Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap iii

Table of Contents

Executive Summary ...... v

1—Overview of the Forest Products Industry ...... 1

2—Vision for Nanotechnology in the Forest Products Industry ...... 7

3—R&D Strategy ...... 11 R&D Focus Area 1 Polymer Composites and Nano-Reinforced Materials ...... 17 R&D Focus Area 2 Self-Assembly and Biomimetics ...... 23 R&D Focus Area 3 Cell Wall Nanotechnology ...... 27 R&D Focus Area 4 Nanotechnology in Sensors, Processing, and Process Control ...... 33 R&D Focus Area 5 Analytical Methods for Nanostructure Characterization ...... 37 R&D Focus Area 6 Collaboration in Advancing Programs and Conducting Research ...... 43

4—Implementation Plan: Next Steps and Recommendations ...... 45

Appendices ...... 49 A—Workshop Agenda...... 51 B—List of Participants ...... 55 C—Breakout Group Members ...... 63 D—Selected Workshop Presentation Summaries...... 67 E—Workshop Organizing Committee and Contacts for Further Information .... 75 F—Tools for the Characterization of Nanometer-Scale Materials ...... 77 G—Nanoscience User Facilities ...... 87 References ...... 89 iv Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap v

Executive Summary

Introduction A nanometer is a billionth of a meter, Nanotechnology is defined as the or 80,000 times thinner than a manipulation of materials measuring 100 human hair. nanometers or less in at least one dimension. Nanotechnology is expected to be a critical economical and sustainable production of driver of global economic growth and these new generations of forest-based development in this century. Already, this materials—materials that will meet societal broad multi-disciplinary field is providing needs while improving forest health and glimpses of exciting new capabilities, contributing to the further expansion of the enabling materials, devices, and systems that biomass-based economy. can be examined, engineered, and fabricated at the nanoscale. Using nanotechnology to Nanotechnology can be used to tap the controllably produce nanomaterials with enormous undeveloped potential that trees unique properties is expected to revolutionize possess—as photochemical “factories” that technology and industry. produce rich sources of renewable raw materials using sunlight, water, and carbon The forest products industry relies on a vast dioxide. The consumption of carbon dioxide renewable resource base to manufacture a in the production of these raw materials wide array of products that are indispensable provides a carbon sink for this important to our modern society. American paper and greenhouse gas. By harnessing this potential, wood products companies produce over 225 nanotechnology can provide benefits that million tons of products each year that touch extend well beyond fiber production and new every aspect of our lives, contribute over materials development and into the areas of $240 billion per year to the gross domestic sustainable energy production, storage, and product, and employ over 1.1 million utilization. For example, nanotechnology Americans. Emerging nanotechnologies offer may provide new approaches for obtaining the potential to develop entirely new and utilizing energy from sunlight—based on approaches for producing engineered wood- the operation of the plant cell. Novel new and fiber-based materials. They can also ways to produce energy, chemicals, and other enable the development of a wide range of innovative products and processes from this new or enhanced wood-based materials and renewable, domestic resource base will help products that offer cost-effective substitutes for address major issues facing our nation, non-renewable materials used in the including national energy security, global manufacture of metallic, plastic, or ceramic products. Nanotechnology could transform Nanotechnology could transform the the forest products industry in virtually all forest products industry in virtually all aspects—ranging from production of raw aspects—ranging from production of materials, to new applications for composite raw materials, to new applications for and paper products, to new generations of composite and paper products, to new functional nanoscale lignocellulosics. generations of functional nanoscale Research and development (R&D) in nanotechnology is critically important to the lignocellulosics. vi Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

climate change, air and water quality, and and particles to allow customized property global industrial competitiveness. enhancement in processing.

Many challenges stand in the way of Potential Uses for Nanotechnology exploiting the potential benefits of in Forest Products nanotechnology in the forest products industry and much research will be needed to move Potential uses for nanotechnology include forward in this arena. Researchers will need to developing intelligent wood- and paper- address technical challenges such as the lack based products with an array of nanosensors of fundamental understanding of built in to measure forces, loads, moisture lignocellulosic material formation at the levels, temperature, pressure, chemical nanoscale and the absence of adequate emissions, attack by wood decaying fungi, et technology for measuring and characterizing cetera. Building functionality onto these materials at the nanoscale. Participants lignocellulosic surfaces at the nanoscale in this effort will need to come from not only could open new opportunities for such things academia but from industry and government as pharmaceutical products, self-sterilizing as well; they will need to come together to surfaces, and electronic lignocellulosic form an infrastructure and move forward as a devices. Use of nanodimensional building cohesive unit working simultaneously towards blocks will enable the assembly of functional a single goal—the advancement of materials and substrates with substantially nanotechnology into the forest products higher strength properties, which will allow the industry. production of lighter-weight products from less material and with less energy Advancing the nanotechnology research requirements. Significant improvements in agenda efficiently and effectively will require surface properties and functionality will be gaining consensus on research needs and possible, making existing products much priorities among the forest products industry, more effective and enabling the development universities with forest products research and of many more new products. Nanotechnology education departments and programs, can be used to improve processing of wood- technology developers and suppliers, based materials into a myriad of paper and research institutes and laboratories serving wood products by improving water removal the forest products industry, and mission- and eliminating rewetting; reducing energy oriented federal agencies with supportive usage in drying; and tagging fibers, flakes, goals, such as the National Science Foundation, the U.S. Department of Potential Uses Agriculture (USDA), and the U.S. Department of Energy (DOE). In building consensus, the ! Intelligent products with nanosensors forest products sector can capitalize on the for measuring forces, loads, moisture good working relationships that the forest levels, temperature, et cetera. products industry has with its university research community, and with federal ! As building blocks of products with agencies such as the USDA Forest Service; the substantially enhanced properties. USDA Cooperative State Research, Education, and Extension Service (CSREES); the DOE ! As coatings for improving surface Industries of the Future Program; and the qualities to make existing products DOE Biomass Program. In addition, the forest more effective. products sector can take advantage of the linkages it has with research communities ! As basis for making lighter-weight across the globe. As the industry’s operation products from less material and with and markets become more and more global fewer energy requirements. in nature, international cooperation and collaboration is imperative. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap vii

Increased cooperation must also occur for nanotechnology applied to forest products between the forest products and manufacturing processes and forest-based nanotechnology research communities, the lignocellulosic materials. Workshop federal departments and agencies with participants identified the fundamental ongoing programs in nanotechnology R&D, research challenges in nanoscale and the National Nanotechnology Initiative lignocellulosic biopolymer structures, novel (NNI). Linkages between the forest products surface phenomena, biosynthesis, systems sector research communities and the NNI integration, education, and introduction of umbrella centers and user facilities (such as nanomaterials into the marketplace. An those sponsored by the National Science overview of the Forest Products Nanotechnology Foundation, DOE, and National Institutes of Roadmap is shown in Figure 1. Health) are critical to capturing synergies, enhancing accomplishments, and avoiding Workshop participants also identified some of needless duplication of facilities and other the unique properties and characteristics of resources. wood lignocellulosic biopolymers that make them an exciting avenue for research, including: Workshop

In a first step towards reaching the goals of 1) Lignocellulosic biopolymers are some of applying nanotechnology in the forest the most abundant biological raw products industry, a workshop to explore materials, have a nanofibrillar structure, opportunities and research needs was have the potential to be made convened on October 17-19, 2004, at the multifunctional, and can be controlled in National Conference Center in Lansdowne, self-assembly. Virginia. Over 110 leading researchers with diverse expertise from industry, government 2) Lignocelluloses as nanomaterials and laboratories, and academic institutions from their interaction with other nanomaterials North America and Europe were in are largely unexplored. attendance. Workshop objectives were as follows: 3) New analytical techniques adapted to biomaterials are allowing us to see new ! Develop a vision for nanotechnology in possibilities. the forest products industry It is hoped that this vision and roadmap will inspire researchers to pursue these ! Develop a roadmap for nanotechnology opportunities and encourage the formation of in the forest products industry (identify collaborative research programs. potential applications and uses, identify knowledge gaps and the research needed)

! Interest federal funding entities in Vision Statement nanotechnology as applied to forest products industry manufacturing processes To sustainably meet the needs of present and lignocellulosic materials and future generations for wood-based materials and products by applying ! Foster cooperation and collaboration nanotechnology science and among industry, academia, and engineering to efficiently and effectively government to fill knowledge gaps capture the entire range of values that This document represents a report of the wood-based lignocellulosic materials are workshop, and the first roadmap of capable of providing. technological needs and research priorities viii Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Figure 1. Overview of the Forest Products Nanotechnology Roadmap Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 1

1—Overview of the Forest Products Industry1

The U.S. forest products sector is often Industry Overview described as a mature industry, with moderate profit opportunities and stable ! A mature industry that plays a vital revenues. Research and investment have the role in U.S. economy. potential to reinvigorate this key American industry, which is largely based on renewable, ! Energy use remains disproportionately carbon-neutral raw materials, and expand its high—a very energy-intensive sector. global opportunities in the decades ahead. These research and development (R&D) efforts ! Pressures from global competitiveness must focus on the most exciting new industrial demand advances in process technology to come along in years—the use technologies. of nanomanufacturing techniques, which are expected to revolutionize traditional industrial ! Nanotechnology could revitalize the processes over the next decades. industry.

Strategic Drivers for The many thousands of products derived Nanotechnology in the Forest from our forests are ubiquitous and are taken Products Industry for granted in our everyday world—the hallmark of a great product and great Strengthening U.S. Industrial Competitiveness material. Nanotechnology now offers the and Sustainability opportunity to re-invent how we utilize wood and wood-based materials and the industry Nanotechnology represents a major that converts it to the myriad of products in opportunity to generate new products and use today. It can enable the development of industries in the coming decades. The ability a wide range of new or enhanced wood- to see materials down to atomic dimensions based materials and products that offer cost- and determine and alter how materials are effective substitutes for non-renewable constructed at nano- and atomic scales is materials used in the manufacture of metallic, providing the opportunity to develop new plastic, or ceramic products. materials and products in unprecedented ways. In the past, materials scientists By employing nanotechnology to revitalize concentrated efforts on simple, single-crystals the forest products industry, we can strengthen and homogeneous materials that were easier one of America’s core manufacturing to understand and could be analyzed by the competencies (Figure 2). The U.S. has a techniques of the time. We now have much massive infrastructure in place for growing, improved tools to investigate and understand harvesting and processing wood products, how wood, a composite cellular material, is which provides a key employment base in synthesized in a tree; how the molecular and almost every state. This infrastructure nanoscale components are assembled; and provides a fundamental strategic advantage how this architecture and assembly controls to build on for preserving the global material properties. economic competitiveness of this industry.

1 Matos and Wagner 1998; Wagner 2002; United Nations 2005; United Nations 1997; U.S. Department of Energy 2004; Paperloop 2004; McNutt and Cenatempo 2003; Ince et al. In press. 2 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

FIgure 2. Consumption of Materials in the U.S., 1960-1995

Source: Matos and Wagner 1998

Large forest resources combined with prudent forest management and a good system of roadways, canals, and railways has allowed the U.S. to develop and maintain the world’s largest forest products industry. As shown in Figure 3, even Canada—our largest competitor— produces only a fraction of the U.S. industrial roundwood harvest. Other major competitors, such as Brazil, Indonesia, Finland and Sweden, produce even smaller fractions. At the current rate of timber production (400 million cubic meters (m3) per year), the U.S. is still far short of depleting the almost 31 billion m3 of standing timber in America’s forests, which is being added to at the rate of over 850 million m3 per year. Not only could more wood be obtained from U.S. forestlands without detriment to the environment, but there would also be a variety of positive environmental benefits. More intense forestry practices such as the use of fast growing

FIgure 3. Industrial Roundwood Production, 1997

Source: United Nations 1997 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 3

tree species and plantations would be and protection. The United States is the expected to further increase forest productivity world’s leading producer of lumber and and increase our ability to sustainably wood products used in residential produce timber. construction and in commercial wood products such as furniture and containers. Improving Industrial Environmental The United States is also the leader in the Performance pulp and paper business, producing approximately 28 percent of the world’s

Trees utilize carbon dioxide (CO2) from the pulp and 25 percent of the world’s paper atmosphere, water and nutrients from the soil, and paperboard. Total U.S. shipments are and the energy of the sun (via photosynthesis) valued at $243 billion annually, of which to produce the nano-dimensional arrays that nearly two-thirds, or $156 billion, come comprise the three-dimensional cellular from the pulp and paper sector. composite materials known as wood. Increasing our use and dependence on wood Forest products manufacturing continues to and wood-based materials for new play a vital role in the U.S. economy. As a generations of nanomaterials and products major national employer, the industry can provide a number of environmental operates thousands of manufacturing benefits. For example, trees provide an facilities throughout the country, ranging efficient way to sequester CO2 and lock it up from large, state-of-the-art paper and in wood. Forests also provide an efficient and board mills to small, family-owned saw mill effective means of controlling water run-off operations. In this sector more than 1.1 from rainfall, which helps to recharge million workers are employed in good- aquifers, maintain flows of surface waters, paying jobs. Pulp, paper, composite, and and prevent erosion of valuable topsoil. saw mills are particularly vital to rural Other environmental benefits of properly areas, where they are often a region’s managed commercial forestlands include leading employer. In all, forest products forest fire hazard mitigation, improving forest account for 1.2 percent of the total U.S. health and condition, and slowing conversion Gross Domestic Product (GDP). of privately-held forest land to non-forest uses by providing increased economic returns for Yet it has become ever more difficult for the forestlands. In addition to the benefits industry to generate the capital it needs to provided by forests, new or enhanced wood- stay competitive in an increasingly global based materials offer a renewable alternative marketplace. Along with increased global in a world that will see exponential growth in competition, the cost of energy, raw demand for consumer goods and products in materials, and labor has escalated in the developing countries. Nanotechnology can United States, placing severe competitive also be used to make manufacturing pressures on U.S. producers. As a U.S. processes more efficient and effective, Department of Energy (DOE) report notes, enabling products to be made with “Energy-intensive industries face enormous substantially less raw material and energy competitive pressures that make it difficult inputs, and increasing the ability of these to make the necessary R&D investments in products to be recovered and recycled. technology to ensure future efficiency gains.”

The Industry Today Additionally, while the United States still The U.S. forest products industry produces maintains a relatively low-cost position in thousands of products that are essential for the cost of wood, relative to many of its everyday needs in communication, education, competitors, equatorial nations such as packaging, construction, shelter, sanitation, Brazil and Indonesia have developed fast- growing wood species such as eucalyptus 4 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Figure 4. Changes in Pulp Production Figure 5. Bleached Hardwood Kraft 1990-2000 Market Pulp Manufacturing Cost Curve

Source: Paperloop 2004

Source: Ince, P. et al. In press and acacia that have put U.S. wood limit the industry’s ability to take risks and to producers at a competitive disadvantage. invest in new technology research and Moreover, the United States has one of the development. The industry’s response has highest labor costs in the world. Without been to pursue pre-competitive, collaborative significant gains in productivity, U.S. industry R&D in partnership with government agencies will continue to lose out to offshore such as the DOE, and with public and private production of traditional pulp and paper research universities. The results have been products. Figures 4 and 5 illustrate global extremely fruitful. shifts in pulp production from 1990 to 2000 and the 2003 global cost-capacity curve for hardwood market pulp producers. Figure 6. Loss of U.S. Markets to Imports Forest products have traditionally been a strong export market for U.S. manufacturers, but global competition from lower-cost producers is increasing. By 2001, the U.S. paper industry exported $18 billion; however, imports totaled $33 billion. For wood products, exports were valued at $3 billion and imports at $10.6 billion. As shown in Figure 6, U.S. wood and paper products producers have lost a significant percentage of the U. S. market to imports. Clearly, R&D to create newer, higher-value products for global markets is imperative for U.S. manufacturers.

Recent trends on Wall Street have offered other challenges to reinvestment and growth. Domestically produced shares of U.S. consumption in The industry’s high capital intensity and the four leading forest product sectors from 1990 to 2002 short-term focus on quarterly results tend to Source: Ince, P. et al. In press Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 5

Energy Efficiency Pays Off The significance of energy use to the forest products industry, and to the pulp and paper sector in particular, can hardly be overstated. Fully a third of all energy used in the United States is consumed in industrial processes, and forest products ranks among the top eight energy-intensive industries, along with chemical, mining, steel, and petroleum refining. At least 18 percent of U.S. industrial energy use can be attributed to forest products manufacturing—and of the 3.2 quads used by the industry in 1998, 2.7 quads were consumed in pulp and paper processes. and the replacement of fossil fuel (down 17 percent) with biomass (up 19 percent) have New technologies that reduce energy aided this effort. Contributing to this effort are consumption will improve the industry’s the partnerships with the DOE and leading economic competitiveness and also reduce academic research institutions, as well as the the nation’s overall energy consumption. ever-growing portfolio of energy-saving and Already, the industry has made great strides, cost-cutting techniques and the more than decreasing primary energy intensity by 27 100 collaborative research projects that have percent since 1972 while at the same time been funded since 1994 as part of the Forest dramatically expanding output. Process Products Industry of the Future Program. This efficiency advances such as cogeneration (the successful partnership can provide both a industry generates more than half of its model and a springboard for a new area of energy and two-thirds the electricity it uses on- emphasis on nanotechnology. site through steam and cogeneration systems) 6 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 7

2—Vision for Nanotechnology in the Forest Products Industry

Vision Statement

To sustainably meet the needs of present and future generations for wood-based materials and products by applying nanotechnology science and engineering to efficiently and effectively capture the entire range of values that wood-based lignocellulosic materials are capable of providing.

Nature has utilized nanostructures since the nano-scale structures. The distinctive feature earth began to cool 4.5 billion years ago of nanoscience is the increased understanding and has blessed us with a rich legacy of and technical control of nanoscale structure examples to stimulate our imaginations. and functionality. This is not about new These range from the microstructures of materials but about new processes, new minerals to the intricate molecular forms, and new functionalities for old mechanisms of life. While it is now possible materials. for us to manufacture structures that do not occur in nature, we are strongly guided by the Modern analytical and microscopy tools are immense variety of those that do. Some of the allowing us to see, in more detail, the nature most important applications of of wood fibers down to nano- and atomic biotechnology are likely to be the tuning up scales. We can now appreciate the fact that of useful cellular machinery that nature has they are made of nanodimensional not yet had time to evolve to its most efficient components that produce the unique form. We have been doing something similar properties of wood. Indeed, paper, for a century and a half with organic paperboard, and other wood-based molecules – dyes, for example, or synthetic materials are typically made from a range of fibers – and Japanese metallurgists were components that inevitably have some inventing new microstructures much earlier degree of nanodimensional scale, put than that to create edged tools and weapons together empirically to make valuable of legendary quality. They were not aware of performing substrates. the nanoscale origins of their products, but they were producing them just the same. The distinctive feature of nanoscience is Today the increased understanding and Some of the most important developments in technical control of nanoscale structure nanotechnology are occurring at the interface and functionality. This is not about new between biological and inorganic systems. materials but about new processes, new The current emphasis of the new branch of forms, and new functionalities for old chemistry know as “nanotechnology” is the materials. development of macro-scale materials with 8 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Already, nanotechnology is being Nanotechnology In Forest Products incorporated into a variety of products. Computer and cell phone chips have ! Traditional manufacturing works from nanoscale circuits; cotton khakis contain the top down—nanotechnology works nanosized particles that repel stains and from the bottom up, manuipulating water; automobile manufacturers have molecules to achieve precise and novel employed a nano-finish so its cars never need effects. waxing. Nano particles or fibrils are found in stronger automobile bumpers, more effective ! Nanotechnology is the most promising sunscreens, bouncier tennis balls, and more breakthrough towards production powerful golf clubs. The National Science growth since the Internet—some say a Foundation (NSF) predicts that within a second industrial revolutionrevolution. decade nanotechnology will provide a $1 trillion market, and provide two million new ! Last year alone, 7,000 research papers jobs. Federal research funding will average were published on nanotechnology. $1 billion a year over the next four years— one of the largest infusions for industrial R&D ! To reach its goals, the forest products since the early days of the space program. industry must align with the greater nanotechnology research community. Tomorrow

In just a few years, nanotechnology has The vision for the forest products industries is moved from science fiction into the forefront to better utilize all the components that are of research and new product applications. available in wood and wood-based Already, it is considered the most promising materials. New methods for liberating these breakthrough toward productivity growth materials, including nanodimensional since the Internet became part of the cellulose fibrils, macromolecules, and workplace. Last year alone, more than 7,000 nanominerals, will be needed in order to use research papers devoted to nanotechnology the techniques developed for other were published, and the pace of development nanomaterials as platforms for creating new is quickening as well. wood-based materials and products. Nanotechnology holds the promise of While predictions vary, it is clear that changing virtually all of the processes by applications for nanotechnology are closer to which wood and paper products are now reality than the public realizes, and may even made, transforming the sector from a qualify as a second industrial revolution. resource-based to a knowledge-based Because self assembled nano-structures industry with much greater prospects for long- require researchers to work at the atomic or term stability. molecular scale, it changes the very definitions of raw materials and manufacturing processes. Manufacturing The National Science Foundation (NSF) traditionally builds things from the top down, predicts that within a decade hewing lumber from trees, extracting stone nanotechnology will provide a from quarries, assembling computer chips $1 trillion market, and provide two from silicon. Nanotechnology works from the million new jobs. Federal research bottom up, manipulating molecules and funding will average $1 billion a year atoms to achieve precise and novel effects, over the next four years—one of the improving and altering existing materials. largest infusions for industrial R&D since the early days of the space program. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 9

the bulk properties of wood will allow Nanotechnology holds the promise of reconstructing traditional wood and changing virtually all of the processes by wood-based materials into new shapes which wood and paper products are now and applications. made, transforming the sector from a ! resource-based to a knowledge-based For paper, paperboard, and composites new polymerization techniques can allow industry with much greater prospects for for the synthesis of reinforced fibers long-term stability. compatible with either water or organic liquids. Incorporating biochemical and Research biomimetic techniques can make these products more recyclable while also Research is already showing the way to improving performance. increase performance and add value in a host of traditional forest products sector ! Among the many possibilities suggested products. Initiatives to provide greater to date for new woodfiber-based products strength, water resistance, fire-retardancy, and incorporating nanomaterials are new forms of packaging are showing great moisture-resistant cell-phone components, promise, as described in the subset of advanced membranes and filters, emerging opportunities presented below. improved loudspeaker cones, and additives for paints, coatings, and adhesives. ! New methods to produce biodegradable polymers and perform surface/interface It should be noted that many of these new modification of wood and pulp fibers techniques may draw substantially on the could lead to biomaterials with attractive wealth of the advanced chemistry already in structural and functional properties (e.g., use in the industry. As one report concludes, clay nanocomposites). “It should be remembered that substantial parts of the cell wall structure engineered ! New types of adhesives and surface during traditional pulping, bleaching and coatings could provide enhanced fiber processing are in the nanometer range.” durability, resistance to moisture and decay, and fire retardancy. Indeed, nanocomposite fire retardant treatments are already available and may be adaptable to wood products.

