Nanotechnology is moving forward, are you ready?...–Optical Particle Counter with collection...

Nanotechnology is moving

forward, are you ready?

Laura Hodson, MSPH, CIHCoordinator Nanotechnology Research Center

Centers for Disease Control and PreventionNational Institute for Occupational Safety and Health

2017 Ohio Safety CongressColumbus, OH

The findings and conclusions in this presentation have not been formally reviewed by the National Institute for Occupational Safety and Health and should not be construed to represent any agency determination or policy.

The National Institute for

Occupational Safety and Health

The U.S. Federal agency responsible for conducting research and making recommendations for the prevention of work-related injury and illness.

Mission: Generate new knowledge; convert research to practice; and collaborate globally to prevent work-related illnesses and injuries

What is a nanomaterial?

• One dimension 1 -100 nanometer size

• Special properties

• Naturally occurring (incidental) and specifically engineered

Small size Large surface area

Nanoparticles: Some Old, Some New

Naturally occurring Man-made by-product

Engineered Nanomaterials (ENM)

Nanomaterial Science: Opening the 3rd Dimension of the Periodic Table

”Carbon just isn’t carbon anymore”

Engineered Nanomaterials• Carbons

– e.g., nanotubes, nanofibers, fullerene, graphene

• Oxides

– e.g., metal oxides, ceramics, TiO2, ZnO, SiO2, CeO2, Fe3O4

• Metals

– e.g., Ag, Fe, Al, Si, Zn, Cu, Ni

• Cellulose

– e.g., nano fibrils, nano crystals

• Semiconductors

– e.g., CdSe, CdS, InAs, InP

• Polymers/organics

– e.g., liposomes, dendrimers

Next generation enabler for materials-

some key application areas

• Materials– Nano-enabled composites– Reinvented material science

• Energy/Electronics– Power generation– Computing ability– Electrical Storage

• Medical/Biological– “Smart” drugs– Disease detection and treatment

• Food and Agriculture– Production– Nutrition

• Pollution– Prevention/treatment– Sensors– Air quality– Water Quality

Over 1,880 commercial productswww.nanotechproject.org/cpi/products/

Merging Initiatives

Nanotechnology: AKA Nanomaterial Science

Brings us…

Advanced MaterialsNanomaterials, Nano-bio Functional materials, and more

All Moving into…

Advanced Manufacturing Technology

Why is it important to learn

about Advanced Manufacturing?

Manufacturing: Huge Economic Impact

If U.S. Manufacturing

were a separate country,

9th largest economy

worldwide

U.S. manufacturing

fundamentals strong

again: 900,000 direct

jobs added since

recession

Manufacturers contributed $2.17 trillion to the U.S. (NAM News)

Data from National Association of Manufacturers and Bureau of Labor Statistics

Source: The Future of Manufacturing: P. Manenti

“Industry and Manufacturing in the Future” is not too far off.

“Capacity”

“Capability BasedCustomer Fulfilment”

Focus on AM

Trends, Examples?

• Semiconductors

– Foundation of information technology applications

– Rapid research to improve performance

– New materials and structural technology

• Advanced (Nano) Materials

– Superior performance properties tuned needs

– Enhanced performance; reduced quantities

– Computational engineering

More Trends, Examples?

• Additive Manufacturing: Not new but advances and implementation – 3D Printing, Rapid Prototyping, Layering and Deposition,

Selective Laser Sintering , and more

• Synthetic Biology– Manufacture biological substances from engineered

biological systems

– Biomanufacturing: using biological templates or processes for manufacture of materials systems

Additive Manufacturing: a simple view(Subtractive)

Slide courtesy G. Roth, NIOSH

Industries using Additive Manufacturing

• Telecommunications

– Mobile phone cases, camera cases

• Automotive

– Molds for engine parts, interior trim

• Medical devices

– Implants, Invisalign™ orthodontics, hearing aids, tableting

• Aerospace and military

– Engine fuel nozzles

– Components (clips, etc.)

