1 Considerations for LCA of Nanotechnologies Jackie Isaacs Center for High-rate Nanomanufacturing Associate Director and Professor Mechanical & Industrial Engineering Northeastern University, Boston MA Nanotechnology and Life Cycle Analysis Workshop Chicago, IL November 5-6, 2009 EEC

CHN Vision: The Path from Nanoscience to Nanomanufacturing Environment, Health and Safety Regulation, Ethics and Education Nanomanufacturing CHN Mission To bridge the gap between nanoscale scientific research and the creation of nanotechnology-based commercial products Nanoelements and templates Assembly and Transfer Reliability Manipulation of Trillions of Nanoelements Applications in Energy Electronics Biomedical Materials

Education & Outreach NEU; UML; UNH Thrust 3: Applications NEU; UML; UNH Thrust 1: Nanoelements and Nanotemplates NEU; UNH; UML Thrust 4: Societal Implications NEU; UML Thrust 2: High-rate Assembly and Transfer NEU; UML; UNH CHN Path to Nanomanufacturing Thrust 4: Responsible Manufacturing NEU; UML

What is High-rate Nanomanufacturing? CHN: Directed Assembly and Transfer

Technology Platfom Materials EnergyElectronics Bio/Med Structural EMI- shielding Flexible Electronics Memory Devices Biosensors Photovoltaic Batteries Drug Delivery CHN Applications Roadmap

TemplatesNanoelements Assembly Processes Transfer Processes Substrates Potential Applications Microwires template NanoparticlesElectrophoretic Direct transfer (no functionalization) Silicon SWNT switch for nonvolatile memory devices Nanowires templates Carbon nanotubes (SWNTs and MWNTs) Chemical Functionalization Direct transfer with chemical functionalization Polymer Polymer-based Biosensors Nanotrench template Conductive polymers (PANi) Electrophoretic and chemical functionalization No transfer needed Metal Nanoparticle- based Biosensors Template-freePolymer blendsDielectrophoretic SWNT Batteries Fullerenes Photovoltaics Nanowires EMI Shielding CHN Toolbox Connects Research to Applications

CHN Toolbox: Process Flow for SWNT Switches TemplatesNanoelementsAssembly Processes Transfer Processes SubstratesPotential Applications Microwires template NanoparticlesElectrophoretic Direct transfer (no functionalization) Silicon SWNT switch for nonvolatile memory devices Nanowires templates Carbon nanotubes (swnts and mwnts) Chemical functionalization Direct transfer with chemical functionalization Polymer Polymer-based biosensors Nanotrench template Conductive polymers (PANi) Electrophoretic and chemical functionalization No transfer needed Metal Nanoparticle- based biosensors Template-freePolymer blendsDielectrophoretic SWNT batteries Fullerenes Photovoltaics Nanowires EMI shielding

Thrust 3: Testbeds, Applications and Reliability NEU; UML; UNH Thrust 1: Nanoelements and Nanotemplates NEU; UML; UNH Thrust 2: High-rate Assembly and Transfer NEU; UML; UNH Education & Outreach NEU; UML; UNH Thrust 4: Responsible Manufacturing NEU; UML CHN Path to Nanomanufacturing End-of-Life Impacts High-rate Toxicity Screening Environmental and Economic Uncertainties Exposure Assessment & Control Regulatory Issues Social & Ethical Issues

9 From Geraci, Jan 2008 Risk Management of Engineered Nanoparticles:

Fundamental Environmental Health/Safety Issues 1.Are exposures occurring ? 2.Are the exposures harmful ? Answers lead to development of best practices to avoid harmful exposures Project Leader: Ellenbecker, Tsai,UML Project Leaders: Rogers, Bello, UML

Worker Health & Safety Issues Airborne Exposure –Where do nanoparticles reside? –Personal protective equipment required? Dermal Exposure –Can particles penetrate skin? –Gloves effective? –Personal protective equipment required? Respiratory System Undertaken by Partner UML Toxics Use Reduction Institute

Different Air Flow and Vortex Patterns Conventional hood Air-curtain hood

Compare Other Powder Handling Systems Biological safety cabinets scheduled for testing Development of best practices for powder handling Local enclosures (not conventional glove box) may provide improved protection for both workers and environment

Numerous Properties Impact Toxicity Characterization of exposure hazards hampered by ability to measure multiple necessary physicochemical parameters implicated in the toxicity Biological significance of measured properties and exposures is often unclear Surface Area Metals/Impurities Surface Charge Morphology Crystallinity Solubility in biological fluids Etc…. Nanomaterial Properties Are these exposures high, dangerous?