! Nanosized particles could replace current chemical treatments for preserving wood products with direct impregnation of titanium dioxide, zinc oxide, and other particles shown to improve wood longevity. This will be especially useful given that many countries are already banning current forms of preservative- treated wood.

! Nanocellulose fibrils are the principal structural elements of wood. Understanding how they are organized with other cell wall materials to provide 10 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Partnerships Moving ahead in the area of Moving ahead in the area of nanotechnology, nanotechnology, the forest products the forest products industry must seize the industry must seize the opportunity to opportunity to link with larger link with the larger nanotechnology nanotechnology research and industrial research and industrial communities communities such as the ongoing efforts of such as the National Nanotechnology the National Nanotechnology Initiative (NNI). Initiative (NNI). The NNI is a visionary R&D program that coordinates the activities of 22 federal agencies and a host of collaborators from ! Develop educational resources, a skilled academia, industry, and other organizations. workforce, and the supporting The total federal funding investment for the infrastructure and tools to advance NNI is $988 million in fiscal year 2005 and a nanotechnology request of $1,052 million in fiscal year 2006. The goals of the NNI include: ! Support responsible development of nanotechnology2 ! Maintain a world class research and By linking with communities such as the NNI, development program aimed at realizing the forest products industry will be able to the full potential of nanotechnology expand its knowledge of nanotechnology, pool its resources with those of others ! Facilitate transfer of new technologies into pursuing common R&D goals, and advance products for economic growth, jobs, and its own agenda towards its short-, mid-, and other public benefit long-term goals for nanotechnology in the industry.

2 National Science and Technology Council, Committee on Technology, Subcommittee on Nanoscale Science, Engineering and Technology, National Nanotechnology Initiative Strategic Plan, December 2004. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 11

3—R&D Strategy

Research in nanotechnology for the forest industries. This direction potentially will products industry will be focused on the lead to radically different products, fundamental composite material in wood: processing techniques, and material lignocellulose. Lignocellulose is an abundant applications. material that is nanodimensional at the basic level—these dimensions hold the keys to the R&D Strategy ability to develop materials from the bottom up. In addition, many existing products, such ! as paper and paperboard, have empirically NEEDED: Fundamental and cross- evolved from the use of micro-scale cutting research for basic understanding materials, such as microfibers and clay fillers of material properties at the nanoscale. that have turned out to incorporate ! NEEDED: New concepts and design nanodimensional fibrils and particles. Substantial improvements in performance methodologies for nanoscale tools and and economy can be achieved by successfully devices. using these nano-dimensional components ! Nanotechnology by Design will yield more intelligently. new tools for precisely building material function around end-use application. Two Approaches ! Networking with other interested parties The R&D strategy for the forest products is vital. industry encompasses two approaches: TWO APPROACHES— 1) Nanotechnologies developed in the broad NNI effort will be adopted and (1) Incorporate knowledge and deployed into materials, processes and technologies developed through the products used in or produced by the NNI effort into forest products industry current forest products industry. The materials and processes. expected gains of this research direction (2) Focus on completely new platforms for will be in improving processing radically different products, processing efficiencies, improving end-use techniques, and applications. performance of existing products, and some degree of new product development using much of the existing capital infrastructure—with some minor-to- Key Research Challenges moderate modifications and additions. Major scientific and engineering breakthroughs will be required to take 2) Develop completely new materials or advantage of the opportunities that product platforms using the improved nanoscience offers the forest products knowledge of nanoscale structures and industry. The Nanotechnology for the Forest properties of the materials used in the Products Industry Workshop participants forest products industry and other identified fundamental research challenges in 12 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

nanoscale lignocellulosic biopolymer ! Fundamental Understanding and structures, novel surface phenomena, Analytical Tools biosynthesis, systems integration, education, and introduction of nanomaterials into the ! Nanomaterials by Design marketplace. The following discussion ! provides a synthesis and summary of the New Nanoscale Building Tools research challenges and opportunities that ! were identified at the workshop in the various Nanotechnology for Manufacturing concurrent breakout sessions. A summary of the major research opportunities identified by workshop The research challenges span a range of participants is shown in the box below. scientific focus areas including:

Summary of Major Research Opportunities

" Directed design of biopolymer nanocomposites (e.g., combining lignocellulosic materials with other nanomaterials).

" Use of self-assembly of nanodimensional building blocks to produce functional structures and coatings (can also take advantage of installed industry infrastructure for rapid technology transfer and adoption).

" Nanoscale architecture from renewable resource biopolymers (e.g., creating novel biopolymers; active functional surfaces; and synergistic coupling of biopolymers with inorganic nanomaterials).

" Biofarming lignocellulosic nanomaterials with unique multifunctional properties by understanding and exploiting the architecture and ultrastructure of plant cell walls.

" Liberating nanodimensional cellulose fibrils with a view to exploring the anticipated beneficial properties, for example, cellulose nanofibrils appear to offer very high strength, up to one-quarter the strength of carbon nanotubes.

" Develop biomimetic processes for synthesizing an array of nanodimensional lignocellulosic materials.

" Using nanomaterials, nanosensors, and other applications of nanotechnology science and engineering to dramatically improve the efficiency of forest products raw material conversion processes by reducing energy consumption in processing by 50 percent, using up to 60 percent less raw materials per unit of product output, and reducing product degrade/off-specification.

" Developing, enhancing, and adapting physical, chemical, optical, and electrical property instrumentation and analytical methodologies used in nanotechnology and nanoscience to lignocellulosic biopolymers’ unique nanofibrillar and cellular morphology. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 13

Fundamental Understanding and Analytical Cross-cutting fundamental research that Tools combines biology, physics, chemistry, As an R&D effort organized around the unique materials science, computer science, and properties of lignocellulose and its processing engineering will be vital. into consumer products, research is needed to develop fundamental understanding of nano- manufacture nanostructured products, biostructures and processes, including novel biomaterials, improved nanobiotechnology, and techniques for a delivery of bioactive molecules, broad range of applications in biomaterials, nanoscale sensory systems, biochips, and biosystem-based electronics, agriculture, the modification of existing biomolecular energy, and health. Lignocellulosics are challenging materials insofar as they have an machines for new functions. architecture comprised of mixtures crystalline ! Genomic modifications of trees or other polymeric materials, oriented molecules, and lignocellulosic feedstock that modify the randomly designed components. Analytical characteristics of the components in wood techniques being developed in the studies of to better suit the requirements for “soft matter” and nanotechnology will be of processing or end-use products. great value. But it must be recognized that new approaches will be needed to help ! Development of more efficient ways to elucidate the fundamental structures involved. liberate and stabilize nanodimensional In this respect it will be necessary to reach out cellulose fibrils so that they can be used to disciplines previously not strongly linked most effectively. with forest products. Increasingly, biologists, physicists, chemists, materials scientists, and Nanomaterials by Design engineers will need to work together to provide the range of techniques and skills “Nanomaterials by Design” is a uniquely needed. A major resource to be included will solutions-based research goal. As described be national laboratories, where a number of in the nanomaterials roadmap developed by x-ray, neutron, and advanced-light sources the chemicals industry, “nanomaterials by will enable a more detailed analysis of design refers to the ability to employ scientific lignocellulosics. Some fundamental areas of principles in deliberately creating structures research will include: (e.g., size, architecture,) that deliver unique functionality and utility for target applications.”3 This research area will focus ! Progress in the study of biological and on the assembly of building blocks to biologically inspired systems in which produce nanomaterials in technically useful nanostructures play an important role. forms, such as bulk nanostructured materials, This includes developing an dispersions, composites, and spatially understanding of the relationships among resolved, ordered nanostructures. It will yield chemical composition, single molecule a new set of tools that can provide nearly behavior, and physical shape at the limitless flexibility for precisely building nanoscale and in terms of biological function and material properties. Nanomaterials by Design Creating “Nanomaterials by Design” is a ! The study of cell biology and nanostructured tissues, as well as synthesis uniquely solutions-based goal. It will of nanoscale materials based on the yield a new set of tools that can provide principles of biologically guided self- nearly limitless flexibility for precisely assembly. Biosynthesis and bioprocessing building material function around an end offer fundamentally new ways to use application.

3 U. S. Department of Energy and Chemical Industry Vision2020 Technology Partnership, Chemical Industry R&D Roadmap for Nanomaterials by Design: From Fundamentals to Function, December 2003. 14 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

material function around an end-use Fostering Networks and application. Such a powerful, function-based Fostering Networks and design capability holds the potential to solve Collaboration critical, unmet needs throughout society. To make the vision a reality, it will be Techniques being developed in the areas of necessary to facilitate intensive coordination self-assembly and directed self-assembly will and integration among interdependent and allow us to use the building blocks available multidisciplinary research areas. A Steering in the forest products industry to manufacture Group could be used to foster this materials with radically different performance coordination and guide research along the properties. lines identified by this and future roadmaps. More importantly, it will be vital to network New Nanoscale Building Tools with centers already funded as part of the NNI (Figure 7) so that full advantage can be taken Novel concepts and design methodologies of the investments in facilities and programs are needed to create new nanoscale devices already under way. Examples include the and integrate them into architectures for nanofabrication facility at Pennsylvania State various operational environments. These University, where researchers are investigating require a profound understanding of the the production of cellulose nanofibrils, the physical, chemical, and biological self-assembly group at Harvard, where basic interactions among nanoscale components. principles are being developed, and the Research in this area includes development of nanocomposites groups at Rensselaer new tools for sensing, assembling, processing, Polytechnic Institute and Wright Patterson Air manipulating, and manufacturing. It will also Force Base. In each case, there are existing require integration along scales, controlling bodies of knowledge that can be leveraged and testing of nanostructures and devices, by the forest products industry. Networks will design and architecture of concepts, software include the R&D User Centers established by specialized for nanosystems, and design the U. S. Department of Energy, the National automation tools for assembling systems Science Foundation (NSF) and the National containing large numbers of heterogeneous Institute of Standards and Technology. These nanocomponents. facilities, such as those provided by the NSF’s National Nanofabrication Infrastructure Novel concepts and design Network (NNIN) (Figure 8), make staff, methodologies are needed to create new facilities, and equipment necessary for nanoscale devices. nanoscale research accessible to researchers at businesses and academic institutions around the country. Manufacturing at the Nanoscale Networking with existing NNI centers Research in this area will focus on creating is vital. nanostructures and assembling them into nanosystems and then into larger-scale structures. This research should address understanding nanoscale processes, developing novel tools for measurement and manufacturing at the nanoscale, developing novel concepts for high-rate liberation and stabilization of nanoscale building blocks, and understanding the processing of nanostructures and nanosystems, as well as the scale up of nanoscale processing methods. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 15

Figure 7. NNI Centers and User Facilities

Source: National Science and Technology Council 2004

Figure 8. National Nanotechnology Infrastructure Network

The National Nanotechnology Infrastructure Network (NNIN) provides provides open on-site and remote access to teaching tools and instrumentation as well as capabilities for fabrication, synthesis, charaterization, design, simulation, and integration to users in academia, small and large industry, and government. The NNIN also has extensive education, training, and outreach capabilities. 16 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

4) Nanotechnology in Sensors, R&D Focus Areas Nanotechnology in Sensors, Processing, and Process ControlControl— The Steering Committee for the Using non-obtrusive, nanoscale sensors Nanotechnology for the Forest Products for monitoring and control during wood Industry Workshop considered a number of and wood-based materials processing, to different options for organizing the technical provide data on product performance focus areas for the breakout discussion and environmental conditions during end sessions. The following five R&D focus areas use service, and to impart multifunctional were selected on the basis that they 1) provide capabilities to products. the best path forward for a nanotechnology roadmap by helping to identify the underlying 5) Analytical Methods for science and technology needed, and 2) foster Nanostructure CharacterizationCharacterization— essential interactions among visionary, Adapting existing analytical tools or interdisciplinary research and technology creating new tools (chemical, mechanical, leaders from industry, academia, research electrical, optical, magnetic) that institutions, and government. accurately and reproducibly measure and characterize the complex nanoscale architecture and composition of wood 1) Polymer Composites and Nano- and wood-based lignocellulosic reinforced Materials—Combining materials. wood-based materials with nanoscale materials to develop new or improved A sixth focus area is also included here as a composite materials with unique part of the R&D Strategy: Collaboration in multifunctional properties. Advancing Programs and Conducting ResearchResearch. This section emphasizes the 2) Self-Assembly and BiomimeticsBiomimetics— importance of collaboration and cooperation Using the natural systems of woody plants among researchers from various disciplines as either the source of inspiration or and organizations, including universities, template for developing or manipulating research institutes, National Laboratories, unique nano-, micro-, and macro-scale and government agencies and departments. polymer composites via biomimicry and/ or direct assembly of molecules. The following sections describe the R&D focus areas, including the key technical challenges 3) Cell Wall NanostructureNanostructure— and research priorities. Manipulating the cell wall nanostructure of woody plants in order to modify or enhance their physical properties and create wood and wood fibers with superior manufacturability or end-use performance. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 17

Description Figure 10. Diagram of a Wood Fiber Wood can be viewed as a polymeric composite of cellulose, hemicelluloses, protein, and lignin, as well as a composite of Arrows indicate the orientation nanofibrils, microfibers, tracheids, vessel of cellulose microfibrils in the elements, and parenchyma cells (See Figures different layers of the 8-11). In addition, wood and wood-based secondary wall. materials, such as glued laminated beams, oriented strandboard, plywood, medium density fiberboard, hardboard, paper, and paperboard, are increasingly being Adapted from Smook 1992 manufactured as composites of non-wood and wood-based materials. Non-wood Figure 11. Assemblies of Tracheids, Ray materials, used as films, fillers, and matrices, include a wide array of materials such as Cells, and Parenchyma Cells in Wood clays, calcium carbonate, waxes, high-density polyethylene, titanium dioxide, adhesives, resins, Portland cement, polypropylene, polyethylene terephtalate, et cetera.

Figure 8. The Chemical Structure of Cellulose Images courtesy of W.C. Brow Center, State University of New York

The availability of new nanomaterials offers the forest products industry the opportunity to improve its existing composite products and create new high-value and high-performance Source: Fibersource composite products. High-performance, (www.fibersource.com/f-tutor/cellulose.htm) nano-based chemistry and additives for coatings, for example, are producing surface Figure 9. Cellulose Nanofibrils Within a enhancements and providing more flexible Plant Cell Wall and effective use of valuable raw materials. The development and use of nanomaterials and nanotechnology offers forest products producers opportunities for reduced material and energy inputs; added functionality to wood, wood-based composites, and pulp, Image courtesy of Candace Haigler and Mark paper, and paperboard products; and Grimson, North Carolina State University, improved process efficiency—all of which will Raleigh, NC help secure the sustainability and viability of the forest products industry. 18 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

! Research Goal and Objectives Understand the inter-relationships between lignocellulosic nanoscale The overall goal of this focus area is to material characteristics and resulting utilize—via adapting, developing, measuring, product end-use property improvement and implementing—a wide array of nanomaterials and nanotechnologies that will ! Utilize, develop, and investigate use of 1) improve the end-use performance of nanoscale materials and nanotechnology current wood, wood-based composites, pulp, to improve conversion efficiencies of paper, and paperboard products; 2) allow wood and wood-based materials to final development of new generations of high- products such as by reducing raw material value, high-performance products from forest- needs and process energy consumption based materials; and 3) reduce the overall costs to manufacture wood, wood-based Outcomes & Impacts composites, pulp, paper, and paperboard Outcomes & Impacts products. The following examples, while by no means all-inclusive, illustrate some of the potential The goal is to develop the capability to applications of successful R&D in this area. use a wide array of nanomaterials that improve end-use performance of current 1) Value-added, durable products and wood-based products, allow products with improved properties that development of new generations of would benefit the consumer (for example, high-performance products, and reduce the addition of nanoscale fillers to manufacturing costs. polymeric materials yields dramatic strength increases even at low addition levels [<5 percent]. If strength properties Individual objectives include: of wood, wood composites, paper, and paperboard could be dramatically ! Utilize, develop, and investigate novel improved, the material content of wood-based and non-wood-based products could be decreased by up to 60 nanoscale materials with enhanced percent without losing end-use properties (e.g. films, coatings, fillers, performance). matrices, pigments, additives, and fibers) 2) Improved water removal processes and ! Determine the physical, chemical, other processing efficiencies in paper mechanical, optical, magnetic, and products nanotechnology that would electronic properties of nanoscale lower energy costs by 50% (and, thus lignocellulosic structures and enhance environmental sustainability). lignocellulosic nanofibrils in wood Water removal (typically accomplished via thermal drying process) usually ! Liberate nanodimensional cellulose fibrils constitutes the biggest portion of the from the lignocellulosic matrix existing in energy costs required to produce wood, wood wood-based composites, pulp, paper, and paperboard products. Modification of ! Investigate the ability of wood nanofibrils water absorption leading to faster to be converted into carbon nanotubes, draining fibers and 100 percent solid nanotubules, and nanowires coatings would minimize the energy Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 19

required and maximize the productivity of R&D Priorities paper and wood products converting and finishing processes. Novel Materials Develop and investigate novel materials with Key Research Challenges enhanced properties (e.g., films, coatings, The primary barriers to achieving the goals of fillers, matrices, pigments, additives, and the Polymer Composites and Nano- fibers—especially lignocellulosic nanofibrils). Reinforced Materials focus area can be grouped into three categories: technical, This research would be both fundamental and organizational, and behavioral. developmental in nature. Cross-disciplinary teams of material scientists, biological 1) Technical—The number of nanoscale scientists, polymer chemists, paper scientists, materials currently available in the forest products technologists, and chemical and mechanical engineers would need to marketplace capable of providing the share their expertise and expand the desired properties or benefits to the forest knowledge base of the development group. products industry is limited. Also, there is A range of advanced tools including particle generally a lack of experience within the characterization, electrokinetic properties, forest products industry with the high-power microscopes, surface methodologies needed to characterize spectroscopy, pressure reactors, small-angle and develop nanomaterials with X-ray scattering, and high-consistency mixers beneficial properties. would be needed to perform this research. It is estimated that it would take 3 to 10 years to 2) Organizational—Cross-disciplinary teams develop and characterize beneficial of scientists and technologists are needed, materials. The work would best be along with research funding and facilities, accomplished at or among institutions to accomplish the goals. capable of forming cross-disciplinary teams 3) Behavioral—Many forest products and in possession of the majority of the companies are unwilling to participate in needed equipment. Cross-disciplinary teams anything but pre-competitive research would need to work with industrial partners directives; therefore, research projects and a variety of national research laboratories to further expand their must be selected carefully. Also, because capabilities. of the nature of the industry (high-volume production, low-profit-per-ton, and capital-intensive, large-scale equipment and facilities), sufficient economic and technical feasibility studies will have to be performed before any new technologies are implemented.

