Graphene and Industrial Hygiene
Good Stewardship and Safe Nanomaterial Handling Practices
for Graphene Products
Industrial Hygiene and Graphene
Graphene and Industrial Hygiene
Industrial Hygiene and Graphene
This webinar will:
Describe the type and characteristics of the most common forms of graphene produced and used in commercial products.
Review good health and safety processes for nano-material production and handling from an Industrial Hygiene perspective.
Discuss what users of this material need to know regarding handling and use.
Graphene and Industrial Hygiene
About AIHAIndustrial hygienists anticipate health and safety concerns and design solutions to prevent them. They are the guardians of workplace safety, applying science to identify and solve health and safety problems.
Founded in 1939, AIHA is devoted to achieving and maintaining the highest professional standards for its members. More than half of the nearly 8,500 members are certified industrial hygienists (CIHs), and many hold other professional designations.
AIHA administers comprehensive education programs that keep occupational and environmental health and safety (OEHS) professionals current in the field of industrial hygiene.
Graphene and Industrial Hygiene
About The Graphene Council
The Graphene Council is the largest community in the world for graphene professionals; producers, researchers, academics, end-users and regulators.
We reach more than 50,000 materials science specialists world-wide.
The Graphene Council is a formal member of the ISO/ANSI/IEC graphene standards development working groups and is a leading advocate for the commercial development of this amazing material.
Graphene and Industrial Hygiene
Presenters
Her work has spanned the chemical, specialty metals, and explosives industries. She is currently an occupational health manager with the U.S. Air Force at Wright Patterson Air Force Base near Dayton, Ohio.
Christine Knezevich is a certified industrial hygienist with 30 years experience and a member of the American Industrial Hygiene Association (AIHA) Nanotechnology Working Group.
Graphene and Industrial Hygiene
Presenters
John Baker, CIH is a Principal Consultant for BSI EHS Services and Solutions. He holds a B.A. in Physics and an M.S. in Environmental Engineering with 40 years of experience in industrial hygiene and environmental management and consulting. He served as Deputy Director of the Center for Biological and Environmental Nanotechnology at Rice University.
Mr. Baker is the Chair of the American Industrial Hygiene Association Nanotechnology Working Group, a member of the American Society of Safety Engineers Industrial Hygiene Special Interest Group, and a technical member of ASTM Committee E56 on Nanotechnology.
Graphene and Industrial Hygiene
Forms of Graphene
Graphene is a two dimensional (i.e. one atom thick) planar sheet of sp²-bonded carbon atoms in a dense honeycomb shaped crystal lattice.
Graphene has extraordinary material properties including ultimate tensile strength of 130 gigapascals, electron mobility of 15,000 cm2·V−1·s−1, thermal conductivity between 2000–4000 W m−1K−1 and optical transparency of 97.7%. (Eric Pop, 2012) (Sheehy DE, 2009)
ISO/TS 80004-13:2017(en) Nanotechnologies — Vocabulary — Part 13: Graphene and related two-dimensional (2D) materials. Recognizes material up to and including 10 carbon layers as “graphene”.
Definitions
Graphene and Industrial Hygiene
Forms of Graphene
Graphene production methods can be classified broadly as “Top Down” and “Bottom Up”.
“Top Down” methods start with a feedstock material such as graphite and through various methods (physical, electrical, chemical, etc.) exfoliate individual layers of carbon.
“Bottom Up” methods start with a carbon feedstock such as methane gas that under controlled conditions (such as Chemical Vapor Deposition-CVD) is deposited on a substrate material (such as copper) in single or multiple layers.
Production
Graphene and Industrial Hygiene
Forms of Graphene
A wide range of materials in the commercial market are currently referred to as “graphene”.
Graphene Materials
Number of Carbon Layers Description
1 CVD, Mono-layer or “Pristine” Graphene
1 - 3 Very Few Layer Graphene (vFLG)
2 - 5 Few Layer Graphene (FLG)
2 - 10 Multi-Layer Graphene (MLG)
> 10 Exfoliated graphite or “Graphene nanoplatelets” (GNP)
Graphene and Industrial Hygiene
Forms of Graphene
In addition to the number of carbon layers, additional characteristics define the material.
