DI's arbejdsmiljøkonference Nanoteknologi og arbejdsmiljø. Per Langholz

Transcription

1 DI's arbejdsmiljøkonference 2013 Nanoteknologi og arbejdsmiljø Per Langholz

2 Content Short about Dyup and PPG Where to use nanomaterials for paints PPG's Nano HSE initiatives - Guidelines and registration Regulation of nanomaterials

3 PPG industries PPG business: Paints and coatings Optical Specialty materials Chemicals Glass and fiberglass PPG has manufacturing facilities and equity affiliates and operates in more than 60 countries. PPG Architectural Coatings EMEA was created in 2008 through the acquisition of SigmaKalon Group, a worldwide Dutch based coatings producer and the acquisition of Dyrup, a Danish based European Coatings producer.

4 Dyrup In January 2012 PPG Industries completed the purchase of Dyrup from its owner, Monberg & Thorsen, Dyrup is now a part of PPG Architectual Coatings EMEA. Strong brands and a broad range of quality products in paints and wood care made up the Dyrup Group s core business in the European market. Dyrup manufactures and markets products sold via two primary sales channels: - the DIY market, consisting mainly of paint retailers and builders merchants - the professional market (PRO), consisting of wholesalers and professional decorators

5 Unique properties of nanoparticles Size Optical Electronic Color Scattering Surface chemistry Mechanical Mobility Surface area Catalysis Reactivity Melting / sintering Rheology Composites Adsorption Dispersion Weight reduction Composition New possibilities Electronic Color Bioactivity Density / weight Mechanical Reactivity

6 PPG s Nano Commercialization Thin Film PVD and CVD Development Sungate 100 World s 1 st Low E Glass Solarban Low E Solar Control Glass CeramiClear Mar Resistant Clearcoat SunClean Self-Cleaning Glass Andaro TM Colorants Electrochromic Cabin Windows

7 Improvements using nano materials? Improved penetration into wood cells Less water uptake through coating film Less stress in the coating film/absorb stress Adjust surface hydrophilicity/hydrophobicity Improve adhesion to wood structure Improve UV protection of wood: In the wood Better UV protection from transparent coating

8 UV-degradation of wood Lignin degradation The glue for the wood is destroyed and wood fibres will fall out

9 Where to use nanomaterials for paints - raw materials Nano Titandioxide Nano Siliciumdioxide Carbon Black Nano Zinkoxide Nano silver

10 PPG Nanotechnology Guidelines Internal Hazard Communication MSDSs & labels from suppliers Indicators: nano and if yes what category (1-4) Categories 3 & 4 specific written instructions for safe handling Train affected personnel Workplace exposure assessment No accepted IH method, instrument, or exposure limits to date TSI P-Trak particle counter to check exposure control efficiency Can collect samples on TEM/SEM grids for analysis NIOSH published a field sampling guide Medical Surveillance NIOSH interim guidance- use existing surveillance and respiratory protection users process until specific protocol can be recommended NIOSH recommends each company keeps its own registry for now

11 PPG Nanotechnology Requirement Nanotechnology- one physical dimension in the range nanometers May possess entirely new physical and chemical characteristics, resulting in properties that are neither well described by those of a single molecule of the substance, nor by those of the bulk material Limit the scope to PPG employees, contractors and visitors who may have potential exposure to engineered nanomaterials with unknown or limited toxicological information. Materials like carbon black and welding fumes have particles in the nano-size range however they are excluded because toxicology data is available. It also does not apply to polymeric organic materials (e.g. resin dispersions or latex paint that may possess nano-structured features or particle sizes at the nano scale) unless engineered nanomaterials have purposely been added.

