Good Stewardship and Safe Nanomaterial Handling … Stewardshi… · Graphene and Industrial...

Graphene and Industrial Hygiene

Good Stewardship and Safe Nanomaterial Handling Practices

for Graphene Products

Industrial Hygiene and Graphene


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.


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.


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.


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.


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.


Types of Graphene Materials

Forms of Graphene


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


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


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)


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 Applications

There are more than 40 major applications areas for graphene.


Industrial Hygiene and Issues Related to

Working with Graphene

Graphene Handling


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


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


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


Developing Nanomaterial Products

Considerations For Product Realization

Christine Knezevich, CIH AIHA Nanotechnology WG


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


Industrial Hygiene

Industrial Hygiene is a Continuous Process


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


Product Stewardship

Type of End Product (e.g., electronics, medical device, chemical product, etc.)

Geographic Market (e.g., US, EU, etc.)

Considerations Dependent on:


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)


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


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


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?


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


Lab Practices & Procedures


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


Medical Surveillance & Biological Monitoring

There are no specific medical surveillance or biological monitoring requirements for

nanomaterials at this time.


Occupational Exposure Standards

Agency Standard

AmericanConferenceofGovernmentIndustrialHygienists(ACGIH)

ThresholdLimitValues(TLVs)BiologicalExposureIndices(BEIs)

NationalInstituteforOccupationalSafetyandHealth(NIOSH)

RecommendedExposureLimits(RELs)

OccupationalSafetyandHealthAdministration(OSHA)

PermissibleExposureLimits(PELs)

AmericanIndustrialHygieneAssociation(AIHA)

WorkplaceEnvironmentalExposureLevels(WEELs)


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


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


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.


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.)


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.


Discussion and Questions

Date post:	28-May-2018
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