Cross-disciplinary teams of researchers are required to carry out needed research most efficiently and effectively. 20 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Novel Materials for Processing Equipment create a database of nanoscale material properties and elucidate the relationships Develop and investigate novel materials for between constituent nanoscale material processing equipment. properties and product end-use properties, one can employ scientific principles and This research would be of both a fundamental computational modeling in deliberately and developmental nature. It would require creating new and improved products that materials scientists, polymer chemists, paper deliver unique functionality and utility for scientists, forest products technologists, and targeted end-use applications without the chemical and mechanical engineers to form need to go through iterative trial and error cross-disciplinary teams that would work with product development experimentation. equipment and other suppliers on novel materials for processing equipment. For This nanomaterials database, constituent example, pilot-paper machine and coating material interaction, and end-product equipment could be adapted to implement performance modeling research would be the new processes equipment that would be carried out by researchers with backgrounds needed for performing the studies. This and skills in forest products technology, would be shorter-term research focused on pulping and papermaking science and studying the operational and economic engineering, chemical and mechanical benefits of advanced nanomaterials on wood engineering, materials science, mathematical processing, panel products composites modeling, computational modeling, and manufacturing, and paper-making and metrology. The work would require the use of coating equipment. a laboratory equipped with up-to-date physical-property, surface-testing, and other Inter-Relationships Between Nanoscale metrology equipment. Small-scale pilot-plant Material Characteristics and End-Product and wet laboratories would be needed to Properties create composite end products for testing and evaluation. For example, coating labs and Develop and understand the inter- printing facilities would be needed to relationships between nanoscale material generate samples for testing coating and characteristics and the resulting product end- performing paper-print testing and analysis. use property improvements. Implementing New Materials This research focuses on determining the inter- relationships between nanoscale material Determine the best way to implement new characteristics and resulting product end-use materials. property improvements. As nanoscale materials become increasingly used in forest This research would be more developmental products to attain new and improved end use and applied in nature. It would require the performance, inclusion of these materials formation of cross-disciplinary teams of needs to move away from iterative trial and material scientists, forest products error product development approaches where technologists, paper scientists, and chemical such nanoscale materials are included in test and mechanical engineers. The research sample products followed by assessing teams could work with cooperators at resulting product properties. If one can universities, federal laboratories, or commercial pilot-plant facilities equipped Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 21

with appropriate pilot equipment (e.g., paper needed. Such research will help identify the machines, coaters, formers, presses, and most critical areas in which to focus research auxiliary equipment) to determine the best to reduce costs, attain needed end-use way to implement the nanomaterials being performance characteristics, and overcome developed by other cross-disciplinary teams. any negative environmental impacts in If equipment modifications are not needed, production and use. Life-cycle assessments the research could be accomplished in a are increasingly being used to assess and shorter period of time. However, if significant quantify the environmental impacts of modifications to existing equipment need to materials and products and, hence, contribute be made, projects may extend into a longer to achieving social acceptability. Because lifetime. success is expected with respect to use of nanotechnology and nanoscale materials Economic and Life-Cycle Models within the forest products industry, it is necessary that research on life-cycle Develop economic and life-cycle models for assessment and determining and overcoming forest-based nanoscale materials and any unacceptable environmental impacts products. needs to be carried out. Interdisciplinary teams comprised of forest products To be successfully used in consumer products technologists, pulp and paper scientists and and end uses, wood-based products and engineers, business majors (including Masters materials, including nanoscale materials, of Business Administration), economists, must be technically and economically viable chemical engineers, mechanical engineers, as well as socially and environmentally and environmental engineers would best acceptable. The vast majority of work perform this research. The interdisciplinary identified in this forest products industry teams should work with such groups as the roadmap is justifiably focused on technical National Council for Air and Stream issues and overcoming technical barriers. Improvement (NCASI) and The American However, research to assess and model Forest and Paper Association (AF&PA) to impacts and the economic viability of using develop economic and life-cycle models for nanoscale materials in forest products is also nanomaterial-containing products. 22 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 23

Description Research Goal and Objectives Much can be learned by studying the The overall goal of this focus area is to naturally occurring nanostructures found in develop a technical platform that enables forest biomass. Learning how they self- self-assembly of lignocellulosic materials assemble and developing methods that use either singly or in combination with other this self-assembly will be critical to materials at a nanoscale. Individual manufacturing new products from this objectives will include the following: renewable resource. Through biomimicry, we will also be able to take advantage of the ! Create novel, functional, self-assembling efficiencies of these natural structures. surfaces on existing lignocellulosic substrates Learning how woody plants self- ! assemble and developing methods that Develop a fundamental understanding of use self-assembly is critical to developing molecular recognition in plant growth and cell-wall self-assembly in forest products novel nanoscale lignocellulosic-based processes to create new or to enhance biomaterials. existing products

The major constituents of woody materials ! Characterize self-assembled natural and are cellulose, lignin, and the hemicelluloses. synthetic materials Of these, cellulose is by far the most ! predominant and is, in fact, the world’s most Integrate micro- and nanoscale abundant polymer. Cellulose is a renewable organization in new products and resource, and has many unique properties processes that result from its organization at a supermolecular level. Under the guidance of Outcomes and Impacts the cell, the cellulose chains self-assemble The following examples, while not all- into partly crystalline nanofibrils within the inclusive, illustrate some of the potential plant cell wall. Deviations from perfect applications of successful R&D in this area. crystallinity exist and, rather than being truly amorphous, probably reflect the complex nanoscale structure of the biopolymer that is, 1) Barrier coatings and films/laminates for as yet, not completely understood. These use in packaging to protect components, nanofibrils impart specific properties to the indicate the condition of the contents, or composite structure based on the way they provide a security function. are formed and are oriented within the fiber cell wall. By understanding and influencing 2) Extremely light-weight, paper-like how these structures form, and by developing structures that not only significantly reduce practical manufacturing processes to the weight of existing paper products, but manipulate their formation, it may be enable entirely new uses for fibrous webs possible to develop entirely new products that (e.g., matrices for other polymers or take advantage of the material characteristics ceramic materials). manifested at this scale. These material characteristics include unique optical, strength, electrical, and sorptive properties. 24 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

3) An understanding of how molecules in methods currently available. Some may woody biomass self-assemble leading to exist in other industries but are not used in the use of the constituents as a chemical forest products. feedstock (as an alternative to non- renewable chemical raw materials such as 4) Nanoscience—Little knowledge exists petroleum). regarding the self-assembly and incorporation of useful molecules into 4) By modeling the “nanofactories” found in nanomaterials derived from the forest the leaves and other living parts of the resource base. woody plant, we may be able to mimic processes such as photosynthesis and R&D Priorities transpiration. This may enable A fundamental approach will accelerate the development of more efficient methods development of forest-based nanomaterials for manufacturing foodstuffs and fuels and new products incorporating from forest resources, as well as the nanomaterials. To do this, an in-depth production of simple and/or composite understanding of the principles of self- structures for the controlled passage and assembly in these materials must be separation of various materials. developed. To develop a mechanistic understanding of self-assembly, extensive Key Research Challenges knowledge bases in many scientific The primary barriers to achieving the goals of disciplines, new measuring techniques, the Self-Assembly and Biomimetics focus area modeling and the correlation of nano, micro-, can be grouped into four categories— and macro-scale properties must be manufacturing, materials, analysis, and developed. Key R&D priorities as described nanoscience. below.

Manufacturing 1) Manufacturing—Manufacturing in the forest products industry is characterized by Optimize development and product life cycles large, high-throughput processes that are in manufacturing. very capital-intensive. A major barrier is the difficulty of large-scale and high- This will require methods that make maximum speed production of nanomaterials. use of current manufacturing systems and meet the production-rate requirements of the 2) Materials—Biomass as a starting material industries. To do this, the thermodynamics tends to be very non-homogeneous, which and kinetics of self-assembly must be may prove to be a significant barrier to quantified and modified and the macro- and complete resolution followed by self- nanoscales during processing will need to be assembly of specific components of this reconciled. resource. Materials 3) Analysis—The forest products industry’s ability to predict bulk material properties Develop methods to neutralize the impact of from single and assemblies of the heterogeneous nature of the starting nanostructures is limited by the analytical material. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 25

This may include methods that are insensitive Linkages and Implementation to non-homogeneity or that incorporate homogenization of the starting material as a New measurement techniques, modeling, and first step. the ability to correlate nano- and macro- scales are needed. Analysis To gain a mechanistic understanding of self- Develop data bases sufficiently large to assembly and biomimicry, fundamental permit modeling. knowledge will have to be developed in basic disciplines such as biology, biochemistry, To do this structure/property relationships will biophysics, polymer science, surface and have to be developed for lignocellulosic colloid science, thermodynamics, kinetics, materials. High throughput analytical and organic materials science. This will methods will also have to be developed. This require the virtual creation of a new will require multidisciplinary solutions. In multidisciplinary field as it relates to the forest addition, we will need to correlate what resource. Specialized equipment and happens at the micro- and nanoscales to the analytical capabilities currently used in other macro scale. fields and even the development of new techniques and instrumentation specific to this New measurement techniques, area will be needed. Long-term cooperative modeling, and the ability to correlate efforts between academia, research nano- and micro-scales are needed. institutions, and the network of nanotechnology laboratories (currently under development) will also be needed. Nanoscience

Establish/expand the discipline of nanoscience as it pertains to lignocellulosic materials, which today is virtually non-existent.

Developing this area will require multi- disciplinary partnerships. Examples include areas such as new measurement techniques (e.g., for particle/particle interactions), modeling capabilities (quantify the effects of surface chemistry and shape factors), and multi-scale self-assembly. An electron microscope cross section image of a paper coating Image courtesy of IMERYS 26 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 27

Description Improved understanding of the essential nature of the plant cell wall and the Research activities in the Cell Wall nanoprocesses involved in its formation Nanotechnology focus area seek to converges with emerging nanoscience, understand and exploit the architecture and bringing about new challenges and processes of consolidation of wood cell walls, opportunities. New information and insight which are the primary determinants of the concerning nanoscale order and assembly of material properties of wood and wood fibers. the lignocellulosic cell walls is needed. This Wood cell walls are nanocomposites of knowledge will: (a) advance opportunities to cellulose, hemicelluloses, protein, and lignin. control structure within the genetically They form the basis of the forest products engineered plants; (b) suggest new uses of industry and its renewable resources. Wood wood and its constituents individually; and (c) cells contain unique nanomanufacturing provide system prototypes for biomimetic protein complexes that use activated glucose nanoscale engineering processes to produce to assemble cellulose nanofibrils, the most materials in entirely new ways. It is possible to abundant renewable material resource on imagine material production processes that earth. These remarkable cellulose nanofibrils use proteins directly, or the as-yet-unknown exhibit a modulus roughly one quarter to one protein operation mechanisms, allowing fifth of that of a carbon nanotube, yet they are fibrils and composite materials to be produced naturally without the need for manufactured and engineered at the energy-consuming, high-temperature nanoscale outside the cell. Such approaches processing. may dramatically change the manufacturing of wood products by reducing energy consumption, eliminating the delignification Manipulating the architecture and process, and conferring the ability to processes of consolidation of wood cell industrially engineer material properties on walls is key to achieving superior the nanoscale. Ultimately, research into these physical properties at nano-, micro-, areas will benefit the public through value- and macro-scales. added traditional products, novel manufacturing processes, and innovative products, as well as optimized plantation Recent studies of interactions between the forests with minimized impact on natural major cell wall constituents, together with ecosystems. evidence that the assembly of the cell wall is genetically encoded, suggest that the The goal is to develop the capacity to formation of cell walls involves highly manipulate the nanoarchitecture of orchestrated nanoprocesses. Research secondary walls of woody plants. illustrates that the molecular and nanoarchitectural details of these cell walls differ between cell types and tissues and Research Goal and Objectives species. At the present time, our understanding of the native structures, their The overall goal of this focus area is to molecular diversity, and the mechanisms of develop the ability to modify the biogenesis and hierarchical assembly in nanoarchitecture of the secondary walls of woody plant cell walls is very rudimentary. woody plants to achieve significant improvements in properties, and to adapt these properties to different applications. 28 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Achieving this goal depends on controlling ! Establish a more solid foundation for the processes of cell wall assembly through relating the genomic information from genetic and environmental manipulation. To Arabidopsis thaliana to corresponding accomplish this it will be necessary to achieve genomic information for commercially a deep and integrated understanding of the important species of wood complex and highly coupled processes responsible for consolidation of the cell walls ! Develop new methods of investigating cell and how these processes vary in different wall structure by non-invasive microscopic species and tissues and under different and spectroscopic measurements that do environmental growth conditions. New not require isolation of the individual methods for investigating the constituents components in order to acquire and separating them surgically at the information concerning structure and nanoscale need to be developed. Finally, it mechanical properties will be necessary to take advantage of all the new instrumental and technical methods ! Develop new techniques for separating available for investigating nanostructures as the cell wall constituents without altering they occur in their native conditions without the native structures disruption. Ultimately, genetics, cell biology, biochemistry, biophysics, and materials ! Develop methods to economically extract engineering, must be linked in order to lignin without substantially altering its establish causal relationships between structure molecular phenomena and the diverse structures and mechanical properties of plant Outcomes and Impacts cell walls at the nanoscale. The following examples, while not all- inclusive, illustrate some of the potential Specific objectives will include but are not applications of successful R&D in this area. limited to:

1) Improved product diversity and properties ! Characterize the consolidated cell wall through engineering of wood feed stock to structure without resorting to reductionist meet product-specific requirements (e.g., methods that result in the loss of generation of thinner walls in southern information regarding the nature of pine, changed ratio of wall components, individual constituents or the coupling of more flexible fiber, more or less the different constituents absorptive fiber). ! Establish the relationship between genetic 2) Enhanced use of non-merchantable information and its phenotypic expression timber, wood processing residues, and at the nanoscale level with regard to other agricultural residues as sources of mechanisms of biosynthesis and the biomass to compensate for declining structure and organization of the fossil fuels. constituents of the cell wall 3) Improved ecological sustainability ! Identify the influence of environmental through reduced energy costs to extract conditions on native cell wall properties lignin (currently accounts for one half of and stabilizing properties under variable paper manufacturing costs), minimization environmental conditions Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 29

of undesirable chemical byproducts in 1) The speculative models that have been in wood processing, and faster growing trees frequent use over recent decades will not that retain industrially useful properties to prove useful—they are based on maximize productivity of plantation forest adaptation of many of the paradigms land. developed in studies of synthetic polymers. 4) New methods for extracting and isolating the lignin and hemicelluloses in a form 2) Many phenomena that can occur at the that is marketable (may have unique nanoscale level do not lend themselves to properties for applications in the industrial analysis in terms of the concepts of the markets for phenolic-based polymers and classical thermodynamics of macroscopic polysaccharides). systems (e.g., the aggregation of cellulose in the native state). 5) Improved economic vitality of local industry and job creation through 3) Traditional computer modeling of the innovative, high-value processing and atomic scale does not readily deal with fabrication of wood and wood-based molecular and fibrillar interactions at the products. nanoscale. Novel nanoscale modeling methods for fibrous composites need to Key Research Challenges be developed as a means of understanding native cell wall structure, The most challenging part of what lies ahead alterations during processing, and is to establish new paradigms to enable conceptualization of value-added examination of wood cell wall structures at the materials. nanoscale that will be meaningful to the wood science community. The wood science 4) Because cellulose has a predominant community has historically organized its importance in the forest products industry foundational knowledge at the microscale and is the skeleton around which other cell and the molecular scale, with only speculative wall constituents are organized, it models to bridge the gap. With the becomes important to understand the development of vastly more powerful processes by which the cellulose is instruments for examining structure at the formed. nanoscale level, it is now necessary to discard the speculative models and establish new 5) It is equally important to understand how paradigms that are validated by the processes of formation and assembly experimental observations. Ultimately, we of the other cell wall constituents are must obtain a comprehensive view of the coupled with the deposition of the chemical, mechanical, microscopic, and cellulose to form the hierarchically more crystallographic nature of cell wall structure in complex sub-layers of the cell wall. the native state and during processing. 6) Knowledge of changes in composition Some of the specific challenges to be and structure will not necessarily lead to addressed by research in the Cell Wall new value added products unless it is Nanotechnology focus area are described known how these changes alter the below. physical and mechanical properties of cell walls. This relationship of chemical and 30 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

structural changes to mechanical resolution imaging of the native cellulose properties can lead to development of synthesizing complex. improved wood and fiber products. Regulating the Synthesis of Other Cell Wall R&D Priorities Constituents

Regulating Cellulose Nanofibril Formation Characterize the processes that regulate the formation of the other constituents of the cell Investigate the process of formation of wall and the manner in which they are cellulose nanofibrils, including genetic, coupled with the deposition of cellulose. biochemical, cellular, and biophysical regulation. It is important to identify and understand the enzymes and cellular processes that control Here we include both the primary synthesis of the synthesis and interaction of hemicelluloses the molecules and the process that brings and lignin. To aid this research, systems need about their nucleation into a unique, to be developed allowing heterologous unusually stable nanofibrillar form that has expression or reconstitution of polymer- rarely been duplicated in a non-biotic synthesizing systems so that functions of environment. Cellulose biogenesis is altered genes can be rapidly tested. effectively a nanomanufacturing process Important questions include identification of accomplished by a multi-protein complex that where in the cytoplasm, plasma membrane, is highly integrated into the cell structure. We or exoplasmic/cell wall space is each enzyme need to identify all the essential proteins and, system found and determination of the shape, their mechanistic interaction, the regulatory surface area, degree of aggregation and/or mechanisms for the protein complex, and how crystallinity for all the polymeric components it is influenced by environmental factors. We in addition to understanding their interaction. need to accurately characterize the diverse Potential practical benefits of modifying nanoscale structures of native cellulose and existing constituents or of adding determine how variability is controlled. A nanomaterials into the cell wall to generate number of well-characterized model systems novel and useful composite properties should exist that can continue to be the subjects of also be explored. biological research in this area as well as in understanding the biophysics of fibril formation. Ongoing research to synthesize cellulose in vitro from isolated cellular constituents should be extended to characterization of all the constituents of the active complex and reconstituting it outside the cell solely from identified components. In addition, efforts have begun toward generating dynamic computer models of an active cellulose synthesizing complex. Such efforts will be aided by development of methods for theoretical protein modeling at the nanoscale that do not depend on solved crystallographic structure and higher Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 31

