechnologies and nanomaterials.

Developing consensual standards that are widely approved is the only way to make up for the lack of harmonization of protocols for the characterization of nano-objects (sampling, characterization, data processing, …).

Since LNE bears a public service responsibility, it is directly involved in various standardization committees related to nanotechnologies and in particular nanomaterials analysis and characterization methods whether it be at the ISO, the CEN or AFNOR. It aims at ensuring measurement quality is a top priority in the standard projects under study.

>> DIM Nano-K

nano-k

For several years, the Ile-de-France region has supported the DIM (Domaine d’Intérêt Majeur = Major Field of Interest) “Nano-K: Des atomes froids aux Nanosciences”. This DIM is a network which gathers about 320 research teams throughout 109 laboratories of the Ile-de-France region and covers a large spectrum of topics dealing directly with nanosciences, from nano-electronics, nano-photonics and nanobiosciences to nano-chemistry.

Among the three transverse actions supported by DIM Nano-K, LNE is directly involved in the activities of the axis “Nano-fabrication, instrumentation, caractérisation, et métrologie” (Nanofabrication, instrumentation, characterization, and metrology).

Website : www.cnanoifraf.org

Contact : Nicolas Feltin

>> DIM Analytics

DIM Analytics

The Ile-de-France region officialized a new DIM in 2011 entitled “Analytics: analytical challenges, from design to system” which was approved for the period from 2012 to 2015. This new body gathers 20 partners, including LNE, that are all concerned by analytical chemistry, analytical development and innovation in terms of analysis.

LNE and the CEA were asked to lead the part of the research regarding the nanometric characterization by focusing on three main aspects: the characterization of nano-objects’ physical properties, chemical or physico-chemical properties, and the pre- and post-analytical steps (taking and sampling + sample processing through the issue of data reliability and measurement uncertainties).

LNE’s involvement in this field contributes to ensuring metrology is clearly identified in the proposed calls for projects and in the funded R&D studies.

Website : www.dim-analytics.fr

Contact : Sophie Vaslin-Reimann

Publications

Consult the list of publications associated with projects