12 Nanotechnology Definitions PPG has adopted the working definitions of the ISO Technical Committee 229 WG1, (2008). Nanomaterials: Have one or more external dimensions or an internal or surface structure on the nanoscale (< 100 nanometers, nm). Nanomaterials consist of nano-objects which have one or more dimensions on the nanoscale and nano-structured materials Nano-objects: Have one or more external dimensions on the nanoscale One dimension- platelets, nanosheets, nanoplates, ultra thin film coatings Two dimensions- nanofibers consisting of nanorods, nanotubes or nanowires Three dimensions- nanoparticles, quantum dots, spheroidal (nanocrystals) Nano-structured materials: Have an internal or surface structure which measures in the nanoscale, typical examples are agglomerates and aggregates of nano-objects. They may exist bound to surfaces by covalent bonds, bound by van der Waals forces, bound in an adherent matrix, such as a plastic polymer, carried in solution or handled as a dry powder.

13 PPG operations handle four categories of nanostructured materials: CATEGORY DESCRIPTION GUIDELINES 1. Nanocomposite matrix- Solid Matrix Nano-objects bound within a solid matrix and not easily, if at all, able to be released. General safe handling; fire & explosion potential if dust generated in process 2. Nanocomposite matrix-liquid Dispersions 3. Nano-structured Colloids-Liquid Suspensions 4. Nano-objects, agglomerates & nanoaerosols Nano-objects bound within a liquid matrix and not easily, if at all, able to be released. Unbound nano-objects (e.g. nanoparticles) added to a liquid such that they could be released if the liquid evaporates. Liquid vapor pressure and processing conditions need to be considered to determine evaporation potential. Nano-objects are defined above. An agglomerate is a group of particles held together by relatively weak forces, including van der Waals forces, electrostatic forces or surf ace tension. Nanoaerosols are nanoobjects suspended in a gas either in nanoscale or as aggregates or agglomerates due to the attractive forces, which will not readily reform nano-size unless much energy is expended, e.g. grinding or sanding. Micronized powders fall into this category. General safe handling Specific guidance for PPE and respirators, spill clean-up, waste disposal, labeling waste Specific guidance for PPE and respirators, spill clean-up, waste disposal, labeling waste, check of controls, air emission controls, fire & explosion potential

14 PPG Nano Products In addition, PPG has defined a nanotechnology-based product as follows: Nanotechnology-based Product: A finished product or intermediate with the following features: Contains one or more raw materials that contain engineered nanomaterials or nanomaterials have been generated in the manufacturing process; AND The finished product has features and performance characteristics that are due to the use of the nano raw material, and these features would be lost if the nano raw material was replaced by a non-nano raw material; AND Nanomaterials remain present in the final product as distinct materials. They may be present as agglomerates, encapsulated or sterically-hindered but have not reacted with other raw materials to form a new non-nano material. Each SBU shall follow existing Product Stewardship processes to identify raw materials and products that are based on nanotechnology, to generate Safety Data Sheets and warning labels, to comply with applicable regulations and to address customer issues.

15 PPG s Nanotechnology Guidelines Methodology: Use a risk based approach for assessing & controlling potential hazards Divide nanoworld into 4 main categories of increasing potential exposure risk: 1. Nanocomposite matrix (solid) 2. Nanocomposite matrix (liquid dispersions) 3. Nano-structured colloids (liquid suspensions/unbound nano-objects in liquid) 4. Nano-objects & agglomerates/nanoaerosols Safe handling recommendations structured around these 4 categories

16 RISK DETERMINATION: Hazard Band (Toxicity) RANK QUANTITY RANK PHYSICAL STATE RANK High OEL or high hazard 1 1 Nanocomposite- Bound in solid matrix Low quantity 2 2 Nanocomposite-Bound in liquid matrix Nano-structured Colloid-nano-objects suspended in liquid 3 Low OEL or low hazard 4 4 Unbound dry nanoobjects, agglomerates or aggregates if High quantity primary particle size is nano or nanoaerosols, and solid matrices with friable or loosely attached nano-objects 4