Assembling and Consolidating the Woody Cell being characterized, and monoclonal Wall antibodies are being generated that recognize a greater diversity of carbohydrate Determine the manner in which the processes epitopes). Development of computer models of assembly and consolidation are guided by for nanoscale interactions of fibrous the expression of genomic information, the components and for nanoscale mechanical biophysical interactions of the synthesized properties will also help to advance this molecules, and the emerging mechanical research area. properties. Developing Efficient Experimental Systems The impact the composite structure of the cell wall and its components have on the Exploit appropriate model systems to rapidly mechanical properties of the plant cell and accumulate fundamental knowledge. fiber material obtained from woody plants is important for many applications. For genomic studies, the model plant Fundamental questions include how the Arabidopsis thaliana, which has a close additional polymeric constituents influence evolutionary relationship to Poplar, is a the aggregation of cellulose and the valuable tool because it has secondary cell formation of the plant cell wall. It is clear that walls with nanoscale structure that parallels cell wall consolidation involves the commercially important woody species. transformation of components that are first Research has already identified induced deposited in a highly hydrated environment mutations in Arabidopsis that cause into a very tightly aggregated environment alterations in secondary walls, particularly the within which the degree of hydration is cellulose and lignin components. Equally controlled by the characteristics of the important is the genomic characterization of consolidated structure. It is important to model tree species and the development of determine how this process is regulated widely accessible methods for rapid testing of allowing it to be highly predictable within gene function directly in transgenic trees. particular cell types and species yet also Genomic analysis must ultimately be resolved subject to environmental regulation. Other to cellular understanding of the roles of the questions include how the native properties of encoded proteins, and here more unusual the cell wall are changed during industrial model systems like the cellulose-synthesizing processing, and if this can be more moss Physcomitella patens may have advantageously controlled. Moreover, an particular value. Other model systems understanding of the interaction of additives involving bacteria may also be useful for such as adhesives used in wood products with rapid testing and provide additional insight the cell wall structure at the nanoscale could into cellulose synthesis. For example, the allow the properties of wood products to be bacteria Acetobacter xylinum produces large improved. quantities of cellulose and has been used extensively to study cellulose biosynthesis. For understanding the consolidated structure of cell walls in the native state or in mutated Applying Novel Instrumental Methods form, new tools are needed. Some of these are already under development (e.g., Apply new instrumental methods to study the recombinant fungal hydrolases against cell wall native state without significantly diverse plant cell wall polysaccharides are altering its structures. 32 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Much remains to be accomplished in this Developing New Nanocomposites area. Many of the instrumental methods developed to date have been for Develop cell walls as models and materials investigations of inanimate structures and for nanoscale assembly of new composites. inorganic systems. Methodologies that are more sophisticated than those currently used As we understand the subtleties of assembly of in the wood science community will be cell walls at the nanoscale level, we need to needed to isolate the different constituents in be alert to the possibilities that some of these as close to their native state as possible and processes may lend themselves to scaling to a for examine the nanoscale structure of non- higher level, as well as to the possibilities that disrupted cell walls. In some cases, this may they may provide models for nanoscale require the development of new instruments assembly of other materials, whether synthetic or measurement techniques that avoid the or natural. That is, they may provide excellent reductionist approaches used in the well- models for the development of new established methods of wood chemistry. Even nanocomposites with unusual properties. The more far-reaching possibilities include understanding of the physical and chemical nanodevices fabricated to search for and properties of the cell wall constituents may report interactions between molecules in also provide a path for engineering materials normal and altered cell walls. Such devices with new bulk or surface properties needed for could possibly be engineered to allow high emerging applications. Examples include throughput analysis of cell wall structure and sensors, packaging materials, biocompatible properties, including intact plants. These or anti-microbial materials, or substrates capabilities would significantly improve our whose surface properties have been tailored understanding of cellulose fibril synthesis and for compatibility with other electronic or the formation of the plant cell wall. optoelectronic materials or devices. It is Understandings of cell wall mechanical known that cellulose fibrils exhibit properties can be investigated via use of piezoelectric properties. Piezoelectric nanoindentation. materials are widely used for physical, chemical, and biological sensing devices. More fundamentally, cell wall molecules could possibly be used as nanobioelectronic devices. An understanding of the properties and assembly of cell wall molecules may enable the realization of these functionalities. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 33

Description used delignification technologies. The need for pulp bleaching might also be minimized The ability to monitor the environment and or avoided. conditions occurring during the manufacturing and use of wood-based Manufacturing costs could also be reduced by products will help lower production cost and employing nanotechnology to prevent add greatly to the functional value of goods cellulose and hemicellulose degradation and and services. Access to information could be yield loss due to over-processing. For greatly expanded through the availability of example, it is possible that cellulose or other- non-obtrusive sensors that are small and types of nanofibrils/nanomaterials could be affordable. It should be possible to take grafted onto wood fiber surfaces. These advantage of what is being developed in grafted nanofibrils/nanomaterials could other areas for use in the forest products reduce or eliminate the need to do additional arena. Additionally, we can anticipate that the mechanical fiber refining via improving fiber- deeper understanding of the properties of fiber network bonding or allowing a reduction lignocellulosic materials at the nanoscale will in the amount of fiber needed to produce reveal properties or materials that can be products. Water removal (drying) via use of incorporated into sensors or used as part of a thermal (steam) energy is a big cost in the network communicating local conditions. production of most forest products. If nanomaterials could be used to eliminate all The ability to efficiently and effectively rewetting in the press nip (such as in wet press use nanoscale sensors to monitor felts), significant manufacturing energy processing and end-use conditions will savings could be achieved. For example, self- assembling temperature-sensitive nano- reap enormous benefits and cost polymers could be attached to fiber surfaces reductions. in order to convert hydrophilic fiber surfaces to hydrophobic surfaces at temperatures Nanostructured catalysts could be used in above a selected low critical solution processing to efficiently and effectively temperature (LCST) so that water can be more disassemble wood into its various easily squeezed out of fibers network. When components for optimal downstream temperature returns to that below the LCST, processing. For example nanostructured the nano-polymer changes to hydrophilic and catalysts could be used to selectively remove serves to improve fiber-fiber network bonding. lignin; separate lignocellulose into its constituents (cellulose, hemicelluloses, and lignin); or possibly even liberate cellulose Research Goal and Objectives nanofibrils. Examples of the benefits The goal of this focus area is to develop the achieved from such nano-controlled capacity to adapt and use nanoscale sensors disassembly include enhanced material and nanomaterials to reduce manufacturing properties (e.g. lignin and hemicelluloses costs and improve quality and performance could be liberated at near native state) and while imparting multifunctionality to forest reduced environmental impacts. For products. example, energy costs would be reduced in pulping if such nanostructured catalyst disassembly avoided the high temperature processing (>100oC) employed with currently 34 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Some specific objectives include the research is more or less related to following: Analytical Methods for Nanostructure Characterization (R&D Focus Area 5) ! Develop feedstocks and wood-based ! Develop and employ highly selective products that have sensing capability at nanostructured catalysts to efficiently and the nanoscale—this research would be effectively delignify or separate wood into focused on raw material manipulation or its constitutive components in modification genetically so that the environmentally preferable ways (e.g. no building block of feedstock has sensing environmentally troublesome byproducts capabilities to provide moisture control, are produced; high temperature et cetera processing is not needed; product yields ! Develop lignocellulosic-based sensors. are high; and energy consumption is This research is focused on fundamental greatly reduced compared to current understanding of lignocellulosic materials processes) so that it can be modified chemically to ! Develop nanotechnologies that can produce sensing-specific capability, such modify fiber surface nanostructure and as temperature, or self-healing fiber-fiber network bonding ability so that ! Develop the capability to effectively and wood fiber mechanical refining energy efficiently incorporate a variety of and fiber useage can be significantly functional nano materials with wood- reduced based materials and paper at the macro, ! Explore the use of nanofibrils/ micro, and nanoscale to make high- nanomaterials in forest products unit performance, high-value products operations such as water removal as a ! Develop or deploy durable, rugged, and means to significantly reduce energy low-energy or passive nanosensors that consumption can be incorporated into wood and paper-like products to add value. Progress in nanoscale research involving Research will include monitor or control of lignocellulosic materials will be temperature, pressure, volatile organic significantly enabled by metrology that compounds (VOCs), moisture content, allows observation and monitoring of mold, and insect attacks. Research will nanoscale features and properties. also include fiber tagging to increase fiber recyclability/trackability and fiber surface characteristics for identification Outcomes and Impacts ! Develop rugged, robust sensors to Wood and lignocellulose-based materials monitor processes at the nanoscale and can be used as a substrate or as the sensor sampling procedures for their itself. The manufacturing costs for producing effectiveness. This goal is related to forest products will be greatly reduced general sensor development for through increasing final product yields and monitoring nanoscale behavior or process reduced energy consumption. The following in wood products manufacturing. The examples illustrate some of the potential applications: Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 35

1) Nanosensors incorporated into wood- needed research on nanosensors in the based materials that can provide very forest products industry. early warning of either mold or termites. 2) Cultural—The forest products industry is 2) Nanoscale processes that can provide conservative and risk-averse self-healing once the structure is being attacked by mold or termites. 3) Social—Regulatory issues and the perception of the wood, pulp, and paper 3) Nanosensors on packaging materials that industry as low-technology limits driving can detect conditions such as food forces for change. spoilage or medical package tampering or exposure to unsafe conditions. R&D Priorities 4) Intelligent papers that have memory Basic Research in Food and Medical Product capabilities or are responsive to radio or Contamination electronic signals. Identify microbial species or chemical/ 5) Nanosensors that can provide fiber optical/physical agents that are unique tagging for recycling, forensic, or fingerprints or signatures of food spoilage, counterfeiting applications. medical contamination, or product degradation, and develop methodologies for 6) Nanostructured catalysts that can liberate incorporating these agents into non-obtrusive, cellulose nanofibrils from wood as well as low-cost, robust nanosensors for food and selectively remove lignin and/or medical packaging materials. hemicelluloses in environmentally preferable ways. Much research in this area may already be available (e.g., assessments of classes of 7) Nanofibrils/nanomaterials that can be chemical signatures, an indicator that will used in forest products processing to identify the chemical signature, diagnostic significantly reduce manufacturing energy information for health care practitioners, and materials consumption. feedback for remote health care, contamination by pathogens, sterility indicator). However, more may be required, Key Research Challenges especially in integrating the knowledge to The primary barriers to achieving the goals of wood-fiber science or paper-coating Nanotechnology in Sensors, Processing, and chemistry and biosensor research to develop Process Control can be generally categorized paper-deployable molecular-level sensing in three areas: capabilities of the identified species or agent related to spoilage or contamination. 1) Technical—A lack of basic knowledge of the nano-scale architecture and formation Basic Research in Wood-Fiber Science processes of wood and wood components exists, such as a fundamental Investigate genetic and chemical understanding of cell wall structure and modifications of wood lignocellulose materials self-assembly. There is also a limited to enable basic sensing capabilities and self number of scientists and technologists with regulation (e.g., for moisture, temperature, expertise to conduct and apply the VOCs). 36 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Research is needed on modifying fiber Basic Research in Data Synthesis surfaces so that they can easily interact with other species to build nanosensors on the Study and develop methods to synthesize data surface or nanosensors that are responsive to from multimillions of nanosensors in order to radio and electronic signals. Knowledge generate useful information for action or developed in fiber cell wall structure and self- process control. assembly research should be integrated into this effort. This work will require research in mathematics and computer science related to signal Research in Coating Technology and Materials processing and data synthesis.

Investigate and develop paper and wood Research in Nanostructured Catalysis product coating technology and coating materials that can deploy nanosensors to Develop cost effective, efficient, these products through mechanical or environmentally-preferable and highly- chemical means. selective nanostructured catalysts for disassembling wood and lignocellulose. Research is needed in developing new coating material and novel coating Nanostructured catalysts are needed that are deployment techniques (such as inkjet printing able to liberate cellulose nanofibrils from of conductive materials on paper), as well as wood, remove lignin, and have the ability to paper-surface modification to be receptive of separate lignocellulose into its constituent new coating or printing materials and components at high yield and in near native- techniques. Basic research in new “ink” or state. Understanding the principles that coating material interaction with fibers is also control nanocatalysis is key to developing needed. more effective catalysts. In this way rates of reaction can be greatly increased as well as Research in Fiber Tagging increasing selectivity.

Investigate and develop Research in Forest Products Processing to fiber tagging techniques Achieve Manufacturing Cost Savings (e.g., through coating or fiber modification) to Carryout research on the use of nanomaterials enable fiber separation in conjunction with unit operations in the and identification for processing of wood and wood-based recycling, counterfeiting, materials. or forensic applications. Areas of particular importance include Examples include preventing degradation and yield loss, “nanotechnology improving water removal, decreasing fiber watermarks” that code refining, and fiber modification to achieve paper or wood products significant energy and materials savings in for recycling or that the manufacture of wood fiber-based forest identify or certify “chain products. of custody.” Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 37

Description challenge to understand the nature of these objects in the overall systems and how Progress in nanoscience and nanotechnology changes at the nanoscale alter overall system is significantly enabled by tools that allow properties. visual observation and manipulation of the nanosized features and measurement of Lignocellulosic materials are complex properties at the nanoscale. Each of the structures and, as natural materials, can vary preceding four topics Polymer Composites significantly in properties within and between and Nano-Reinforced Materials; Self- species. Many of the techniques being assembly and Biomimetics; Cell Wall developed in the areas of soft-matter physics Nanotechnology; and Nanotechnology in and nanotechnology need to be adapted and Sensors, Processing, and Process Control— developed to meet the challenges presented has needs for tools which are able to describe by lignocellulosic materials. the size and shape (morphology) and composition and chemistry at the nanometer scale of lignocellulosic materials, as well as Research Goal and Objectives take measurements of mechanical, electrical, The overall goal of the analytical methods and electronic properties. focus area is to develop the nanoscale characterization methods and physical Although general statements about nano- (mechanical, electrical, magnetic, optical) scale analysis tools already available can be and chemical property measurements and made, it is important to recognize that it is techniques necessary to adequately often necessary to develop or adapt tools characterize complex wood and wood-based (and specimen preparation) to unique lignocellulosic materials, alone or used in scientific or analysis questions. While the conjunction with other organic or inorganic scientist or engineer always wants more materials, at the nanoscale in three information than is available at any specific dimensions over relevant time and length time, it is often productive to identify how the scales. Specific objectives include: answers to specific well-focused questions can be addressed. Thus, this focus area centers on general issues and identifying analytical 1) Adapt currently available physical and challenges. chemical property instrumentation used in nanotechnology and nanoscience to Two related but fundamentally different types lignocellulosic nanofibrillar and cellular of nanoscale analysis questions exist. morphology. Frequently, questions are asked about the structure, chemistry, or properties of a specific 2) Utilize the intense light sources and nanosized object. Either that specific object is neutron scattering tools being developed of interest or it is assumed to be an example at national laboratories to gain deeper of other similar objects. However, for understanding of the nature of industrial applications, it is equally important lignocellulosic materials. and possibly more important to be able to determine representative properties and 3) Adopt and adapting the techniques used distributions of properties that occur in a in the area of soft matter physics, such as collection of nanoscale objects. When these light scattering and rheology nanosized objects are incorporated into measurements, to quantify the structures larger functional systems, it is a particular encountered in lignocellulosic materials. 38 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

4) Adopt techniques from biological analysis, such as phage display, to Research cooperation and collaboration characterize lignocellulosic surfaces in and information sharing is essential in terms of bonding sites. making rapid progress.

5) Achieve three-dimensional imaging Key Research Challenges capabilities for lignocellulosics at nanoscale. The following include some of the more prominant challenges in this focus area: 6) Achieve nanoscale lignocellulosic measurement methods that are 1) Characterization of self-assembled scientifically sound and artifact-free. (bottom up) nano-, micro-, and macro- systems such as lignocellulosics is Outcomes and Impacts inherently more complex than engineered The goal is to develop characterization (top down) materials and, therefore, methods, measurements, and analysis issues and structure property techniques for the complex nanoscale relations are more challenging. architecture and composition of wood and wood-based materials. 2) The need to determine nanoscale morphology suggests use of microscopy The understanding and use of the unique or scattering techniques. The desire for properties of cellulose, hemicellulose, lignin, chemical information suggests use of and wood extractives in more advanced various forms of spectroscopy. applications requires adequate Unfortunately, the organic/polymeric characterization and control of these nature of lignocellulosic material places properties at the nanoscale. Analysis and special constraints and demands on the characterization tools have proven to be the tools that can be used and the manner in essential and sometimes limiting capability which they can be used. One of these that facilitates the development of constraints is that lignocellulosic materials nanoscience and nanotechnology in specific (like other organic/polymeric materials) areas. It is essential that the range of tools are subject to damage by electrons, ions, currently applied to more conventional and photons. As a result, exposure must materials be made accessible to those be limited and/or evidence of damage working with forest products. This can be and rate of damage must be determined. facilitated by gathering the information available on tools and centers where these 3) The type of information needed tools are available. In addition, development determines the applicable tools. A and training efforts will enable a new chemical analysis that reports simply the generation of tools to be developed or presence of carbon and oxygen is of very applied to lignocellulosic materials. little value. Specific functional analysis is required: aromatic carbon, carbonyl groups, carboxylic acids, hydroxyl groups, et cetera. Fortunately, many well- established tools for characterizing materials on a nanometer scale exist because the needs of the semiconductor Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 39

industry have promoted their Improved Measurement of Hemicellulose development and utilization. However, they must still be adapted to organic Develop techniques and tools to measure polymeric materials. hemicellulose polymer structure and properties at the nanoscale. R&D Priorities Hemicelluloses are inherently difficult to Compendium of Available Tools describe for several reasons. Although glucose is the principal monomer, other Create and maintain a compendium of sugars are also incorporated. Much of the available analysis tools. polymer is linear; however, branches exist, and the repeat structure is irregular. It is recognized that many types of analysis Furthermore, some side chains are methods exist that can be used to characterize acetylated. Hemicelluloses are also much materials at the nanoscale. Many of these lower in molecular weight than cellulose, and methods are not commonly available to they are somewhat water-soluble and subject workers in the forest products industry. to modification by hydrolysis. Because it is important to researchers and engineers to understand what is available The morphology of woody plant cell and how different techniques might be used, a walls is complex. frequently mentioned need is a compendium of characterization tool descriptions that includes their outputs, limitations, and Measurement of Lignin specimen requirements. A comprehensive list may be difficult to produce and maintain, Develop techniques and tools to measure however, because new tools are constantly lignin structure and properties at the being developed, and existing tools and nanoscale. methodologies are always being improved. Nonetheless, the beginning of such a Lignin is the most poorly defined plant cell compendium is provided in Appendix F. Also wall component. It appears to be a highly included in the appendix is a listing of user cross-linked polymer composed of facilities where some special instruments are phenylpropene monomers (p-coumaryl, available for research use. coniferyl, and sinapyl alcohols) produced late in the growth of plant cells and embedded in a complex cell wall structure. It could be described as the product of free radical polymerization; however, no consensus exists on the details of the process or molecular structure. Part of the reason is that lignin is such an intractable material. It is not soluble and must be isolated from cellulose and hemicellulose by aggressive destruction of those components. It is subsequently broken into small fragments that can be characterized. During this process, there is always some concern that alteration of the original polymer has occurred. 40 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Methodologies and Instrumentation These irregularities often result in contact with the side of the scanning tip rather than the Develop methodologies and instrumentation to point, which results in images that are very determine cell wall morphology and measure difficult to comprehend. properties at the nanoscale. Achieving a realistic representation is a The morphology of plant cell walls even at common problem in microscopy. There is the micrometer scale is complex. There are widely held consensus that morphological many different types of cells that perform information from different length (size) scales different functions and change function as the must be integrated. This implies using plant matures. In a very crude different microscopical techniques and approximation, a plant stem is composed of working from low resolution toward high tubular cells fused together by lignin-rich resolution to be certain that the fields studied layers (middle lamella). The walls of the in high resolution are not unique. tubes consist of a few distinct layers composed of varying amounts of Compositional information is needed in hemicellulose and lignin reinforced by addition to the description of size, shape, and cellulose nanofibrils. structure. Perhaps the most confounding problem is that cellulose and hemicellulose The morphological information are chemically similar (both polymers of obtained at the various lengths of scale simple sugar). If one is concerned with the must be integrated and self-consistent. composition of nanomaterials, then one is most likely to be employing spectroscopical methods; solution chemical analysis does not There are several types of technical seem applicable. The differences in challenges for the description of cell wall vibrational and electronic spectra are very structure, which are illustrative of the small; mass spectra may exhibit better difficulties involved in working with any wood selectivity. Perhaps some means of selectively nanomaterial. One would like to describe labeling one material may improve each distinct wall layer, but we do not know discrimination. Antibodies tagged with gold how to isolate the layers without damage. have been employed in some electron Even to prepare an ultrathin cross section (ca. microscopy studies. 100nm) of a cell for study by transmission electron microscopy or x-ray microscopy is a Secondary ion mass spectrometry (SIMS) is difficult task. Alternative methods for another means of obtaining chemical preparing cross sections must be developed. information with high resolution imaging. It is very surface-sensitive (1-10 nm) and has fair The size and shape of plant cell walls offer a lateral resolution (50-100 nm) and very good challenge for scanning probe microscopy. chemical specificity. Sputtering with small The vertical range of most scanning probe ions (e.g., helium, argon, cesium) creates microscopes is on the order of 5 µm. This is smaller than the diameter of most cell lumens, which range from about 10 to 30 µm. No single spectroscopic technique will be This limits the portions of a specimen that are approachable by the scanning tip. The sufficient to characterize woody plant irregularity of cell structure also presents materials at the nanoscale. problems for scanning probe microscopy. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 41

damage deep beneath the surface which has been demonstrated to be self-sufficient. The frustrated the use of SIMS for composition- application of more than one instrument depth profiling or organic/polymeric provides good validation of the accuracy of materials. Recently, progress has been made results. For example, SIMS provides good in using ‘cluster ions’ like SF5, Aun, and chemical specificity, but the detection limits buckyballs as sputtering ions. These cluster for different species varies widely. X-ray ions are very efficient at sputtering and reduce photoelectron spectroscopy (XPS, ESCA) damage to a very shallow layer. SIMS can be provides more uniform sensitivity but has very useful for obtaining three-dimensional poor chemical specificity. The combination of imagewise chemical information in organic/ both techniques provides robust chemical polymeric materials. information. Oftentimes, the most useful nanoscale studies combine information on Strategies that Employ Multiple Techniques morphology and chemistry. Computer modeling of experimental results can also be Develop and deploy new collaborative extremely helpful. strategies for analysis involving multiple techniques. Many of the tools we need are not commonly available and have been developed to The need to combine spectroscopy and support the semiconductor industry. This microscopy and/or apply multiple techniques suggests that progress will require and disciplines is a recurring theme in the collaboration between scientists who may discussion of nano-scale analysis tools. To have to struggle to find a common language. date, no single spectroscopical technique has 42 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 43

In conducting the research identified in the five preceding R&D focus areas—polymer composites and nano-reinforced materials; self-assembly and biomimetics; cell wall nanotechnology; nanotechnology in sensors, processing, and process control; and analytical methods for nanostructure characterization—it is essential that research collaborations and sharing of science and technology knowledge occurs. Collaboration and cooperation needs to occur among:

! Individual researchers

! Researchers with differing disciplines

! Basic and applied researchers and research teams

! Research institutions including universities, research institutes, and national laboratories

! Industry, universities, research institutions, and federal agencies and departments

! All of these groups from countries around the world

Table 1 shows a partial listing of research organizations and their possible roles in advancing the development and application of nanotechnology in the forest products industry sector. 44 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Table 1. Roles and Responsibilities of Potential Research Partners Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 45

4—Implementation Plan: Next Steps and Recommendations

Next Steps Next Steps and Recommendations To efficiently and effectively advance the ! Consensus on needs, priorities, and an nanotechnology research agenda for the agenda among all key stakeholders forest products industry, this roadmap should will ensure proper organization, be used as a starting point for further allocation, and deployment of engaging key stakeholders and stakeholder resources. groups in dialogue, consensus building, and partnership building. The following are ! To advance the nanotechnology some of the key stakeholder groups: research agenda, partnerships should be established among industry, ! Forest products industry—primary government, and academia. producers, converters, suppliers, and collective industry groups such as the ! This roadmap is a living document that American Forest and Paper Association should be reexamined by convening (AF&PA), the Southern Forest Products experts every 3 to 5 years. Association, the APA (Engineered Wood Association), the Composite ! Strong, focused leadership in the form Panel Association, the China Clay of a Steering Committee is essential to Producers Association, and the Georgia achieving the goals outlined in this Mining Association roadmap.