• Boeing – 200+ parts for 10 of its aircraft – including 32 on 787 Dreamliner

Feedstock materials for Additive Manufacturing • Powders

– Plastics, metals, ceramics, glass, alloys

– Micronscale to nanoscale (including ENM)

Ex: Ni, Co-Cr, stainless/tool steels, WC, Ti, Ag, Au, alloys (Ti, Cu, Al)

• Filaments– Thermoplastics (ABS, PLA, PC, nylon, etc.)

– Additives (colorants, metals [Co-Cr], ENM [graphene], etc.)

• Liquids– Photopolymers

• Sheets

Possible emissions from Additive Manufacturing

• Particulate

– Ultrafine particles (fume)3-9

– Feedstock materials (ENM, micronscale powder)?

• Organic vapors– Alcohols, aldehydes, BTEX

– Sensitizers (styrene, 4-oxopentanal)9

• Post-processing

– Finishing object (grinding, etc.)

– Powder recovery (sieving)3 Stephens et al. (2013); 4Kim et al. (2015); 5Afshar-Mohajer et al. (2015); 6Steinle. (2015); 7Azimi et al. (2016); 8Yi et al. (In Press); 9Stefaniak et al. (In Preparation)

Fume from 3D printing with blue ABS filament using

FDM9

Contains Cr

3D Printing is not just for desk tops.

Is the focus on creating ‘jobs’ that can be done better by robots?

Advanced Manufacturing

DARPA Strategic Plan (2007).pdf, Public Domain

Interagency Advanced Manufacturing

National Program Office (AMNPO)

21

NSTC - Advanced

Manufacturing

Subcommittee

Executive Office of the President

Advanced

Manufacturing

Partnership

(AMP/PCAST)

Advanced Manufacturing

National Program Office(hosted by DOC - NIST)

NIOSH as a collaborator

Focus Areas• Invest in innovation in emerging

manufacturing technologies• Accelerate commercialization• Securing the talent (worker)

pipeline• Improving business climate for

innovative manufacturing firms• Sustainable manufacturing

including worker health and safety

“ A broad public-private coalition involving business, labor, academia, government, and the community”.

A National PriorityAdvanced Manufacturing Partnership (AMP)

The US Landscape:

Manufacturing USA

National Network of Manufacturing Innovation

– FY 2016 Budget: $1 Billion investment matched by private sector

– Create 15 Manufacturing Innovation Centers over the next 5 years, as many as 45 in 10 years

manufacturing.gov

Manufacturing Innovation Institutes so far…

America MakesAdditive

ManufacturingDOD–Youngstown OH

LIFTLightweight &

Modern MetalsDOD – Detroit MI

DMDIIDigital Mfg & Design

InnovationDOD – Chicago IL

PowerAmericaPower Electronics

ManufacturingDOE – Raleigh NC

IACMIAdv. CompositesManufacturingDOE – Knoxville

TN

Integrated Photonics

DOD Rochester NY

Smart Manufacturing

DOELos Angeles,

CA

Flexible Hybrid Electronics

DODSan Jose, CA

Advanced Functional Fabrics

DODMIT

Robots in Manufacturing Environments

DOD Solicitation

Advanced Tissue Fabrication

DOD Solicitation

NNMI Highlights of 2 Centers

• National Additive Manufacturing Innovation Institute (now known as America Makes)

– Launched in 2012 in Youngstown, OH

– A 94-member consortium of business, academia and non-profits

– Focus on additive manufacturing, AKA, 3D Printing

• Advanced/nano materials• Growing numbers• Exposures not well known• Entry barriers are low for small

devices

The technology is being taught, but does it include health and safety?

America Makes: Key Objectives

IACMI, The Composites Institute

Knoxville, TN

Launched June 16, 2015

Agency sponsor: DOE

Startup funding: $70M public,

$159M co-investment

+344,000 square feet in five core regions

manufacturing, laboratory, instructional collaboration space

Advanced Composites Institute Profile

A partnership of world-class companies including:

Top universities including:Economic Development Council to leverage state support and investment

ICAMI: Strong Private-Public Partnership

Each Institute is operated by a consortium; serving a partnership of Industry, Academia and government

A Life Cycle View of Two Initiatives

Basic Proof of Scale Up EarlyCommercialization

Research Concept Production

“Involvement”

High

Low

NNI AM

Merging Point

Nanomaterials

Research

EHS helps bridge the

‘Valley of Death’

Commercialization

EHS as a Facilitator not a Barrier to Commercialization

Occupational Safety and Health

Opportunities

• Advanced materials– Nano metals,

carbonaceous, cellulose, quantum dots, etc.