17 Controls A-3 CONTROLS (These are guidelines, specific project reviews may yield other recommendations) Product of ranking above Control needed 12 or less Employ good work practices, general ventilation, PPE, housekeeping & cleaning procedures. Treat all materials contaminated with dispersible nano-objects or colloid-unbound nano-object liquid suspensions as nanomaterial waste stream. Spill clean-up for dry nanos with disposable clothing, gloves, shoe covers, and full-face P3/P100 cartridge respirator or PAPR Restrict work/storage area, good work practices, partial or totally enclosed system, local exhaust ventilation, PPE & fullface respiratory protection (P3/P100 filters minimum). Treat all materials contaminated with dispersible nano-objects or colloidunbound nano-object liquid suspensions as nanomaterial waste stream. Spill clean-up for dry nanos with disposable clothing, gloves, shoe covers, and respirators Restrict work/storage area, closed process & use local exhaust ventilation/wet methods when system is opened, PPE & fullface respiratory protection (P3/P100 filters minimum). Treat all materials contaminated with dispersible nano-objects or colloidunbound nano-object liquid suspensions as nanomaterial waste stream. Spill clean-up for dry nanos with disposable clothing, gloves, shoe covers, and respirators. Consult Corporate IH as appropriate. MEDICAL: Site EHS is to inform site Medical of names of individuals working with a defined subset of nanomaterials. Medical shall keep copy of completed Risk assessment or Nanoregistry list in affected employee medical files.

18 PPE & RESPIRATOR SELECTION BASED ON RISK & LEVEL OF CONTROLS: Category 1: Activities with limited potential to create exposure to nanomaterials. Example: Nanocomposite/Solid Matrix. Take measures to prevent generation of nano-objects through abrasion, sanding, grinding etc. If nanoobjects can be generated during processing follow guidance in category 2-3. Category 2: Activities with potential for exposure to Nanocomposite/Liquid Dispersions. Use process controls where applicable such as closed systems, LEV, proper work practices and PPE to protect eyes and skin e.g. safety glasses with side shields, face shield, and impervious gloves, clothing. Category 3: Activities with potential for exposure to Nano-structured Colloids- liquid suspensions of unbound nano-objects or Nano-objects/Nanoaerosols: follow table below

19 PPE & RESPIRATOR SELECTION BASED ON RISK & LEVEL OF CONTROLS: POTENTIAL FOR GENERATION OF LIQUID OR DRY NANO-OBJECT (UNBOUND) AEROSOLS ACTIVITY Processing (closed system) Processing with exposure potential (not closed system) CONTROLS Test efficacy using TSI P-Trak Conduct in lab fume hood, laminar-flow hood, glove box or enclosed process Use exterior hood or LEV e.g. Nederman arm, as close as possible to source & consider use of a Perspex (clear plastic) barrier for enclosure RESPIRATOR None Full-face mask w. P100/P3 cartridge or PAPR Processing outside of closed system (or LEV) and the nanoobjects have been modified to neutralize the charge or size < 10 nm Not available Supplied Air (SA) or SCBA w. hood or full-face mask Spills Small-< 10 g Large->10 g, or uncharged nano-objects Wet wipe small dry spills carefully, wipe wet spills, place cloths in sealed bag. Do not brush/sweep. Use HEPA vacuum for larger spills. For small spills wear full face mask, larger spills wear PAPR or supplied air. Cleaning Activities e.g. process equipment, LEV = local exhaust ventilation ductwork, hoods, spray booth Use exterior hood or LEV e.g. Nederman arm, as close as possible to source & use HEPA vacuum and wet wipes. Full-face mask w. P100/P3 cartridge or PAPR or Supplied Air PPE None/ Impervious gloves Impervious gloves, e.g. nitrile or per solvent used, Tyvek suit Impervious gloves, e.g. nitrile or per solvent used, Tyvek suit, shoe covers Impervious gloves, e.g. nitrile or per solvent used. Large spills- Tyvek suit, shoe covers Impervious gloves, e.g. nitrile or per solvent used. Tyvek suit, shoe covers