! Federal Departments and Agencies—the USDA Forest Service, USDA Cooperative demonstration, and deployment, such as State Research, Education and Extension the various Nanotechnology Research Service, Department of Energy (DOE) and Centers located at universities and its national laboratories, National Science Federal national laboratories Foundation (NSF), and National Institute ! International research communities of Science and Technology (NIST) involved in nanotechnology research and/ ! University and Research Institute/ or focused on the forest products industry Laboratory Communities—1) universities In addition, technical societies can help with forest products and pulp and paper provide important opportunities for departments and programs, umbrella interactions, dialogue, and technical university groups such as the Pulp and information exchange through conferences, Paper Education and Research Alliance workshops, technical courses, and symposia. and the Society of Wood Science and Examples of technical societies include the Technology, and research institutes and Technical Association of the Pulp and Paper laboratories focused on the forest Industry and the Forest Products Society. products industry; 2) the established These two groups regularly schedule research communities already involved in conferences, workshops, and continuing nanotechnology research, development, education courses to serve the needs of 46 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

primary pulp, paper and wood products activities. Finding, allocating, organizing, producers, suppliers, and converters as well and deploying resources is much easier when as the basic and applied research a broad consensus exists among the key communities serving the forest products stakeholders for critical technological needs, sector. Technical societies serving the priorities are set for exploiting marketplace nanotechnology communities include such opportunities, and a visionary, forward- organizations as the Materials Research thinking agenda is developed. Society, the American Chemical Society, the American Society of Mechanical Engineers, Consensus on research direction will and the American Institute of Chemical dictate proper research, development, Engineers. and deployment. In building consensus on nanotechnology opportunities and R&D priorities within the Recommendations forest products industry itself, the industry can capitalize on already established working This technology roadmap provides a starting relationships between forest products point for systematically focusing the many companies and universities and federal potential and diverse efforts in agencies with active forest products research nanotechnology for the forest products programs. The industry has established a set industry. It identifies priority needs and of technological themes in its Agenda 2020 research directions for the next five, ten, fifteen Initiative overseen by the AF&PA. years. It should be viewed as being a Nanotechnology is part of this research dynamic, living document and should be agenda. While not all forest products reexamined by convening experts every three companies currently take part in the Agenda to five years—experts who will review the 2020 initiative, it does provide forums for the industry’s progress, redefine goals, and broader industry to participate. Agenda assess accomplishments versus resources 2020 fosters collaborative, cost-shared available and resources expended. research on pre-competitive priorities of the forest products industry. A portfolio of research projects commensurate with the size and impact Increased linkages need to be made between of the forest products industry is research communities of the forest products needed. sector and the broader community of nanotechnology researchers in order to capture synergies, enhance accomplishments, A critical first step in moving nanotechnology and avoid needless duplication of facilities for the forest products sector forward is to and efforts. This broader community of gain consensus on what the specific focus nanotechnology researchers includes should be for the short term, mid term, and established university nanotechnology long term. It is important that efforts be research centers; federal departments, focused on high-impact, high-priority agencies, and laboratories having ongoing activities that will be the most critical to programs in nanotechnology R&D; federal commercial producers of nanomaterials and laboratories with nanotechnology user nanoproducts. Achieving consensus on facilities; and the National Nanotechnology critical activities should be accomplished by Initiative (NNI). engaging all the key stakeholders in assessing market potentials, determining technological From these linkages and interactions, barriers and the feasibility of overcoming consensus on the technological roadmap them, identifying assets and resources needs to be achieved among all the key available, identifying champions for the stakeholders, or little will be accomplished various program activities, defining funding other than uncoordinated piecemeal needs, and identifying risk factors. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 47

Specific next steps include: group should include representatives from individual forest products companies, the AF&PA, Pulp and Paper Education and 1) Identifying and prioritizing specific Research Alliance, Society of Wood Science avenues of promising research and Technology, USDA Forest Service, USDA 2) Initiating a portfolio of R&D projects that CREES, DOE national laboratories, NSF, NIST, is commensurate with the size and and appropriate technical societies. importance of the forest products industry The forest products industry should seek to 3) Developing effective funding strategies to become part of the NNI and participate in its support collaborative multi-disciplinary activities. The industry should have as its goal research activities, demonstration and to establish a $40 to $60 million-per-year validation of technology, and education nanotechnology R&D program under the NNI of a workforce skilled in developing and by 2008. applying nanotechnology for the forest products industry The forest products industry should have 4) Identifying precompetitive technological a nanotechnology R&D program of $40 needs to help set and focus research to $60 million per year. targets Realizing the potential of the emerging This roadmap represents the first step in nanotechnology industry will require a solid, communicating the needs and opportunities supporting foundation in instrumentation and associated with applying nanotechnology in measurement methodologies. Significant the forest products industry. Appropriate challenges must be addressed to apply representatives from the forest products sector nanoscale instrumentation to wood and (including members of industry, universities, lignocellulose. and federal agencies) should begin to interact and increase contacts with the existing Strong, focused leadership will be required to nanotechnology research community. In this make implementation of this roadmap a regard, the USDA Forest Service will seek to reality. Steps should be taken to establish a participate on the Nanoscale Science, steering group that includes key stakeholder Engineering, and Technology (NSET) groups and key funding groups. The steering Subcommittee of the National Science and group would serve as a focal point and Technology Committee. champion for the overall national roadmap and aid in accelerating nanotechnology in the forest products industry. The steering

Strong, focused leadership will be required to make implementation of this roadmap a reality. 48 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 49

Appendices 50 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 51

Appendix A: Workshop Agenda

Nanotechnology Workshop for the Forest Products Industry The National Conference Center 18980 Upper Belmont Place Lansdowne, VA 20176

October 17-19, 2004

Sunday, October 17 5:30 pm Dinner in Guest Dining

OPENING SESSION AND INTRODUCTORY SPEAKERS – General Session Room N3-365

7:00 pm Welcome – Phil JonesJones, IMERYS, and Ted Wegneregner, USDA Forest Service, Forest Products Laboratory; Workshop Co-Chairs

7:10 pm USDA Nanotechnology Roadmap – Hongda ChenChen, National Program Leader, Bioprocessing Engineering, USDA-CSREES

7:40 pm Overview of Roadmapping Process – Shawna McQueenMcQueen, Energetics

8:10 pm Workshop Deliverables – Phil Jones and Ted Wegner

8:30 pm Adjourn for Evening 52 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Monday, October 18 6:30-8:00 am Breakfast in Guest Dining

PLENARY LECTURES – General Session Room N3-365

8:00 National Nanotechnology Initiative: Overview and Planning for the Future – Mihail RocoRoco, Chair, National Science & Technology Council’s Subcommittee on Nanoscale Science, Engineering & Technology

8:45 Department of Energy Nanotechnology Programs – Paul BurrowsBurrows, Pacific Northwest National Laboratory

9:30 Nanobiomaterials – Art RagauskasRagauskas, Georgia Institute of Technology

10:15 Discussion

10:30 Break

10:45 BREAKOUT SESSIONS MEET

• Polymer Composites and Nano-reinforced Materials – Art Ragauskas and Margaret JoyceJoyce, Session Chairs – Room N3-365

• Self-Assembly and Biomimetics – Wolfgang GlasserGlasser, Derek Gray and Pete Lancasterancaster, Session Chairs – Room N3-247

• Cell Wall Nanotechnology – Rajai Atalla and Candace HaiglerHaigler, Session Chairs – Room N3-148

• Nanotechnology in Sensors, Processing and Process Control – Yulin DengDeng, Steve Kelleyelley, and JY ZhuZhu, Session Chairs – Room N3-555

• Analytical Methods for Nanostructure Characterization – Jim Beecher and Tim RialsRials, Session Chairs – Room N3-249 12:30 Lunch – Guest Dining

1:30 CONTINUE BREAKOUT SESSIONS

3:30 Break

3:45 Progress Reports from the Breakout Sessions – Session Chairs/ Representatives – General Session Room N3-365

5:30 Announcements – Phil JonesJones, Ted Wegneregner, and Jane Kohlman Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 53

Monday, October 18—Continued 5:30 – Dinner – Guest Dining

Evening Speakers – General Session Room N3-365

7:00 Nanotechnology – The European Forest Products Perspective – Tom LindstromLindstrom, STFI

7:30 Forest Products Industry Perspectives for Nanotechnology – Del RaymondRaymond, Weyerhaeuser

Tuesday, October 19 6:30-8:00 am Breakfast in Guest Dining

8:00 CONTINUE BREAKOUT SESSIONS

10:30 Break

Morning Speaker – General Session Room N3-365

10:30 Nanotechnology – The National Nanotechnology Initiative – Sharon HaysHays, Deputy Associate Director, Technology Division of the Office of Science & Technology

11:00 Roadmapping Report-outs from the Breakout Sessions – Session Chairs/Representatives – General Session Room N3-365

12:30 Lunch – Guest Dining

1:30 Depart 54 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 55

Appendix B: List of Participants

Dr. Donald B. Anthony Dr. Donald Baer Dr. Joseph J. Bozell President & Executive Director Laboratory Fellow Principal Scientist The Council for Chemical Research Pacific Northwest National National Renewable Energy Lab. 1620 L Street, NW, Suite 620 Laboratory 1617 Cole Blvd. Washington, DC 20036 Box 999 MS KB-93 Golden, CO 80401 Phone: 202-429-3971 Richland, WA 99352 Phone: 303-384-6276 Fax: 202-429-0436 Phone: 509-376-1609 Email: [email protected] Email: [email protected] Fax: 509-376-5106 Session: Sensors Session: Composites-Speaker Email: [email protected] Session: Analytical-Speaker Dr. Paul Burrows Mr. Sven Arenander Laboratory Fellow Manager Paper Science Solutions Dr. Fred Barlow Pacific Northwest National International Paper Consultant Laboratory 6285 Tri-Ridge Blvd. 901 Rose Cottage Road MS#K3-59, PO Box 999 Loveland, OH 45140 St. Simons Island, GA 31522 Richland, WA 99338 Phone: 513-248-6694 Phone: 912-399-6552 Phone: 509-375-5990 Email: [email protected] Fax: 912-634-1150 Fax: 509-375-3864 Session: Composites Email: [email protected] Email: [email protected] Session: Analytical Session: Self-Assembly Dr. Dimitri Argyropoulos Professor Dr. James F. Beecher Dr. Alan F. Button North Carolina State University Group Leader, Analytical Chemistry President Biltmore Hall & Microscopy Lab. Buttonwood Consulting, LLC Raleigh, NC 27615 USDA FS, Forest Products 8 Inverness Circle Phone: 919-515-7708 Laboratory Appleton, WI 54914 Fax: 919-515-6302 One Gifford Pinchot Dr. Phone: 920-730-5670 Email: [email protected] Madison, WI 53726 Fax: 920-968-0254 Session: Analytical Phone: 608-231-9475 Email: [email protected] Fax: 608-231-9538 Session: Cell Wall Dr. Rajai Atalla Email: [email protected] Sr. Scientist Session: Analytical Dr. Jeffrey Catchmark USDA FS, Forest Products Operations Manager Laboratory Ms. Janice Bottiglieri Penn State University One Gifford Pinchot Dr. Editor University Park, PA 16802 Madison, WI 53726 TAPPI Phone: 814-865-6577 Phone: 608-231-9443 704 Preston Lane Fax: 814-865-7173 Fax: 608-231-9538 Schaumburg, IL 60193 Email: [email protected] Email: [email protected] Phone: 847-466-3891 Session: Cell Wall Session: Cell Wall Fax: 630-237-6120 Email: [email protected] Dr. Daniel F. Caulfield Dr. Sundar Atre Research Chemist Professor Dr. Brian S. Boyer USDA FS, Forest Products Oregon State University Patent Attorney Laboratory 118 Covell Hall Squire, Sanders & Dempsey L.L.P. One Gifford Pinchot Dr. Corvallis, WA 97331 One Maritime Plaza Madison, WI 53726 Phone: 541-737-2367 San Francisco, CA 94111 Phone: 608-231-9436 Fax: 541-737-5241 Phone: 415-954-0230 Fax: 608-231-9262 Email: [email protected] Fax: 415-393-9887 Email: [email protected] Session: Self-Assembly Email: [email protected] Session: Self-Assembly Session: Self-Assembly 56 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Dr. Hongda Chen Ms. Sara Dilllich Dr. Alexander Fridman National Program Leader, Lead Technology Manager Professor Bioprocessing Engineering DOE-Materials, Sensors & Drexel University USDA/CSREES Automation 3141 Chestnut Street 1400 Independence Ave., SW, MS 1000 Independence Ave SW Philadelphia, PA 19104 2220 Washington, DC 20585 Phone: 215-895-1542 Washington, DC 20250 Phone: 202-586-7925 Fax: 215-895-1478 Phone: 202-401-6497 Fax: 202-586-9234 Email: [email protected] Fax: 202-401-4888 Email: [email protected] Session: Composites Email: [email protected] Session: Sensors Session: Composites & Guest Dr. Charles R. Frihart Speaker Dr. Mahendra Doshi Proj. Leader, Wood Adhes. Science Executive Editor & Tech. Dr. Charles Cleland Progress in Paper Recycling USDA FS, Forest Products SBIR National Program Leader 18 Woodbury Court Laboratory US Department of Agriculture Appleton, WI 54913 One Gifford Pinchot Dr. 800 9th St., SW, Suite 2312 Phone: 920-832-9101 Madison, WI 53726 Washington, DC 20024 Fax: 920-832-0870 Phone: 608-231-9208 Phone: 202-401-6852 Email: [email protected] Fax: 608-231-9592 Fax: 202-401-6070 Session: Self-Assembly Email: [email protected] Email: [email protected] Dr. Ray Drumright Session: Cell Wall Session: Sensors Dow Chemical 1604 Building Dr. Gil Garnier Dr. George Cody Midland, MI 48640 Kimberly-Clark Geophysical Laboratory Phone: 989-636-6084 2100 Winchester Road Carnegie Institution of Washington Fax: 989-638-6356 Neenah, WI 54956 5251 Broad Branch Road, NW Email: [email protected] Phone: 920-721-2557 Washington, DC 21015 Session: Composites Fax: 920-721-7748 Phone: 202-475-8980 Email: [email protected] Email: [email protected] Mr. Gerald M. Dykstra Session: Composites Session: Analytical-Speaker Pulp & Paper Technology Director Buckman Laboratories Mr. Paul Gilbert Dr. Scott Cunningham 1256 N. McLean Blvd. Engineer New Market Development Manager Memphis, TN 38108 SAPPI Fine Papers NA DuPont Phone: 901-272-8389 89 Cumberland Street Chestnut Run Plaza, Bldg. 728- Fax: 901-274-8035 Westbrook, ME 04098 1415 Email: [email protected] Phone: 207-856-3835 4417 Lancaster Pike Session: Composites Fax: 207-856-3770 Wilmington, DE 19805 Email: [email protected] Phone: 302-999-2969 Dr. Thomas Elder Session: Sensors Fax: 302-999-4930 Research Forest Products Email: Technologist Dr. Wolfgang Glasser [email protected] USDA FS, Southern Research Station Prof. Emeritus Session: Self-Assembly 2500 Shreveport Hwy. Virginia Tech Pineville, LA 71360 230 J. Cheatham Hall Mr. Yulin Deng Phone: 318-473-7008 Blacksburg, VA 24061 Professor Fax: 318-473-7246 Phone: 540-231-4403 IPST at Georgia Institute of Email: [email protected] Fax: 540-231-8176 Technology Session: Analytical Email: [email protected] 500 10th St., NW Session: Self-Assembly Atlanta, GA 30318 Dr. Alan R. Esker Phone: 404-894-5759 Assistant Professor Dr. Derek Gray Fax: 404-894-4778 Virginia Tech, Dept. of Chemistry, Professor, Chemistry Email: [email protected] (0212) McGill University Session: Sensors Blacksburg, VA 24061 3620 University Street Phone: 540-231-4601 Montreal, QC H3A 2A7 Fax: 540-231-3255 Phone: 514-398-6182 Email: [email protected] Fax: 514-398-8256 Session: Self Assembly Email: [email protected] Session: Self-Assembly Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 57

Dr. Michael G. Hahn Dr. Kevin T. Hodgson Dr. Phil Jones Associate Professor Professor Director, Technology & New Ventures University of Georgia University of Washington IMERYS CCRC/315 Riverbend Road Box 352100 100 Mansell Ct. E Athens, GA 30602 Seattle, WA 98195 Roswell, GA 30076 Phone: 706-542-4457 Phone: 206-543-7346 Phone: 770-331-0325 Fax: 706-542-4412 Fax: 206-685-3091 Fax: 770-645-3391 Email: [email protected] Email: [email protected] Email: [email protected] Session: Cell Wall Session: Composites Workshop Co-Chair