– Powders, slurries, composites

• Complex Environment– Multiple chemicals– Biologicals– Energy (lasers, electron

beams)

• Exposures and Controls

– Material Handling

– Emissions

– Waste management

– Machine maintenance

• Risk Management

– Distributed workforce

The Real World Question-Nanomaterials: Are There Risks?

RISK = HAZARD X EXPOSURE

Hazard: Biological activity – toxicity. What is known?

Exposure: Where, to what, to what extent, and can it be measured?

Unknowns and uncertainties = Risk Management approach

Hazard

Carbon Nanotubes and Nanofibers• Considered as one of the few ‘new-to-the-world’

materials coming out of nanomaterial science– Array of chemical and physical properties– Applications from the simple to the sublime being

explored

• Huge market potential being developed– Materials– Electronics– Medicine

• Because of the above: Carbon nanotubes have been the subject of increasing studies.

Nanotoxicology of single-walled carbon

nanotubes (SWCNT) and multi-walled carbon

nanotubes (MWCNT):

Pulmonary Exposure in Mice

• Pulmonary exposure to:

– SWCNT causes rapid and persistent fibrosis in mice

– SWCNT can cause cardiovascular dysfunction in

mice

– MWCNT can reach the intrapleural space in mice (site

of mesothelioma for asbestos)

– MWCNT nanowires can induce inflammatory

mediators in certain regions of the brain in mice

MWCNT in Subpleural Tissues, Visceral Pleura and Pleural Space of Mice Following Oro-Pharyngeal

Aspiration (80 µg) From: Mercer et al., 2010

VP: visceral pleura; Mac: alveolar macrophage; Mo: monocyte; Ly: lymph vessel; PS: pleural space

Day 28

Day 56

Day 28

Day 56

VP VPMac

VP

VP

Ly

Mo

PS

CNT Carcinogenicity?

IARC Working Group: • MWCNT-7, classified as possibly

carcinogenic to humans• MWCNT (excluding MWCNT-7)and

SWCNT “not classifiable as to their carcinogenicity to humans” due to limited and/or inadequate evidence

Important to remember that there are many

types of SWCNTs and MWCNTs

Many different manufacturersMany different production techniquesMany different purifications and residual catalystsMany different lengthsMany different tipsSome produced as “powders”Some produced as “yarns”Some produced as “mats”Many different end purposes from electronics to composites

Exposure

Exposure Assessment

NIOSH Performs On-site Research

• To date, 105 visits to 65 different sites

• Diversity in sites, materials, and applications

• Focused efforts: CNT/CNF, Controls• Evaluate processes and personal

exposures• Use and extend existing methods• Partnerships with the private sector is

a key to success• Guidance and recommendations given

to employers• Summary results published

How can you determine potential exposures?

Photo credits, Laura Hodson, Chris Sparks and Adrienne Eastlake, NIOSH

Nanomaterials with an exposure limit

Assessing Worker Exposure:

Nanomaterials with exposure limits

NIOSH Current Intelligence Bulletins• Recommended Exposure Limits

(RELs) are mass based:

300 µg/m3 for nano TiO2

1 µg/m3 for CNT and CNF

• How and where to measure

43

Sampling for Titanium Dioxide

• NIOSH Method 0600 for Respirable Dust (pre-weighed PVC filter and cyclone)

– This is weighed

– If > 0.3 mg/m3 analyze same filter by NIOSH Method 7300, Metals for Titanium by ICP

• Collect a duplicate open-face sample using MCE filter (for electron micrograph)

Sampling for CNT/CNF

• NIOSH Method 5040 for elemental carbon (EC). Collect the respirable fraction (25mm quartz fiber filters with a cyclone inlet)

• Collect a second open face MCE filter sample to be analyzed by electron microscopy

• Personal breathing zone, source and background samples

Sampling for CNT/CNF

– Verify elemental carbon using electron microscopy• SEM or TEM with energy dispersive X-ray

spectrometry (EDS)

• Helpful for identification ( composite matrix bound vs. free unbound elemental carbon)