High Through-put Toxicity Screening Needed Thousands of functionalization variations for nanomaterials; existing toxicity testing approaches cannot handle in terms of complexity and cost A critical need exists for a simple, high-rate toxicity screening of nanomaterials…. Ferric Reducing Ability of Serum (FRAS) Method developed to address this need… Project Leaders: Rogers, Bello, UML Toxicology In Vitro 2008 Inhalation Toxicology 2008

Measured Endpoints from Testing Analysis of Predictive Utility of FRAS 19 NMs previously FRAS characterized NMs characterized by CEIN and NIOSH Additional NMs from vendors 4. Cellular Toxicity Testing (Eukaryotic Cells) 6. Acellular and Cellular ESR (NIOSH) 5. Gene Expression (Prokaryotic Cells) Intracellular oxidative stress Extracellular oxidative stress Mitochondrial damage DNA damage Apoptosis Cell Viability Various stress genes Genotoxicity biomarkers DNA damage/repair System genes activation Extracellular oxidative damage (includes multiple mechanisms) Extracellular reactive oxygen species 2. FRAS3. Acellular DCFH 1. Physio-Chemical Characterization NMs to Test Characterization and Testing Extracellular reactive oxygen species Intracellular reactive oxygen species Statistical predictive models of endpoints Develop a multi-tiered screening strategy Compare FRAS with DCFH and ESR Funded High-rate Screening Research

LCA Comparison of SWNT Mfg Processes Journal of Industrial Ecology Special Nanotechnology Issue (Healy, Dahlben, Isaacs, 2008) Focus on mfg phase of life cycle Mass balance of processes to quantify products and emissions Toxicological information of engineered nanomaterials not readily available Impacts attributed to energy footprint

Fundamental Tradeoff Issues for Commercialization May 19, 2008 Protecting Nanotech Workers from Health Risks By Laura Walter A study appearing in the May issue of Journal of Occupational and Environmental Medicine points out that nanotechnology companies must consider the steps they plan to take to protect the health of employees exposed to engineered nanoparticles. “Companies currently involved with nanotechnology are faced with the dilemma of balancing a desire to expand a potentially bountiful technology with limited knowledge about the potential hazards.” the dilemma of balancing a desire to expand a potentially bountiful technology with limited knowledge about the potential hazards.” Definitive toxicity results unavailable… Uncertainty in risk of exposure… How can companies responsibly commercialize products?

Possible Risk Assessment Methods for Nanomaterials MethodPros & Cons Monte Carlo models + Allows modeling uncertainty - No tradeoff framework Decision trees + Allows insights with limited data - Can become overly complex Bayesian belief networks + Means for calculating conditional probabilities - No decision nodes Influence diagrams + Accounts for relationships - Compact representation Multi-criteria decision making + Tradeoff frontiers - Deterministic Analytic hierarchy process + Practically useful - Based on subjective opinions Goal programming + Can handle relatively large number of objectives - Deterministic Desirability functions + Can compare discrete alternatives, robust - Abstract approach, arbitrary weights Life cycle assessment + Systematic tool - Comparison of different studies is difficult

Given Current Uncertainty… Monte Carlo Simulation Model Developed for SWNTs Four levels of EHS industrial hygiene defined : None Low LevelMedium LevelHigh Level Engineering Controls Ventilation Fume hoods Enclosure of processes Administrative Controls Annual worker training Air monitoring Medical monitoring Personal Protective Equipment Latex gloves Nitrile gloves Disposable HEPA filters Tyvek suits Respirators Project Leaders: Benneyan, Isaacs NEU; Graduate Student: Ok Gloves

Process-based Cost Model Conceptual Diagram Within TCM Variable Costs Total Variable Cost Raw material Cost Scrapped Material Cost Consumable Materials Cost Direct Labor Cost Energy Cost Indirect Labor Cost Fixed Costs Total Fixed Cost Main Equipment cost Auxiliary Equipment Cost Overhead Labor Cost Building Cost Maintenance Cost Investment Other Costs Costs external to model General Administration Marketing and Sales Shipping and Receiving Research and Development Profit and Taxes Total Production Cost