Dr. Candace Haigler Dr. James Holbery Dr. C.P. Joshi Professor Senior Scientist Associate Professor North Carolina State University Pacific Northwest National Michigan Tech U, SFRES Dept. Crop Science, 4405 Williams Laboratory 1400 Townsend Drive Hall PO Box 999, MS K5-22 Houghton, MI 49931 Raleigh, NC 27695 Richland, WA 99352 Phone: 906-487-3480 Phone: 919-515-5645 Phone: 509-375-3686 Fax: 906-487-2915 Fax: 919-515-5315 Fax: 509-375-2379 Email: [email protected] Email: [email protected] Email: [email protected] Session: Cell Wall Session: Cell Wall Session: Self-Assembly Dr. Margaret Joyce Ms. Karina Hanninen Dr. Sam Hudson Associate Professor Consultant Professor Polymer Chemistry Western Michigan University Jaakko Poyry Consulting North Carolina State Univ. 4601 Campus Drive Suite A234 Jaakonkatu 3, PO Box 4 2401 Research Drive Kalamazoo, MI 49008 Vantaa, FI 01621 Raleigh, NC 27695 Phone: 269-276-3514 Phone: 3589-8947-2119 Phone: 919-515-6545 Fax: 269-276-3501 Fax: 3589-878-2482 Fax: 919-515-6532 Email: [email protected] Email: [email protected] Email: [email protected] Session: Composites Session: Composites Session: Composites Dr. John Kadla Dr. Sharon Hays Dr. Ki-Oh Hwang Associate Professor Deputy Associate Director Lead Research Scientist University of British Columbia Office of Science & Technology Cargill Inc. 4034 Main Mall Policy 1710 16th Street, SE Vancouver, BC V6T 1Z4 Technology Division Cedar Rapids, IA 52401 Phone: 604-827-5254 Washington, DC 20502 Phone: 319-399-6181 Fax: 604-822-9104 Phone: 202-456-6046 Fax: 319-399-6666 Email: [email protected] Fax: 202-456-6021 Email: [email protected] Session: Self-Assembly Email: Session: Composites [email protected] Dr. D. Steven Keller Guest Speaker Mr. Gopal Iyengar Associate Professor Sr. Research Engineer SUNY-ESF/ESPRI Dr. John C. Hermanson Stora Enso North America 1 Forestry Drive Research Scientist 300 North Biron Drive Syracuse, NY 13104 USDA FS, Forest Products Wisconsin Rapids, WI 54494 Phone: 315-470-6907 Laboratory Phone: 715-422-2329 Fax: 315-470-6945 One Gifford Pinchot Dr. Fax: 715-422-2227 Email: [email protected] Madison, WI 53726 Email: Session: Analytical Phone: 608-231-9229 [email protected] Fax: 608-231-9303 Session: Composites Ms. Judith Kieffer Email: [email protected] Contracts/Communication Session: Analytical Ms. Katie Jereza Administrator Chemical Engineer Weyerhaeuser Co. Energetics, Inc. 33330 8th Ave. So. 7164 Columbia Gateway Dr. Federal Way, WA 98023 Columbia, MD 21046 Phone: 253-924-6200 Phone: 410-953-6254 Fax: 253-924-6812 Fax: 410-290-0377 Email: Email: [email protected] [email protected] Facilitator Recorder 58 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Dr. David E. Knox Dr. Tom Lindstrom Dr. Vijay Mathur Research Director STFI - Packforsh AB President Meadwestvaco PO Box 5604 GR International 11101 Johns Hopkins Road Stockholm, SWEDEN SE-11486 32918 6th Street SW Laurel, MD 20723 Phone: 011-468-676-7000 Federal Way, WA 98023 Phone: 301-497-1340 Fax: 011-468-214235 Phone: 253-924-6070 Email: [email protected] Email: [email protected] Email: [email protected] Session: Analytical Session: Self-Assembly Session: Analytical

Ms. Jane Kohlman Dr. Lucian A. Lucia Ms. Shawna McQueen Administrative Assistant Associate Professor of Chemistry Senior Analyst USDA FS, Forest Products North Carolina State University Energetics, Inc. Laboratory Campus Box 8005 7164 Columbia Gateway Dr. One Gifford Pinchot Dr. Raleigh, NC 27695 Columbia, MD 21046 Madison, WI 53726 Phone: 919-515-7707 Phone: 410-953-6235 Phone: 608-231-9479 Fax: 919-515-6302 Fax: 410-290-0377 Fax: 608-231-9567 Email: [email protected] Email: [email protected] Email: [email protected] Session: Analytical Facilitator Workshop Organizer/Recorder Dr. Yuri Lvov Mr. Reid Miner Dr. Alexander Koukoulas Professor Vice President Chief Scientist Louisiana Tech University NCASI International Paper 911 Hergot Avenue PO Box 13318 6285 Tri-Ridge Blvd. Ruston, LA 71270 Durham, NC 27509 Loveland, OH 45140 Phone: 318-257-5144 Phone: 919-941-6407 Phone: 513-348-6614 Fax: 318-257-5104 Fax: 919-941-6401 Fax: 513-348-6615 Email: [email protected] Email: [email protected] Email: [email protected] Session: Self-Assembly Session: Composites Session: Composites Dr. Anthony V. Lyons Dr. Graham Moore Dr. Charles E. Kramer Director of Research Strategic Consulting Manager R&D Director IMERYS PIRA International Albany Intl. Research Co. 140 Saddle Run Court Randalls Road 777 West Street Macon, GA 31210 Leatherhead, Surrey KT22 7RJ Mansfield, MA 02048 Phone: 478-553-5243 Phone: 44-1372-802000 Phone: 508-337-9541 Fax: 478-553-5460 Fax: 44-1372-802249 Fax: 508-337-9617 Email: [email protected] Email: [email protected] Email: [email protected] Session: Analytical Session: Sensors Session: Composites Dr. Christine Mahoney Dr. B.M. Mulder Dr. E. Peter Lancaster National Institute of Standards & Professor Scientific Advisor, Fiber Science R&D Technology Wageningen University Weyerhaeuser Co. 100 Bureau Drive, Stop 8371 Arboretum Lane 4 32901 Weyerhaeuser Way S. Gaithersburg, MD 20899-8391 Wageningen, NETHERLANDS Federal Way, WA 98063 Phone: 301-975-8515 6703 BD Phone: 253-924-6688 Email: [email protected] Phone: 31206081234 Fax: 253-924-5920 Session: Analytical-Speaker Email: [email protected] Email: Session: Cell Wall [email protected] Mr. Steven L. Masia Session: Self-Assembly Research Scientist Dr. Hiroki Nanko SAPPI Fine Paper N.A. Technology Principal Research Scientist Dr. Kaichang Li Center IPST at Georgia Institute of Assistant Professor 89 Cumberland Street Technology Oregon State University Westbrook, ME 04092 500 10th St., NW Dept. of Wood Science & Phone: 207-856-3579 Atlanta, GA 30332-0620 Engineering Fax: 207-856-3770 Phone: 404-894-9520 Corvallis, OR 97331 Email: [email protected] Fax: 404-894-5700 Phone: 541-737-8421 Session: Self-Assembly Email: Fax: 541-737-3385 [email protected] Email: [email protected] Session: Composites Session: Self-Assembly Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 59

Ms. Kimberly Nelson Ms. Lori A. Perine Dr. Chris Risbrudt IPST at Georgia Institute of Exectutive Director, Agenda 2020 Director Technology American Forest & Paper USDA FS, Forest Products Laboratory 500 10th St., NW Association One Gifford Pinchot Dr. Atlanta, GA 30318 1111 19th Street, NW, Ste. 800 Madison, WI 53726 Phone: 404-894-5758 Washington, DC 20036 Phone: 608-231-9318 Email: Phone: 202-463-2777 Fax: 608-231-9567 [email protected] Fax: 202-463-4711 Email: [email protected] Recorder Email: [email protected] Session: Sensors Workshop Integrator Dr. Xuan Nguyen Dr. Alison Roberts Research Fellow Dr. Arthur Ragauskas Associate Professor International Paper Associate Professor University of Rhode Island 6285 Tri-Ridge Blvd. IPST at Georgia Institute of Dept. of Biological Sciences Loveland, OH 45140 Technology Kingston, RI 02881 Phone: 513-248-6073 500 10th St., NW Phone: 401-874-4098 Email: [email protected] Atlanta, GA 30318 Fax: 401-874-5974 Session: Composites Phone: 404-894-9701 Email: [email protected] Fax: 404-894-4778 Session: Cell Wall Ms. Tracy Nollin Email: [email protected] Phone: 408-206-2558 Session: Composites Dr. Mihail Roco Session: Analytical Chair, National Science & Technology Dr. B.V. Ramarao Council’s Subcommittee on NSET Mr. Larry G. Oien Professor & Associate Director National Science Foundation Technology Sourcing Manager ESPRI/SUNY 4201 Wilson Blvd. Flint Ink Forestry Drive Arlington, VA 22230 4600 Arrowhead Drive Syracuse, NY 13260 Phone: 703-292-8301 Ann Arbor, MI 48105 Phone: 315-470-6513 Fax: 703-292-9013 Phone: 734-622-6308 Fax: 315-470-6945 Email: [email protected] Fax: 734-622-6101 Email: [email protected] Guest Speaker Email: [email protected] Session: Sensors Session: Self-Assembly Dr. Augusto Rodriguez Dr. Delmar Raymond Manager R&D Mr. Raymond R. Parent Director, Strategic Energy Georgia-Pacific Corporation VP Technology/R&D Director Weyerhaeuser Co. 2883 Miller Road Sappi Fine Paper N.A. Technology 33330 8th Ave. So. Decatur, GA 30035 Center Federal Way, WA 98023 Phone: 770-593-6807 89 Cumberland Street Phone: 253-924-6850 Fax: 770-322-9973 Westbrook, ME 04092 Fax: 253-924-6812 Email: [email protected] Phone: 207-856-3556 Email: Session: Sensors Fax: 207-856-3770 [email protected] Email: [email protected] Session: Sensors Ms. Melissa Rollins Session: Self-Assembly Administrative Assistant Dr. Timothy G. Rials IMERYS Dr. Robert Pelton Professor 100 Mansell Ct. E Professor University of Tennessee Roswell, GA 30076 McMaster University 2509 Jacob Drive Phone: 770-645-3369 1280 Main St., W Knoxville, TN 37996-4510 Fax: 770-645-3391 Hamilton, ONT L8S 4L7 Phone: 865-946-1129 Email: [email protected] Phone: 905-529-7070 Fax: 865-946-1109 Recorder Fax: 905-528-5114 Email: [email protected] Email: [email protected] Session: Analytical Dr. Maren Roman Session: Composites Assistant Professor Dr. Tom Richard Virginia Tech Professor 230 Cheatham Hall Penn State University Blacksburg, VA 24061-0323 225 Ag. Engineering Bldg Phone: 540-231-1421 University Park, PA 16802 Fax: 540-231-8176 Phone: 814-865-3722 Email: [email protected] Fax: 814-863-1031 Session: Composites Email: [email protected] Session: Composites 60 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Dr. Howard Rosen Mr. Amit Saxena Mr. Glen Tracy Staff Specialist IPST at Georgia Institute of Executive Director USDA Forest Service RVUR Technology Paper Technology Foundation 1400 Independence Ave., SW, 500 10th St., NW Western Michigan University Mailstop: 1114 Atlanta, GA 30318 Kalamazoo, MI 49008-5441 Washington, DC 20250-1114 Phone: 404-894-9701 Phone: 264-276-3856 Phone: 703-605-4196 Email: [email protected] Fax: 269-276-3535 Fax: 703-605-5137 Recorder Email: [email protected] Email: [email protected] Session: Self-Assembly Session: Self Assembly Dr. John Henry Scott Physicist Dr. David L. VanderHart Dr. David Rothbard NIST Chemist Chemical Microscopist 100 Bureau Drive Stop 8371 NIST Bureau of Engraving & Printing Gaithersburg, MD 20899-8371 101 Bureau Drive 14th & C Streets, SW, Room 207- Phone: 301-975-4981 Gaithersburg, MD 20899 25A Fax: 301-471-1321 Phone: 301-975-6754 Washington, DC 20228 Email: [email protected] Fax: 301-975-3928 Phone: 202-874-3102 Session: Analytical-Speaker Email: [email protected] Fax: 202-874-3310 Session: Cell Wall Email: Dr. Rana Shehadeh [email protected] Director Dr. Mark VanLandingham Session: Analytical-Speaker Georgia-Pacific Corporation U.S. Army Research Laboratory 133 Peachtree Street, NE 100 Bureau Drive Dr. Alan Rudie Atlanta, GA 30303 Gaithersburg, MD 20899 Project Leader, Chemistry & Pulping Phone: 404-652-6038 Phone: 410-306-0700 USDA Forest Service, Forest Fax: 404-487-4442 Email: Products Laboratory Email: [email protected] [email protected] One Gifford Pinchot Dr. Session: Composites Session: Analytical-Speaker Madison, WI 53726 Phone: 608-231-9496 Dr. Allan Showalter Dr. Wilfred Vermerris Fax: 608-231-9538 Professor Assistant Professor Email: [email protected] Ohio University Purdue University - Agronomy Session: Analytical Dept. of Plant Biology 915 W. State Street Athens, OH 45701 West Lafayette, IN 47907-2054 Dr. Nigel D. Sanders Phone: 740-593-1135 Phone: 765-496-2645 Technical Manager Fax: 740-593-1130 Fax: 765-496-2926 Specialty Minerals Inc. Email: [email protected] Email: [email protected] 9 Highland Avenue Session: Cell Wall Session: Cell Wall Bethlehem, PA 18017 Phone: 610-861-3457 Dr. Chris Somerville Dr. Kathryn Wahl Fax: 610-861-3412 Director Materials Research Scientist Email: Carnegie Institution U.S. Naval Research Laboratory [email protected] 260 Panama Street Code 6176 Session: Composites Stanford, CA 94305 Washington, DC 20375 Phone: 650-325-1521, Ext. 203 Phone: 202-767-5419 Dr. Jagannadh Satyavolu Fax: 650-325-6857 Fax: 202-767-3321 Process Technology Team Leader Email: [email protected] Email: [email protected] Cargill Industrial Starches Session: Cell Wall Session: Analytical 1710 16th Street, SE Cedar Rapids, IA 52401 Dr. Ian Suckling Dr. Theodore H. Wegner Phone: 319-399-6612 Scientist Assistant Director Fax: 319-399-6666 Ensis Papro USDA FS, Forest Products Email: 49 Sala St. Laboratory [email protected] Rotorua, New Zealand One Gifford Pinchot Dr. Session: Composites Phone: 64-7-343-5867 Madison, WI 53726 Fax: 64-7-343-5695 Phone: 608-231-9479 Email: Fax: 608-231-9567 [email protected] Email: [email protected] Session: Composites Workshop Co-Chair Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 61

Paul West Dr. Joseph D. Wright Dr. JiLei Zhang Phone: 408-206-2558 President & CEO Associate Professor Session: Analytical PAPRICAN Mississippi State University 570 Boul. St-Jean 100 Blackjack Road Dr. R. Sam Williams Pointe-Claire, QUEBEC H9R 3J9 Starkville, MS 39759 Project Leader, Wood Surface Phone: 514-630-4102 Phone: 662-325-9413 Chemistry Fax: 514-630-4110 Fax: 662-325-8126 USDA FS, Forest Products Email: [email protected] Email: [email protected] Laboratory Session: Sensors Session: Analytical One Gifford Pinchot Dr. Madison, WI 53726 Dr. Yibin Xue Dr. Jinwen Zhang Phone: 608-231-9412 Assistant Research Professor Assistant Professor Fax: 608-231-9262 Mississippi State University Washington State University Email: [email protected] 124 Northgate Drive 1445 NE Terre View Dr., Suite A Session: Sensors Starkville, MS 39759 Pullman, WA 99163 Phone: 662-325-5450 Phone: 509-335-8723 Dr. William T. Winter Fax: 662-325-5433 Fax: 509-335-5077 Director, Cellular Res. Inst. Email: [email protected] Email: [email protected] SUNY-ESF Session: Analytical Session: Composites 121 E.C. Jahn Laboratory Syracuse, NY 13210 Dr. Zheng-Hua Ye Dr. Junyong Zhu Phone: 315-470-6876 Associate Professor Project Leader Fax: 315-470-6856 University of Georgia USDA FS Forest Products Email: [email protected] Dept. of Plant Biology Laboratory Session: Sensors Athens, GA 30602 One Gifford Pinchot Drive Phone: 706-542-1832 Madison, WI 53726 Fax: 706-542-1805 Phone: 608-231-9520 Email: Fax: 608-231-9538 [email protected] Email: [email protected] Session: Cell Wall Session: Sensors 62 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 63

Appendix C: Breakout Group Members

Analytical Methods for Dr. Steve Keller Dr. Alan Rudie Nanostructure Associate Professor Project Leader, Chemistry & Characterization SUNY-ESF/ESPRI Pulping Chairs: Jim Beecher and Phone: 315-470-6907 USDA FS, Forest Products Tim Rials Email: [email protected] Laboratory Phone: 608-231-9496 Dr. Dimitri Argyropoulos Dr. Dimitri Argyropoulos Dr. Dave Knox Email: [email protected] Professor Research Director North Carolina State Univ. Meadwestvaco Dr. John Henry Scott Phone: 919-515-7708 Phone: 301-497-1340 Physicist Email: [email protected] Email: NIST [email protected] Phone: 301-975-4981 Dr. Don Baer Dr. Don Baer Email: [email protected] Laboratory Fellow Dr. Lucian Lucia Pacific Northwest National Associate Professor of Chemistry Dr. Mark Van Landingham Laboratory North Carolina State Univ. U.S. Army Research Laboratory Phone: 509-376-1609 Phone: 919-515-7707 Phone: 410-306-0700 Email: [email protected] Email: [email protected] Email: [email protected] Dr. Fred Barlow Dr. Tony Lyons Consultant Director of Research Dr. Kathy Wahl Phone: 912-399-6552 IMERYS Materials Research Scientist Email: [email protected] Phone: 478-553-5243 U.S. Naval Research Laboratory Email: [email protected] Phone: 202-767-5419 Dr. Jim Beecher Dr. Jim Beecher Email: [email protected] Group Leader, Analytical Dr. Christine Mahoney Chemistry & Microscopy Lab. National Institute of Standards & Paul West USDA FS, Forest Products Technology Phone: 408-206-2558 Laboratory Phone: 301-975-8515 Phone: 608-231-9475 Email: [email protected] Dr. Anna Xue Email: [email protected] Assistant Research Professor Dr. Vijay Mathur Mississippi State University Dr. George Cody President Phone: 662-325-5450 Geophysical Laboratory GR International Email: [email protected] Carnegie Institution of Washington Phone: 253-924-6070 Phone: 202-475-8980 Email: [email protected] Cell Wall Nanotechnology Email: [email protected] Chairs: Rajai Atalla and Ms. Tracy Nollin Candace Haigler Dr. Tom Elder Phone: 408-206-2558 Research Forest Products Dr. Rajai Atalla Technologist Dr. Tim Rials Sr. Scientist USDA FS Professor USDA FS, Forest Products Southern Research Station University of Tennessee Laboratory Phone: 318-473-7008 Phone: 865-946-1129 Phone: 608-231-9443 Email: [email protected] Email: [email protected] Email: [email protected] Dr. John Hermanson Dr. David Rothbard Dr. Al Button Research Scientist Chemical Microscopist President USDA FS Bureau of Engraving & Printing Buttonwood Consulting, LLC Forest Products Laboratory Phone: 202-874-3102 Phone: 920-730-5670 Phone: 608-231-9229 Email: Email: [email protected] Email: [email protected] [email protected] 64 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Dr. Jeffrey Catchmark Dr. Wilfred Vermerris Ms. Karina Hanninen Operations Manager Assistant Professor Consultant Penn State University Purdue University - Agronomy Jaakko Poyry Consulting Phone: 814-865-6577 Phone: 765-496-2645 Phone: 3589-8947-2119 Email: [email protected] Email: [email protected] Email: [email protected] Dr. Chuck Frihart Dr. Zheng-Hua Ye Dr. Kevin Hodgson Project Leader, Wood Adhesives Associate Professor Professor Science & Technology University of Georgia University of Washington USDA FS, Forest Products Phone: 706-542-1832 Phone: 206-543-7346 Laboratory Email: Email: Phone: 608-231-9208 [email protected] [email protected] Email: [email protected] Polymer Composites and Dr. Sam Hudson Dr. Michael Hahn Nano-reinforced Materials Professor Polymer Chemistry Associate Professor Chairs: Margaret Joyce and North Carolina State Univ. University of Georgia Art Ragauskas Phone: 919-515-6545 Phone: 706-542-4457 Email: [email protected] Email: [email protected] Dr. Don Anthony President & Executive Director Dr. Ki-Oh Hwang Dr. Candace Haigler The Council for Chemical Lead Research Scientist Professor Research Cargill Inc. North Carolina State Univ. Phone: 202-429-3971 Phone: 319-399-6181 Phone: 919-515-5645 Email: [email protected] Email: [email protected] Email: [email protected] Mr. Sven Arenander Mr. Gopal Iyengar Dr. Shekhar Joshi Manager Paper Science Solutions Sr. Research Engineer Associate Professor International Paper Stora Enso North America Michigan Tech U, SFRES Phone: 513-248-6694 Phone: 715-422-2329 Phone: 906-487-3480 Email: Email: Email: [email protected] [email protected] [email protected] Dr. Bela Mulder Dr. Hongda Chen Dr. Margaret Joyce Professor National Program Leader, Associate Professor Wageningen University Bioprocessing Engineering Western Michigan University Phone: 31206081234 USDA/CSREES Phone: 269-276-3514 Email: [email protected] Phone: 202-401-6497 Email: Email: [email protected] [email protected] Dr. Alison Roberts Associate Professor Dr. Ray Drumright Dr. Alexander Koukoulas University of Rhode Island Dow Chemical Chief Scientist Phone: 401-874-4098 Phone: 989-636-6084 International Paper Email: [email protected] Email: [email protected] Phone: 513-348-6614 Email: Dr. Allan Showalter Mr. Jerry Dykstra Dr. Allan Showalter Mr. Jerry Dykstra [email protected] Professor Pulp & Paper Technology Director Ohio University Buckman Laboratories Dr. Charlie Kramer Phone: 740-593-1135 Phone: 901-272-8389 R&D Director Email: [email protected] Email: [email protected] Albany Intl. Research Co. Phone: 508-337-9541 Dr. Chris Somervill Dr. Alex Fridman Dr. Chris SomervillSomerville Dr. Alex Fridman Email: [email protected] Director Professor Carnegie Institution Drexel University Mr. Reid Miner Phone: 650-325-1521, Ext. 203 Phone: 215-895-1542 Vice President Email: [email protected] Email: [email protected] NCASI Phone: 919-941-6407 Dr. Dave VanderHart Dr. Gil Garnier Dr. Dave VanderHart Dr. Gil Garnier Email: [email protected] Chemist Kimberly-Clark NIST Phone: 920-721-2557 Dr. Hiroki Nanko Phone: 301-975-6754 Email: [email protected] Principal Research Scientist Email: [email protected] IPST at Georgia Institute of Technology Phone: 404-894-9520 Email: [email protected] Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 65