• No counting convention exists

– Particle counters have limitations

with fiber structures

Exposure Assessment in the Real World

Sampling for nanomaterials without

an exposure limit

Highlights of the Nanomaterial Exposure

Assessment Technique

NEAT 2.0

Eastlake A, Beaucham C, Martinez K, Dahm M, Hodson L and Geraci C [2016]. Journal of Occupational & Environmental Hygiene. Sep; 13(9):708-717. ISSN:1545-9632

Key Elements of NEAT 2.0

• Pre-assessment prioritization

• Field measurements

• Risk management

• Routine monitoring (confirmation)

Pre-assessment Prioritization

– Process description and flow

– Number of employees and job description

– Safety Data Sheets or other information

– Walk about to look at process, identify possible exposure potentials

– Review occupational exposure limits and health effects.

– Identify and review pertinent literature.

Photo courtesy Adrienne Eastlake, NIOSH

Field Measurements• Filter-cassette based

– Elements and Electron Microscopy (EM)

– PBZ, Source/ Area, Background

– Full shift and task specific

– With and without cyclones

– Various filter media

• Data logging with DRI’s

– Source/Area and Background

Photos courtesy Adrienne Eastlake, NIOSH

Direct Reading Instruments (DRIs)

• TSI CPC 3007 (TSI Inc., Shoreview, MN)– Condensation Particle Counter

– Measures particles between 10 nm and ~ 1 µm

• TSI OPS 3330 (TSI Inc., Shoreview, MN)– Optical Particle Counter with collection filter

– 16 user defined bins

– Measures particles between 300 nm -10 µm

• TSI DustTrak DRX (TSI Inc., Shoreview, MN)– Optical Particle Counter with collection filter

– 4 pre-determined size bins (1, 2.5, 4.0, and 10 µm)

Mention of a trade name does not constitute endorsement

Interpretation of real-time data

Integrated Sampling

• Personal breathing zone

– “True” indicator of worker’s exposure

– Determines levels of exposure throughout workday

– Can be compared to occupational exposure

limits

• Area

• Survey sources of contaminant

• Evaluate engineering controls

• Background

– Other contributions not related to the process

Filter Media and Methods

• NMAM 7402 (Transmission Electron Microscopy) open-face cassette with Mixed Cellulose Ester filter. Scanning Electron Microscopy collection on Polycarbonate or Teflon filter

• NMAM 5040 (Elemental Carbon) respirable fraction collection with Quartz Fiber filter

• NMAM 7300 (Elements by ICP) both open-face cassette and respirable with Mixed Cellulose Ester filter

NEAT 2.0 includes a set of filter based samples and

data-logging real time particle counters

Elemental Analysis

Particle Counters and Size Analyzers

Electron microscopy

NIOSH Site StudiesExposure characterizations for a wide

variety of materials

No-cost field evaluations have been available from NIOSH since 2006. We have completed over 100 site visits!

Photos courtesy A Eastlake and L Hodson, NIOSH

If you have emissions and exposures, What is the best way to control them?

Physical Form

Task Duration

Quantity

milligrams

kilograms

15 minutes

8 hours

slurry/suspension highly disperseagglomerated

Factors Influencing Control Selection

Engineered Local Exhaust Ventilation

Closed Systems

Occupational Health Hazardmild / reversible

severe / irreversible

Special thanks to Donna Heidel, NIOSH

Manufacturing Containment

Photos courtesy Naocomp Technologies, Inc.

Personal Protective Equipment– Secondary control

– Provide respiratory protection when exposures can’t be controlled below the REL.

• [N95, P100 filtering devices are effective at capturing nanomaterials]

– Provide protective respirators, clothing and gloves when there is potential for contact with contaminated surfaces. Could be task specific:

• Maintenance

• Emergencies

Respirator Use: With nanoparticles between

20 - 400 nm, 40 nm is the most penetrating size

N-95 P-100

Particle Diameter

Key Communication Productshwww.cdc.gov/niosh/topics/nanotech/

NIOSH Nanotechnology Topic Pagehttp://www.cdc.gov/niosh/topics/nanotech/

Thank you!lhodson@cdc.gov

www.cdc.gov/niosh/topics/nanotech/