SWNT HiPco Production Costs Determined Base case assumptions –Production volume: 10,000 g/yr –Operating hours: 2000 hr/yr –Capital recovery rate: 10% –Overhead cost: 40% of direct labor –Maintenance cost: 5% equip. cost –Labor wage: $20/hr –Electricity cost: $0.10/kW*hr –Building cost: $13/ft 2 *yr Ok, Benneyan, Isaacs Journal of Industrial Ecology Special Nanotechnology Issue 2008 Monte Carlo Simulations

MethodObjective CHN Example Application Potential Research Needs Monte Carlo simulation Comparison of alternate occupational health protection strategies Monte Carlo risk models for HiPco nanomanufacturing process Dose response curves could be included to model for better understanding of occupational health risks. Multi-criteria decision making Balancing reliability, exposure, and throughput for a nanomanufacturing process Goal programming model for a nanomaterial production process Nanoparticle monitoring results would inform the safety criteria in the analysis. Desirability functions Determining the most preferred product or process from various alternates Desirability optimization for the selection of a specific product Experimental design studies could help to have accurate process parameters. Stochastic programming Reliability and safety analysis for nanomanufacturing processes Chance- constrained programming for a specific nanomanufacturing process Involvement of researchers from different research areas would improve the theoretical modeling of the problem. Creation of Risk Modeling Tools Work underway on next case study related to fume hood work Project Leaders: Benneyan, Isaacs; Graduate Student: Ok

Energy Use for SWNT Switch Mfg Pre-diffusion Cleaning Oxidation Pirahna Etch + Rinse Cleaning Photoresist Application Bake Electron Beam Lithography Photoresist Development Inductively Coupled Plasma Etch Chrome Gold Deposition Photoresist Stripping Carbon Nanotube Deposition Process Flow Diagram CHN Overview 2008 SWNT Switch Energy Use for SWNT Switch Mfg Project Leader: Isaacs; Graduate Student: Dahlben

Environmental Assessment Using SimaPro CNT Switch Manufacture Major impact categories: –Airborne inorganics Sulfuric acid used in cleaning steps –Climate change CO 2 release from energy use –Fossil fuels Dominated by energy-intensive equipment and operation time

Extend LCA Scope to Use and End-of-Life Mfg. Life Phase CNT switch Conventional Use EOL    TBD  transistor  Environmental / economic comparison of SWNT switch to existing technology  Estimation of energy during use phase  Identification of potential barriers or advantages to recycling CNT materials within existing infrastructure From literature TBD

Path Forward: Environmental & Economic Uncertainty Inherent tradeoffs and enormous uncertainty exist for nanomanufacturing costs and workplace exposure Until EHS research progresses, these modeling tools and analyses provide useful guidance for private & regulatory decisionmakers Multi-criteria modeling in future work will assess tradeoffs among economic, health, environmental, and societal impacts of nanoproducts Results from CHN exposure monitoring inform, enhance and complement this effort Systems approach for development of toolkit will support effective and responsible commercialization Informed Decisions Health & Eco-risks Social Benefit Engineered Nanomaterials Nanotech Products Nanomanufacturing Risk Models

28 Range of social and ethical issues for emerging nanotechnologies Social Context Issues environmental justice, consumer safety/autonomy; privacy, unequal access Contested Moral Issues nano-enabled weapons, synthetic biology, embryonic stem cells Form of Life Issues conceptions of longevity and health, forms of sociability, artificial alternatives Technoculture Issues technofixes, commodification of nature, elitism in decision-making Transformational Issues human enhancement, artifactual persons Significance of issues to responsible development of nanotechnology Steps can be taken to begin addressing these issues Nanotechnology: The Social and Ethical Issues Project Leader: Ronald Sandler Sandler, “Nanotechnology: The Social and Ethical Issues” Woodrow Wilson Center, Project on Emerging Nanotechnologies, 2009 Available on-line

Integrated Systems Approach Required for Appropriate and Efficient Commercialization Responsible Nanomanufacturing 29 Social & Ethical Issues Regulatory Issues Enviro & Economic Uncertainties EHS Assessment, Tox Screening & EOL Impacts  Measure and control to determine best safety practices and screening methods for nanomaterials as well as impact of possible releases  Perform assessment of developing processes / products and evaluate tradeoffs for EHS (environmental health and safety) with costs  Promote informed policymaking  Advocate productive public discourse with UML with Benneyan with Bosso NSF NIRT with Sandler NSF NIRT

Acknowledgements Funded by NSF Award Numbers SES and EEC