Dr. Xuan Nguyen Self-Assembly and Dr. Derek Gray Research Fellow Biomimetics Professor, Chemistry International Paper Chairs: Wolfgang Glasser, McGill University Phone: 513-248-6073 Derek Gray and Pete Phone: 514-398-6182 Email: [email protected] Lancaster Email: [email protected] Dr. Bob Pelton Dr. Sundar Atre Dr. Jim Holbery Professor Professor Senior Scientist McMaster University Oregon State University Pacific Northwest National Phone: 905-529-7070 Phone: 541-737-2367 Laboratory Email: [email protected] Email: Phone: 509-375-3686 [email protected] Email: [email protected] Dr. Art Ragauskas Associate Professor Dr. Brian Boyer Dr. John Kadla IPST at Georgia Institute of Patent Attorney Associate Professor Technology Squire, Sanders & Dempsey L.L.P. University of British Columbia Phone: 404-894-9701 Phone: 415-954-0230 Phone: 604-827-5254 Email: [email protected] Email: [email protected] Email: [email protected] Dr. Tom Richard Dr. Joe Bozell Dr. Pete Lancaster Professor Principal Scientist Scientific Advisor, Fiber Science Penn State University National Renewable Energy Lab. R&D Phone: 814-865-3722 Phone: 303-384-6276 Weyerhaeuser Co. Email: [email protected] Email: [email protected] Phone: 253-924-6688 Email: Dr. Maren Roman Dr. Maren Roman Dr. Paul Burrows [email protected] Assistant Professor Laboratory Fellow Virginia Tech Pacific Northwest National Dr. Kaichang Li Phone: 540-231-1421 Laboratory Assistant Professor Email: [email protected] Phone: 509-375-5990 Oregon State University Email: [email protected] Phone: 541-737-8421 Dr. Nigel Sanders Dr. Nigel Sanders Email: Technical Manager Dr. Dan Caulfield [email protected] Specialty Minerals Inc. Research Chemist Phone: 610-861-3457 USDA FS, Forest Products Dr. Tom Lindstrom Email: Laboratory STFI - Packforsh AB [email protected] Phone: 608-231-9436 Phone: 468-676-7000 Email: [email protected] Email: [email protected] Dr. Nadh Satyavolu Process Technology Team Leader Dr. Scott Cunningham Dr. Yuri Lvov Cargill Industrial Starches New Market Development Professor Phone: 319-399-6612 Manager Louisiana Tech University Email: DuPont Phone: 318-257-5144 [email protected] Phone: 302-999-2969 Email: [email protected] Email: Dr. Rana Shehadeh [email protected] Mr. Steve Masia Director Research Scientist Georgia-Pacific Corporation Dr. Mahendra Doshi SAPPI Fine Paper N.A. Technology Phone: 404-652-6038 Executive Editor Center Email: [email protected] Progress in Paper Recycling Phone: 207-856-3579 Phone: 920-832-9101 Email: [email protected] Dr. Ian Suckling Email: [email protected] Scientist Mr. Larry Oien Ensis Papro Dr. Alan Esker Technology Sourcing Manager Phone: 64-7-343-5867 Assistant Professor Flint Ink Email: Virginia Tech Phone: 734-622-6308 [email protected] Phone: 540-231-4601 Email: [email protected] Email: [email protected] Dr. Jinwen Zhang Mr. Ray Parent Assistant Professor Dr. Wolfgang Glasser VP Technology/R&D Director Washington State University Prof. Emeritus Sappi Fine Paper N.A. Technology Phone: 509-335-8723 Virginia Tech Center Email: [email protected] Phone: 540-231-4403 Phone: 207-856-3556 Email: [email protected] Email: [email protected] 66 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Dr. Howard Rosen Ms. Sara Dilllich Dr. Augie Rodriguez Staff Specialist Lead Technology Manager Manager R&D USDA Forest Service RVUR DOE-Materials, Sensors & Georgia-Pacific Corporation Phone: 703-605-4196 Automation Phone: 770-593-6807 Email: [email protected] Phone: 202-586-7925 Email: [email protected] Email: [email protected] Mr. Glen Tracy Dr. Sam Williams Executive Director Mr. Paul Gilbert Project Leader, Wood Surface Paper Technology Foundation Engineer Chemistry Phone: 264-276-3856 SAPPI Fine Papers NA USDA FS, Forest Products Email: [email protected] Phone: 207-856-3835 Laboratory Email: [email protected] Phone: 608-231-9412 Nanotechnology in Sensors, Email: [email protected] Processing and Process Dr. Graham Moore Control Strategic Consulting Manager Dr. Bill Winter Chairs: Yulin Deng and JY PIRA International Director, Cellular Res. Inst. Zhu Phone: 44-1372-802000 SUNY-ESF Email: [email protected] Phone: 315-470-6876 Dr. Charles Cleland Email: [email protected] SBIR National Program Leader Dr. Ram Ramarao US Department of Agriculture Professor & Associate Director Dr. Joe Wright Phone: 202-401-6852 ESPRI/SUNY President & CEO Email: [email protected] Phone: 315-470-6513 PAPRICAN Email: [email protected] Phone: 514-630-4102 Mr. Yulin Deng Email: [email protected] Professor Dr. Del Raymond IPST at Georgia Institute of Director, Strategic Energy Dr. JY Zhu Technology Weyerhaeuser Co. Project Leader Phone: 404-894-5758 Phone: 253-924-6850 USDA FS, Forest Products Email: [email protected] Email: Laboratory [email protected] Phone: 608-231-9520 Email: [email protected] Dr. Chris Risbrudt Director USDA FS, Forest Products Laboratory Phone: 608-231-9318 Email: [email protected] Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 67

Appendix D: Selected Workshop Presentation Summaries

The following are summaries of selected Extension Service (CSREES) has identified presentations from the Workshop. The specific priority research areas in agriculture complete presentations can be found at and food systems, several of which can www.nanotechforest.org. directly benefit from research in nanotechnology. Research areas, which are USDA Nanotechnology Roadmap – highlighted in the USDA Nanotechnology Hongda Chen, National Program Roadmap, are complementary to and Leader, Bioprocessing Engineering, supportive of the goals and missions of USDA-CSREES CSREES and the Experiment Station Committee on Organization and Policy Nanotechnology, as a new enabling (ESCOP). Research areas include: pathogen technology, has the potential to revolutionize and contaminant detection, identity agriculture and food systems in the United preservation and tracking, smart treatment States. Agricultural and food systems security, delivery systems, smart systems integration for disease treatment delivery systems, new tools agriculture and food processing, nanodevices for molecular and cellular biology, new for molecular and cellular biology, nanoscale materials for pathogen detection and materials science and engineering, protection of the environment are examples environmental issues and agricultural waste, of the important links of nanotechnology to and education of the public and future the science and engineering of agriculture workforce. and food systems. Some overarching examples of nanotechnology as an enabling National Nanotechnology Initiative: technology are: Overview and Planning for the Future – Mihail Roco, Chair, National Science & Technology Council’s Subcommittee on • Production, processing, and shipment of Nanoscale Science, Engineering & food products can be made more secure Technology through the development and implementation of nanosensors for The vision of the NNI is a future in which the pathogen and contaminant detection. ability to understand and control matter on • The development of nanodevices can the nanoscale leads to a revolution in technology and industry. Toward this vision, enable the keeping of historical the NNI will expedite the discovery, environmental records and location development, and deployment of tracking of individual shipments. nanotechnology in order to achieve • Systems that provide the integration of responsible and sustainable economic “Smart Systems” sensing, localization, benefits, to enhance quality of life, and to reporting, and remote control can promote national security. The initiative is a increase efficiency and security. multi-agency, multidisciplinary program that supports research and development (R&D), The USDA is a partner agency of the National develops infrastructure, and promotes Nanotechnology Initiative (NNI). The education, knowledge diffusion, and Cooperative State Research, Education and commercialization in nanotechnology. 68 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Concomitant with development of new • Develop educational resources, a skilled technology options, the NNI is addressing workforce, and the supporting nanotechnology’s various societal infrastructure and tools to advance dimensions. Interagency coordination is nanotechnology. managed through the Nanoscale Science, Engineering, and Technology (NSET) • Support responsible development of Subcommittee of the National Science and nanotechnology. Technology Council (NSTC) Committee on Technology. The NNI will provide a balanced and The goals of the NNI are as follows: coordinated investment in the program component areas and in a broad spectrum of • Maintain a world-class R&D program applications. This will ensure that the United aimed at realizing the full potential of States remains a global leader in the nanotechnology. responsible development of nanotechnology and secures the resulting benefits to the • Facilitate transfer of the new technologies economy, to national security, and to the into products for economic and public quality of life of all citizens. benefit. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 69

Department of Energy Nanotechnology Programs – Paul Burrows, Pacific Northwest National Laboratory 70 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

The National Nanotechnology Initiative applied research through investigator-led – Sharon Hays, Deputy Associate activities, multidisciplinary centers of Director, Technology Division of the excellence, and infrastructure development, Office of Science & Technology and will continue to support activities aimed at assessing the societal implications of The federal government’s investments in nanotechnology, including ethical, legal, science and technology have been guided by public and environmental health, and several fundamental principles. These workforce-related issues. The President’s principles include the following: a) sustain Council of Advisors on Science and and nurture America’s world-leading science Technology (PCAST) reviews the multi-agency and technology enterprise through pursuit of nanotechnology R&D programs and specific agency missions and through articulates a strategic plan for the program, stewardship of critical research fields and defining specific grand challenges to guide scientific facilities; b) strengthen and expand the program and identifying metrics for access to high-quality science, mathematics, measuring progress toward those grand and engineering education, and contribute to challenges. preparing the next generation of scientists and engineers; c) focus on activities that The President’s 2005 Budget provides $1 require a federal presence to attain national billion for the multi-agency NNI, a doubling goals, including national security, over levels in 2001, the first year of the environmental quality, economic growth and Initiative. This investment advances our prosperity, and human health and well being; understanding of nanoscale phenomena— and d) promote international cooperation in the unique properties of matter that occur at science and technology that will strengthen the level of clusters of atoms and molecules – the advance of science and achievement of and enable the use of this knowledge to bring national priorities. about improvements in medicine, manufacturing, high-performance materials, Nanotechnology will likely have a broad and information technology, and energy and fundamental impact on many sectors of the environmental technologies. Agency economy. The NNI incorporates long-term investments must be consistent with research leading to new fundamental interagency planning documents such as the understanding and discoveries of NNI implementation plan. phenomena, processes, and tools for nanotechnology, and applies them towards grand challenges that support agency missions. The NNI creates centers and networks of excellence to encourage research networking and shared academic users’ facilities, develop enabling infrastructures to accelerate commercialization, and prepare a new generation of skilled workers with the multidisciplinary perspectives necessary for rapid progress in nanotechnology.

The President signed the 21st Century Nanotechnology Research and Development Act, which put into law programs and activities supported by the NNI. Consistent with this legislation, in 2005 the Initiative will continue to focus on fundamental and Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 71

Forest Products Industry Perspectives for Nanotechnology – Del Raymond, Weyerhaeuser 72 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Nanotechnology – The European Forest industry/research interactions in consortia Products Perspective – Tom Lindstrom, undertaking projects with substantial critical STFI mass. Research and development activities should promote development of new Nanotechnologies and nanosciences professional skills. For an effective represent a new multi-disciplinary and development, European universities may integrative approach to materials science and have to adapt with respect to education and engineering, as well as designing new systems training in nanosciences and and processes by exploiting effects at the nanotechnologies. Whenever appropriate, nanoscale and controlling the structure and ethical, societal, communication, health, self-assembly of materials. Europe enjoys a environmental and regulatory issues, in strong position in the nanosciences that needs particular metrology and measurement to be translated into a competitive advantage traceability aspects, should be addressed. for European industry. The objective is twofold: to promote the creation of a European nanotechnology-enabled industry, and to promote the uptake of nanotechnologies into existing industrial sectors. Research may be long-term and high- risk but will be oriented towards industrial application and co-ordination of efforts at the European Union (EU) level. Encouraging industrial companies, including start-ups, will be pursued through the promotion of strong Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 73 74 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Nanobioterials—-Arthur J. Ragauskas, Institute of Paper Science and Technology — Georgia Institute of Technology, Atlanta, GA Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 75

Appendix E: Workshop Organizing Committee and Contacts for Further Information

Rajai Atalla Scott Cunningham Margaret Joyce USDA-FS, Forest Products E.I. DuPont de Nemours and Western Michigan University Laboratory Company Kalamazoo, MI Madison, WI Wilmington, DE [email protected] [email protected] [email protected] 269-276-3514 608-231-9443 302-999-4244 Stephen Kelley P. (Bala) Balaguru Yulin Deng National Renewable Energy Rutgers University IPST at Georgia Institute of Laboratory Piscataway, NJ Technology Golden, CO [email protected] Atlanta, GA [email protected] 732-445-3537 [email protected] 303-384-6123 404-894-5759 Jim Beecher Jane Kohlman USDA FS Wolfgang Glasser USDA FS, Forest Products Forest Products Laboratory Virginia Tech Laboratory Madison, WI Blacksburg, VA Madison, WI [email protected] [email protected] [email protected] 608-231-9475 540-231-4403 608-231-9479

G. Ronald Brown Lawrence Gollob Alexander Koukoulas MeadWestvaco Georgia Pacific Resins Inc. International Paper Company Laurel, MD [email protected] Tuxedo Park, NY [email protected] 770-593-6867 [email protected] 301-497-1301 914-577-7275 Derek Gray Paul Burrows McGill Peter Lancaster U.S. DOE, Pacific Northwest Montreal, QC Weyerhaeuser National Laboratory [email protected] Federal Way, WA Richland, WA 514-398-6182 [email protected] [email protected] 253-924-6688 509-375-5990 Wayne Gross TAPPI Lucian Lucia Robert Caron Norcross, GA North Carolina State University TAPPI [email protected] Raleigh, NC Norcross, GA 770-209-7233 [email protected] [email protected] 919-515-7707 770-209-7236 Candace Haigler North Carolina State University Shawna McQueen Jeffrey Catchmark Raleigh, NC Energetics Pennsylvania State University [email protected] Columbia, MD University Park, PA 919-515-5645 [email protected] [email protected] 410-953-6235 814-865-6577 Philip Jones IMERYS Roswell, GA [email protected] 770-645-3373 76 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Raymond Parent Augusto Rodriguez Joseph Wright Sappi Fine Paper N.A. Georgia-Pacific Corporation PAPRICAN Westbrook, ME Decatur, GA Pointe Claire, Quebec [email protected] [email protected] [email protected] 207-856-3556 770-593-6807 514-630-4102

Lori Perine Douglas Stokke Jinwen Zhang American Forest & Paper Iowa State University Washington State University Association Ames, IA Pullman, WA Washington, DC [email protected] [email protected] [email protected] 515-294-2115 509-335-8723 202-463-2777 Theodore Wegner Junyong Zhu Art Ragauskas USDA FS USDA FS IPST at Georgia Institute of Forest Products Laboratory Forest Products Laboratory Technology Madison, WI Madison, WI Atlanta, GA [email protected] [email protected] [email protected] 608-231-9434 608-231-9520 404-894-9701 Michael Wolcott Timothy Rials Washington State University University of Tennessee Pullman, WA Knoxville, TN [email protected] [email protected] 509-335-6392 865-946-1129 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 77

Appendix F: Tools for the Characterization of Nanometer-Scale Materials

Before discussing some of the contemporary tools which are available and might advance Specimen Preparation our understanding of cell wall structure, lets Drying review some limitations. When employing a technique in which photon or particle beams Drying methods for wood and artifacts are used to form images by transmission, the created by critical-point drying, freeze drying, specimen must be thin. and air drying are reviewed by Duchesne and Daniel (Duchesne 1999). Another challenge is discriminating different materials. Lignin and holocellulose are distinguishable because lignin has mostly Microtomy aromatic carbon structures, and celluloses are It is a serious challenge to prepare 20- to 30- mostly aliphatic carbon structures. There are nm cross sections of homogeneous materials few differences between cellulose and by ultramicrotomy. The challenge is greatly hemicelluloses: molecular weight, branching, increased with heterogeneous and fibrous some side groups, non-glucose sugar materials. The microtome knife is really monomers. initiating a crack which will grow along the path of least resistance (Jesior 1986). The Another general shortcoming is the presence of fibrous materials such as interpretation of microscopy/spectroscopy cellulose fibrils will redirect the progress of the without an understanding of the probe/ crack. specimen interaction. This was mentioned many times during the Workshop discussions. For thin cross sections, which are appropriate It was suggested that computational models for visible light microscopy, the common should be employed for interpretation. This practice is to ‘soften’ wood by swelling in appears to be particularly problematic in water or other liquid mixtures. This practice microscopy because images tend to be may not always be appropriate. An interpreted as a scene before our eyes lit by alternative means of ‘softening’ wood could the sun. be to heat the specimen. This is equivalent to the widely employed practice in synthetic Duchesne and Daniels recently reviewed polymer microtomy–cryoultramicrotomy–of wood cell wall structure, the techniques used lowering the specimen temperature to to learn that structure and some of the achieve the desired hardness. limitations (Duchesne 1999). Some tools which may be useful in advancing our Distortions introduced by microtomy have knowledge are reviewed below. been systematically examined (Jesior 1986), and means to reduce distortion with diamond and glass knives have been reported (Matzelle 2000; Matzelle 2003). H. Sitte, who has extensively studied microtomy and 78 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

directed the design of commercial Most of the published examples involve instruments, has thoroughly reviewed inorganic semiconductor materials (Veirman microtomy practice (Sitte 1996). 1999; Phaneuf 1999) or inorganic composites (Kim 2000). There are reports of Polishing biological specimen cross sections–human hair and housefly eye (Ishitani 1995). An FIB Grinding and polishing are frequently used to was used to prepare a cross section of color prepare flat specimens for analysis (ASTM photographic film which was subsequently 1960). Specimens of metals and alloys for imaged by the ion beam (Phaneuf 1999). SEM/EDX or optical microscopy are routinely John Henry Scott showed a wood cross prepared by cutting cross sections and section which was prepared by FIB in his polishing the surface with abrasives of presentation at the Workshop. increasing fineness (Metallographic sectionssections). There is no special difficulty if all Estimates of the damage caused by FIB can phases of the specimen have similar be made by Monte Carlo simulations (Kim hardness. 2000) or by determining the depth to which gallium ions are implanted. These have been These techniques have been adapted for reported to agree well (Giannuzzi 1999). preparing large cross sections of paper by Specific results depend upon material embedding the paper in epoxy resin composition and ion energy, but the ion (Williams 2000; Rothbard 2003). implantation depth is usually about 20 nm, and atom displacements are confined to Focused Ion Beam Cutting about 30 nm for gallium ions in low atomic number materials. The depth of the damage Ions with kilovolt energy interact with solid layer is strongly dependent upon ion specimens in a number of ways. The primary accelerating voltage and the incident ion ions implant within the specimen and milling angle (McCaffrey 2001). Single crystal displace specimen atoms in the process. silicon layers cut by FIB still show evidence of Along this interaction path, secondary ions crystallinity where the ion damaged layers and neutrals are sputtered from the specimen would be expected to be amorphous along with electrons and photons. Ultimately, (Giannuzzi 1999). some of the energy raises the specimen temperature. These interactions can have Another consideration for biological useful effects and some create damage materials is that the specimens will necessarily (Meingaills 1987). be exposed to vacuum during preparation. However, this may not be a concern because Focused ion beams (FIBFIB) are often used in the the preparations are intended for TEM, STXM, semiconductor electronics industry for or EXAFS examination where further vacuum manufacturing and specimen preparation. exposure will occur. Typically, 30-keV gallium ions focused to about 100 nm with beam currents of The focused ion beams are often used to

nanoamperes (nA) are used to cut specimens. decompose gases such as W(CO)6 at the In the usual process, stair-stepped depressions specimen surface to deposit metal decoration are carved into the specimen with a rastered on the specimen for protection or to reduce ion beam on either side of a thin (~ 100 nm) charge accumulation. section to be studied. Finally, the edges of the thin section are cut free from the specimen, which is recovered and mounted on a transmission electron microscopy grid (Giannuzzi 1999; Overwijk 1993). Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 79