Graphene Oxide (GO) - a compound of carbon, oxygen and hydrogen (typically approx. 65% carbon / 35% oxygen by weight).
Reduced Graphene Oxide (rGO) - Graphene Oxide in which removes much of the oxygen content resulting in approximately 95% carbon by weight.
Graphene Powder, Solution or Paste - Graphene material can be prepared in various physical forms including as a dry (usually black) powder, in solution (e.g. water or alcohol) or in a paste form (often as a dull reddish brown color).
Graphene Nano Platelets (GNPs) - GNPs typically have thickness of between 1 nm to 3 nm and lateral dimensions ranging from approximately 100 nm to 100 µm.
Functionalized Graphene - Chemical functionalization (adding specific elements to the surface of the graphene) is important in many applications where untreated graphene would be difficult or impossible to work with.
Graphene and Industrial Hygiene
Graphene Applications
There are more than 40 major applications areas for graphene.
Graphene and Industrial Hygiene
Industrial Hygiene and Issues Related to
Working with Graphene
Graphene Handling
Graphene and Industrial Hygiene
Occupational Exposure Limits
Basis: Health, Risk, Administrative
Route of exposure/ Duration
OELs will NOT be set for all MNMs
Options:
OELs per hazard characteristic:
Granular, Biopersistent
Fibers
Soluble or not Biopersistent
Specific such as carbonaceous
Hazard/Exposure/Control Banding
Graphene and Industrial Hygiene
Safety Data Sheets (SDS)
➡ Globally Harmonized System for Classification and Labeling of Chemicals (GHS) in section 2
➡ Composition/CAS number found in section 3
➡ OELs found in section 8
➡ Toxicology found in section 11
➡ Results of SDS review
Graphene and Industrial Hygiene
Material Characterization
Chemical composition
Size distribution
Shape
Surface charge
Functionalization
Agglomeration
Solubility
BET surface area
Raman spectra
Toxicology
Graphene is not the same as Graphite
Graphene and Industrial Hygiene
Developing Nanomaterial Products
Considerations For Product Realization
Christine Knezevich, CIH AIHA Nanotechnology WG
Graphene and Industrial Hygiene
Objectives
Various considerations will be reviewed during the following product realization steps:
Research & Development (R&D)
Prototype Testing (alpha testing)
Prototype Testing at a Customer Site (beta testing)
Production
Product Stewardship
Graphene and Industrial Hygiene
Hierarchy of Controls
Most Effective
Elimination
Substitution
Engineering Controls
Administrative Controls
PPE
Physically remove the
hazard
Replace the hazard
Isolate people from the hazard
Change the way people work
Protect the worker with Personal Protective Equipment
Approach
Graphene and Industrial Hygiene
Product Stewardship
Type of End Product (e.g., electronics, medical device, chemical product, etc.)
Geographic Market (e.g., US, EU, etc.)
Considerations Dependent on:
Graphene and Industrial Hygiene
US Regulatory Agencies
Product RegulatedByChemicals EPA(ToxicSubstancesControl
Act/TSCA)Pesticides,includingAntimicrobials
EPA(FederalInsecticide,Fungi-cide&RodenticideAct/FIFRA)
Food,Drugs&MedicalDevices FDAListI&ListIIsubstances DOJ(DrugEnforcement
Administration/DEA)ChemicalsofConcern DeptofHomelandSecurity(DHS)
ConflictMinerals SEC(Frank-DoddsAct)
Graphene and Industrial Hygiene
EU Requirements
In Europe, chemicals, including biocides, are regulated under the Registration, Evaluation, Authorisation, and Restriction of Chemicals (REACH) by the European Chemical Agency (ECHA)
EU Conflict Mineral Regulation 2017 was passed in May & goes into full effect January 2021
For electronics, there are also the Restriction of Hazardous Substances and Waste from Electrical and Electronic Equipment Directives
Graphene and Industrial Hygiene
Research & Development Considerations
Chemical Approval Forms completed for raw materials
Review raw material Safety Data Sheets (SDSs)
Add raw materials to lab chemical inventory
Ensure proper chemical labeling (29 CFR 1910.1450, OSHA’s Chemical Hygiene Plan)
Health, Safety & Environmental (HSE) review for handling, storage, disposal, engineering controls, and personal protective equipment (PPE) considerations
Graphene and Industrial Hygiene
R & D Chemical Approval Process
Includes a product stewardship review for:
TSCA status of raw materials (i.e., R&D exemptions & import requirements)
FIFRA (domestic/import)
DEA (domestic/import)
DHS Chemicals of Concern
Conflict Minerals
REACH – will finished product be shipped to the EU?