20 NATIONAL REGULATORY DEVELOPMENTS REGARDING NANOMATERIALS AND NANOTECHNOLOGIES ORGALIME, The European Engineering Industries Association, December 2012 EU General Eg.: survey of nano-products, Nano centre, Action plan, research activities AU, B, DK, FIN, F, D, IRL,NL,E,S,CH,UK Sectoral Register/Declaration Production phase Products End of life OHS Waste Mandatory: F, DK Guidelines etc. AU, B, DK, F, D, I IRL,NL,E, S,CH,UK No specific provision for nano AU, B, DK, FIN, F, D, IRL,NL,E,S, UK No specific provision for nano AU, B, DK, FIN, F, D, IRL,NL,E,S,CH,UK AU, B, D, IRL, NL, CH, UK CH

21 France Environment Code Livre V titre II chp 3 and 4 Decree no of 17 February 2012 Ministerial Order of 6 August 2012 Mandatory declaration of substances produced, imported or distributed at nanoparticulate state (yearly; > 100 gr) Entering into force on 1/1/2013 Website for declaring substances with nanoparticle status

22 Denmark Plans to create a national register of Nano-database products containing nanomaterials (digital registration system using IUCLID as a basis in view of having a register compatible with EU register if it is set up) to be finalised in June 2013 Only products containing nanomaterials, which deliberately engineered nanoscale, reported. If the release of nanomaterial can be safely ruled out using or waste treatment, the product is exempt from reporting. Triviality limit: All products containing nanomaterials in a total quantity per nanomaterial above 100 g per legal entity (CVR) per. year regardless of how many products they are used in.

23 DG Environment commission DG Environment commissioned this study on the 'Development of an inventory for consumer products containing nanomaterials

24 REACH Definition of nanomaterial Commission Recommendation of 18 October 2011 on the definition of nanomaterial Text with EEA relevance A natural, incidental or manufactured material containing particles, in an unbound state or as an aggregate or as an agglomerate and where, for 50 % or more of the particles in the number size distribution, one or more external dimensions is in the size range 1 nm 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 from the above, fullerenes, graphene flakes and single wall carbon nanotubes with one or more external dimensions below 1 nm should be considered as nanomaterials.

25 Nanomaterials in REACH and CLP Nanomaterials are covered by the definition of a substance in REACH, even though there is no explicit reference to nanomaterials. Nanomaterials that fulfil the criteria for classification as hazardous under Regulation 1272/2008 on classification, labelling and packaging (CLP) of substances and mixtures must be classified and labelled.

26 Reach guidance documents The three appendices concerning information requirements (appendices to R7a, R7b and R7c) have been developed in order to provide advice to registrants for use when preparing registration dossiers for nanomaterials Chapter R7a Endpoint specific guidance, testing strategy for solubility, hydrolysis and pka, granulometry (as particle size distribution) Chapter R7b Endpoint specific guidance, Aqua toxicity, Degradation/Biodegradation Chapter R7c Endpoint specific guidance, Aquatic bioaccumulation, Effects on terrestrial organisms, Toxicokinetics Chapter R.8 Characterisation of dose [concentration] - response for human health Chapter R.10 Characterisation of dose [concentration] - response for environment Chapter R.14 Occupational exposure estimation

27 Eco-label products criteria for nanomaterial Eco-label to indoor paints and varnishes - No Eco-label to outdoor paints and varnishes No Nordic Ecolabelling of Chemical building products -Yes Nordic Ecolabelling of Indoor paints and varnishes No

28 Nano criteria Nordic Ecolabelling of Chemical building products Nano particles Nano metals, nano carbon compounds and/or nano fluoride compounds must not be actively added to chemical building products, unless documentation exists that they will not entail problems in terms of health or the environment. For these purposes Nano particles are counted as particles where at least one of the dimensions is smaller than 100 nm. Nano metals, for example, are nano silver, nano gold and nano copper.

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