Graphene and Industrial Hygiene
Nanomaterial HSE Considerations
Matrix EngineeringControls
AdministrativeControls
PPE
Polymer FumeHood Stdlabpractices Labcoat,safetyglasses(w/sideshields),gloves
Liquiddispersion
FumeHood Wetwipesurfaces Labcoat,goggles,nitrilegloves
DryPowder
FumeHood HEPAvacuumsurfaces
Labcoat,goggles,nitrilegloves.N95respiratorsoutsidecontainment
Ref: UNC Chapel Hill Lab Nanomaterials Safety Policy
Graphene and Industrial Hygiene
IH Considerations
IH monitoring of lab personnel
Medical surveillance of lab personnel (respirators?)
Employee training
Employee feedback & monitoring results may modify engineering controls, administrative procedures & PPE
TSCA R&D Exemptions: document incidents, injuries and illnesses
Graphene and Industrial Hygiene
Medical Surveillance & Biological Monitoring
There are no specific medical surveillance or biological monitoring requirements for
nanomaterials at this time.
Graphene and Industrial Hygiene
Occupational Exposure Standards
Agency Standard
AmericanConferenceofGovernmentIndustrialHygienists(ACGIH)
ThresholdLimitValues(TLVs)BiologicalExposureIndices(BEIs)
NationalInstituteforOccupationalSafetyandHealth(NIOSH)
RecommendedExposureLimits(RELs)
OccupationalSafetyandHealthAdministration(OSHA)
PermissibleExposureLimits(PELs)
AmericanIndustrialHygieneAssociation(AIHA)
WorkplaceEnvironmentalExposureLevels(WEELs)
Graphene and Industrial Hygiene
R&D Produces Sample Batch of Product
Create product SDS
Create product technical information sheet
Determine Dept of Transportation (DOT) class
Create product label
Export considerations – does sample batch need to be sent out of the US for testing? Export Administration Regulations (EAR) apply.
File for TSCA Pre-Manufacturing Notice (PMN) or Significant New Use Notice (SNUN) if applicable
Graphene and Industrial Hygiene
Prototype Manufacturing (Alpha Testing)
Complete HSE review to ensure environmental permits & control equipment are in place & valid
The HSE review must include storage areas (e.g., flammable, toxic, etc.) for raw materials, products & wastes
Ensure IH & medical surveillance programs are in place
Train employees on HSE requirements
Graphene and Industrial Hygiene
Beta Testing (at Customer Site)
Ensure that IH monitoring results, medical surveillance, and employee feedback from the Alpha testing are incorporated in the production process before testing at a customer site.
Incorporate any feedback from the customer site into the product SDS & technical information sheet.
Graphene and Industrial Hygiene
Full Production
Full production may require additional environmental permit modifications if alpha testing is considered “R&D” activity & exempt from operating permits.
Complete a HSE review to ensure all recommendations from previous product stages are in place.
If the finished product is being shipped out of the US, ensure export compliance requirements are in place (i.e., EAR, TSCA, etc.)
Graphene and Industrial Hygiene
Production: Life Cycle Management
Impact RawMat’lStorage
Manufacture Storage&Transport
Environmental(air,water&waste)
Energy(electricity,naturalgas,etc.)
Health(physical,biological&radiation)Safety(chemical,electrical&mechanical)
*IncludeTeamMembersfromProduction,HSE,Marketing,Quality&SupplyChain.
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