Microscopy and Spectroscopy One excellent and comprehensive review by Microscopy and Spectroscopy an SPM-pioneer offers a good place to begin learning of the promise and pitfalls of SPM Scanning Probe Microscopies (Colton 2004). This review begins with Scanning probe microscopy techniques, scanning tunneling microscopy (STMSTM) and especially tapping mode atomic force follows its evolution and concludes with the microscopy, are the most frequently measurement of mechanical properties mentioned techniques for characterizing utilizing nanoindentation methods. nanometer-scale structures. These techniques are reported in well over 10,000 research Atomic Force Microscopy papers each year. Their potential use is evident, and the potential for abuse is much Atomic force microscopy (AFMAFM) is the most more subtle. Like all microscopy techniques, often applied SPM method for describing SPM can be self-satisfying—an image will be molecular solids or biological specimens. In obtained (often just what you were looking its first mode, contact AFM, the stylus tip was for); the instruments are readily available and maintained in contact (or very near contact) convenient to operate. with the specimen as in a miniature profilometer. Currently, it is most often used in The early use of AFM by Hanley and Gray et. a tapping mode in which the stylus and al. to describe wood cell structure illustrates supporting cantilever are set into vibration some of the specimen preparation problems near their resonant bending frequency and limitations (Hanley 1992; Hanley 1994). (nominally ~ 100 kHz). Cell structures were subjected to physical and chemical treatment in the preparation The tip makes only intermittent contact with process. Although such methods are the specimen surface. The tip/specimen commonly used, it leaves concern that the interactions alter the amplitude, resonance resulting specimen is an accurate frequency, and phase angle of the oscillating representation of native plant morphology. cantilever. The relative vertical position of the The AFM images illustrate the problem of tip is moved to maintain constant amplitude probe tip shape convolution with specimen of oscillation; this is often described as morphology. amplitude modulation (AM-AFMAM-AFM). The reduced surface forces result in less specimen Interpretation of the images requires a damage. The change in vibration phase (i.e., thorough understanding of the probe/ the delay between the cyclic motive force specimen interactions. Quantitative modeling applied to the cantilever and the resultant of the contrast mechanism is encouraged. The movement of the cantilever) often is used to use of other microscopy techniques along with discriminate between areas with different SPM is beneficial in two ways: 1) examination composition on the specimen surface. The at larger scale will establish a context for phase image thus contains chemically high-resolution studies and help to select sensitive information. However, the representative fields, 2) other imaging interpretation of this information is not always methods will reinforce the SPM findings clear (Colton 2004; Raghavan 2000). because scanning probes frequently create artifacts. Frequency modulation (FM-AFMFM-AFM) is another dynamic mode of operation in which the This is a case where collaboration with an cantilever amplitude is maintained constant experienced SPM microscopist may be the while the stylus/specimen interaction alters the best path to understanding. frequency. FM-AFM is used with the stylus near the specimen surface but not in contact. An Fortunately, there have been many reviews of exhaustive review of dynamic AFM, including this field recently (Poggi 2004; Meyer 2004). theory and operation, is available (Garcia & Perez 2002). 80 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

Interactions between the stylus and specimen lithographically defined patterns of distinct arise from many different mechanisms—van functional groups. der Walls attraction, electrostatic, friction, viscoelastic, wetting, et cetera. It is not always Friction–nanotribology–is another force which evident which forces are involved. One has been studied using SPM (Burns 1999; frequent effect which is not always anticipated Carpick 2004). An in-depth review of friction is the condensation of water on the specimen force measurement applied mostly to atomic surface about the stylus. This results in a solids was prepared by Carpick and capillary force which is large enough to Salmeron (Carpick 1997). The non-vertical dominate the probe/specimen interaction. It component of stylus motion is often attributed is difficult to get the atmosphere dry enough to friction or viscosity. However, as Carpick to eliminate this water condensation. The points out: “If the sample surface is not flat, most frequent practice for very high resolution the surface normal force will have a studies is to work in ultrahigh vacuum (usual component directed laterally and will result in for atomic solids) or under fluids (water for contrast in the lateral force image.” We can biological materials). anticipate that there will not be a lot of flat surface on biological materials. AFM has been used to measure the van der Walls’ force between regenerated cellulose Nanoindentation surfaces (Notley 2004). Measurements were made in an aqueous environment with low pH Vertical forces may be used to measure and high ionic strength to suppress DLVO material properties of specimens such as charge effects. elastic modulus or hardness. This has been done with AFM for measurement of material properties as well as identification of phases Force Spectroscopy (VanLandingham 2001; Bischel 2000). The To learn some chemical or physical spatial resolution afforded by AFM must be information about a specimen in addition to tempered with inherent limitations due to the the topographical image, some microscopists definition of stylus tip shape and the non- have gained information by studying the vertical component of force. changing forces that occur as the probe approaches and retracts from the surface. Recently a review of the contact mechanics This is often called force spectroscopy and relevant to SFM has been published (Unertl can be performed at selected individual 1999). This emphasizes the assumptions locations or at each point in an entire image underlying and restricting the application of field (Dufrene 2002; van der Aa 2001). Stylus most commonly used models and their tips have been modified for force implications for SFM measurements. spectroscopy by chemical modification or by bonding cells to the surface. This has been More rigorous and quantitative material particularly valuable in characterizing cell property measurements can be obtained at a surfaces (Ahimou 2002; Ong 1999; Frederix sacrifice of spatial resolution using a 2004). Functionalized AFM tips were used to nanoindenter (Bhushan 1996; Colton,2004). study intermolecular interactions with epoxy With a nanoindenter the force on the probe polymers in different liquids (Vezenov 2002). and the position of the probe are measured independently. This is not the case with an A similar process, chemical force microscopy AFM probe; the force on the stylus point is (CFMCFM), was first described by Frisbie et. al. determined by the deflection of the cantilever (Frisbie 1994). Chemically modified probes which is related to the position relative to the were used to measure the adhesive and specimen. The nanoindenter probe only friction forces between the probe tip and moves vertically; whereas, an AFM stylus is organic monolayers terminating in always tilted from the vertical and often Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 81

twisted by lateral force. However, Near-Field Scanning Optical Microscopy nanoindenter probes are on the order of 50 nm in tip radius, which is much broader than The spatial resolution attainable with AFM styli. conventional optical techniques is limited to about half the wavelength of the light source Nanoindentation has been used to used. For visible radiation, this results in a quantitatively measure dynamic mechanical theoretical resolution limit of 200-300nm. properties as well as static measurements on Higher resolution—near-field scanning the nanometer scale (Syed Asif 2001; Syed optical microscopy (NSOMNSOM)—can be Asif 2000; Syed Asif 1999). With the obtained by illuminating a specimen through application of a small vertical oscillation to a very small aperture (ca. 50 nm) positioned the probe, quantitative stiffness imaging of very close to the specimen (about one mechanical properties can be mapped at the aperture diameter away). An extensive and nanoscale. This offers an excellent way to detailed review of NSOM is recommended transition between the optical microscopy (Dunn 1999). scale (micrometer scale) to the AFM scale (nanometer scale). These techniques are much To interpret NSOM images it is necessary to easier to apply to flat specimens than highly understand how these devices deliver light to textured surfaces. subwavelength dimensions and to characterize the fields at the aperture. One of Probe Shape the current limitations is due to the high temperatures developed at the end of the When characterizing non-planar specimens, scanning tip. Most of the radiant energy is the shape and size of the probe becomes absorbed by the conductive coating which important. The tip of the probe is often defines the aperture; this has resulted in described as a hemisphere having a temperatures near the tip of nearly 500°C. particular radius. Real probe tips are more NSOM tips can be used in the tapping AFM complex and are not often characterized. mode by synchronizing the detection with the However, the SPM image is a convolution of tip vibration. the probe tip shape and the morphology of the specimen; thus, it is important to Many examples involve the illumination of characterize the tip (Villarrubia 1997). specimens with NSOM and recording fluorescent emission from the specimen. Carbon nanotubes with diameters of about 1 Spectra from single molecules have been nm have been suggested as the ultimate high- measured using this approach. resolution probe. These probes have limitations, especially when they are not Scanning Electron Microscopy exactly perpendicular to the specimen surface. These effects have been analyzed Scanning electron microscopy (SEMSEM) offers and their use for non-contact imaging the possibility of nanometer resolution with examined (Snow 2002). Isolated protein little sample preparation. This is especially molecules on mica were imaged using the case with variable pressure or carbon nanotube non-contact AFM (Bunch environmental (ESEMESEM) in which specimens 2002). can be examined in a low pressure atmosphere without any conductive metal Multi-walled carbon nanotubes used a probes coating. This atmosphere could be water in tapping mode AFM offer a more complex vapor; therefore, plant or wood specimens situation. The nonlinear dynamics can be examined in great detail in their native appropriate for this interaction have been state. investigated experimentally and theoretically (Lee 2004). 82 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

The difficulty of achieving sharp images with Transmission Electron Microscopy good contrast increases with increasing atmospheric pressure. It also depends upon Transmission electron microscopy (TEMTEM) the experience and skill of the microscopist offers the possibility of sub-nanometer spatial and the characteristics of the microscope. resolution along with limited imagewise chemical information. The most serious There is little difference in the probability of limitations are that specimens must be thin secondary electron or backscatter electron enough that only single electron scattering emission for materials composed of carbon, events are likely—ca. 100 nm or less—and oxygen, and nitrogen. This means that the specimens must resist electron damage. SEM images convey little chemical Carbon replicas have been employed to information and mostly describe texture or avoid the problem of thick specimens (Cote topography. 1964; Norberg 1968).

Substantial advantage may be obtained by Images in TEM are created by the diffraction operating an SEM with a beam voltage in the of electrons. The materials with which we are range 0.5—5 keV. Low voltage (LVSEMVSEM) often mostly concerned are made of carbon, affords good voltage contrast on uncoated oxygen, and nitrogen, which have very similar specimens and reduces charging and electron scattering cross sections. There is very damage (Goldstein 1984). The difference in little contrast between different components. secondary electron emission between One approach to developing image contrast polymeric materials of different composition is to preferentially label a component with a can be optimized at low accelerating voltage higher atomic number element. Lignin has (Berry 1988). The LVSEM images only been labeled using bromine, potassium interrogate a shallow surface layer because permanganate, and osmium tetroxide the penetration depth of these electrons is (Duchesne 1999). limited (Goldstein 1984). The highest resolution images of cellulose Beam electrons stimulate the excitation of fibril morphology are a result of the inner-shell electrons, which result in the examination of developing wood cells. Cells emission of characteristic x-rays or Auger in different stages of development are rapidly electrons. For low atomic number atoms, the frozen (so quickly that water does not form probability of Auger electron emission is ice). The frozen specimens are cleaved, and greater than x-ray emission. X-rays emitted by the exposed surface is replicated with carbon this process can be quantified imagewise by and shadowed with platinum. The replica is energy dispersive x-ray analysis (EDXEDX). It is examined by TEM (Itoh 2002) difficult to quantify the low energy x-rays from low atomic number elements (Goldstein Our current knowledge of hemicellulose 1984). disposition is from TEM of specimens which have hemicellulose labeled with gold tagged EDX analysis is somewhat complicated in antibodies to hemicellulose (Baba 1994). The ESEM because of the large number of use of nanometer gold tagged antibodies is secondary electrons generated by interactions routine in biological microscopy (Baschong with the gas surrounding the specimen. These 1998). Software has been developed to secondary electrons stimulate x-ray emission create 3-dimensional images from a from everything in the specimen chamber; this collection of rotated images containing these increases the amount and complexity of the small gold particles (Ziese 2002). background signal. Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 83

EELS nanotube (Zuo 2003). The diffraction intensities were recorded and Fourier- In addition to being deflected, some beam transformed into an image. Iterative software electrons suffer energy losses due to was employed to find a unique solution to the interactions with specimens. Many beam phase problem. electrons lose small amounts of energy (<50 eV) by exciting valence electrons to nearby X-ray Beam Probes unoccupied states. Less often, beam electrons lose energy by ionization of specimen atoms The intense energetic beams generated by (i.e., exciting electrons from inner shell bound synchrotrons can be collimated to very small states). These are discrete losses and are dimensions (ca. 10 to 50 nm) and resolved to characteristic of different elements; this gives 0.3 electron volts (eV). Scanning transmission rise to the descriptive term ‘core edge.’ Thus, x-ray microscopy STXM has been used to the electron energy loss spectrum (EELSEELS) for a describe the morphology of polymer carbohydrate would exhibit a carbon core composites (Ade 1992; Hitchcock 2002). By edge near 285 eV from the primary beam selecting x-radiation of different wavelengths, energy and an oxygen core edge near 532 eV contrast can be developed between different (Leapman 1992). materials (this is the same phenomenon as EELS, described above, except that x-rays Different types of carbon bonding can be instead of electrons are used to stimulate core distinguished if the EELS spectra can be electron transitions). Very thin specimens (100 obtained with sufficient energy resolution. – 150 nm thick) are necessary because this is Thus, amorphous carbon can be a transmission probe technique. Intense high distinguished from diamond or graphite, or energy radiation could alter the specimens aromatic carbon can be distinguished from (although x-radiation is not as directly aliphatic carbon. This can readily be damaging as electrons). achieved with 70 meV resolution currently available. It is best to use a field emission It may be difficult to develop contrast between electron source for this purpose because they cellulose and hemicellulose. However, a have an energy spread <.3 eV compared recent study of mixtures of ethylene-butene with the 1.0—1.5 eV energy spread (FWHM) copolymer with ethylene-octene copolymer of a thermionic electron source. demonstrated STXM images of separate phases of these polymers. They differ only in Quantitative chemically specific images may the length of the side chair (i.e., ethyl versus be obtained imagewise using energy filtered hexyl groups) (Appel 2002). TEM (EFTEMEFTEM), or a spectrum may be collected at each image pixel by scanning X-ray spectroscopies are often used along transmission electron microscopy (STEMSTEM). with STXM (Cody 1995a, 1995b). NEXAFS Rapid advancement in this instrumentation (near edge x-ray absorption) and XANES (x- has occurred in the past 10-12 years. There is ray absorption spectroscopy) use x-rays to still concern about electron damage to excite core level electrons to unoccupied specimens because beam currents of about 1 states. In near-edge spectroscopy, the fine nA are required for acquisition times of a few structure at lower energy than the absorption minutes to obtain good signal to noise. edge is investigated with high energy resolution. This fine structure depends on A new approach which is still limited by many parameters such as the oxidation state, specimen thickness but promises higher local symmetry, or ligands around the resolution is NAEDNAED–nano-area electron absorbing atom. The perceived difficulties are diffraction. A nanometer-sized coherent the same as those for STXM. electron beam was used to resolve the structure of a single double-walled carbon 84 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

At energies higher than the absorption edge is Spatial resolution of 10 nm has been a weak periodic modulation which may reported at the Wisconsin Synchrotron extend for hundreds of electron volts. This Radiation Center (SRC) (De Stasio 1999; extended energy-loss fine structure (EXELFSEXELFS) Frazer 2004). arises from a modulation in the ionization cross section caused by interference between Infrared Microspectroscopy the outgoing electromagnetic wave emitted from the ionized atom and components Coupling infrared and visible light through an reflected from neighboring atoms (Leapman infrared microscope, this technique combines 1981; Joy 1986). the chemical specificity afforded by infrared spectroscopy with the visual imaging of In x-ray photoelectron spectroscopy (XPSXPS), an optical microscopy. Spatial resolution claims incoming monochromatic x-ray photon range from 3 to 30 micrometers (Koenig causes the removal of a core or valence 1998). Synchrotrons may be used as a source electron. The escaping electron has a kinetic of high-intensity infrared radiation; they energy that is determined by the energy of the provide a small spot source (ca. 100 mm) photon and the binding energy of the with between two to three orders of electron. XPS is an ultrahigh vacuum magnitude brightness increase over technique which provides information from blackbody sources (Dumas 2003). In spite of the outermost 3- to 5-nanometer layer of the the high brightness, synchrotron sources have specimen. The binding energy depends upon not produced evidence of damage to the element and its chemical state. This is biological specimens. Focal plane mercury- inherently a surface technique because of the cadmium-telluride array detectors are low energy of the photoelectrons (Briggs routinely used to obtain spectral information 1983). It has limited chemical specificity (can imagewise. distinguish lignin from cellulose but not cellulose from hemicellulose) and can be The spatial resolution is poor compared with performed imagewise with resolution of about some other techniques, but the chemical 20 nm (Fulghum 1999). specificity is very high. Infrared microspectroscopy is an excellent Another method for obtaining spatially complement to other spectroscopic tools. resolved chemical information is X-PEEM Sample thickness greater than a few tens of (Tonner 1988). In this technique, micrometers can be a problem unless photoelectrons emitted from a specimen are reflectance modes are employed. recorded as the wavelength of x-rays is changed. Synchrotron radiation is used as a Spectroscopic maps with 8-mm spatial source of x-rays which are dispersed with a resolution have been obtained using an monochrometer. This is an ultrahigh vacuum attenuated total reflectance objective lens technique which requires conductive or thin with a focal plane array detector (Sommer (ca. 100 nm or less) specimens to avoid 2001). Even better spatial resolution has been charge accumulation on the specimen attained by applying near-field optics with a (Gilbert 2000). modified AFM head and using synchrotron radiation (Bozec 2002). A good illustration of the application of X- PEEM, STXM, and AFM to the study of an Similar information may be obtained by immiscible blend of polymers was reported Raman microspectroscopy, but often the recently (Morin 2001). In addition to intense laser radiation used in Raman illustrating the value of the different spectroscopy creates damage in organic techniques, it is a good example of how a materials. Infrared absorbance is a single more complete picture is created by photon, direct process while the Raman combining the data from multiple techniques. process is a two-photon scattering process; Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 85

the underlying physics are different. The This is inherently a surface probe with 1- to selection rules are different and thus the two 10-nm depth resolution. The sensitivity to spectroscopic methods can provide different chemical species varies greatly complementary information. Spatial because only ions are detected, whereas most resolution for Raman microspectroscopy can of the products of sputtering are neutral approach 1 mm. There are two common fragments (Briggs 1992). problems: 1) the excitation laser frequently causes fluorescence which masks the Raman The use of primary beams with cluster ions signal and 2) the efficiency of the process is (ions of high molecular weight such as Csn, 6 very low (about 1 photon out for 10 in) (Adar SF5, C60, and Aun) has improved the value of 2003). SIMS for molecular solids (Wagner 2004; Gillen 2001; Postwa 2003). Cluster ions Secondary Ion Mass Spectrometry produce greater useful signal intensity and sputter rate while limiting damage and In secondary ion mass spectrometry (SIMSSIMS), a penetration depth. Cluster ions may be used focused ion beam is directed to a solid for analysis at low ion current (static SIMS) surface, removing material in the form of and may be used to systematically remove neutral and ionized atoms and molecules (as layers from the specimen at higher ion discussed in FIB above). The secondary ions currents. Sputter depth profiles have been are accelerated into a mass spectrometer and demonstrated for polymethyl methacrylate separated according to their mass-to-charge (Wagner 2004). This is a promising way of ratio. The lateral resolution is between 1 obtaining imagewise chemical data in three micrometer and 50 nanometers in different dimensions. instruments. The mass spectra provide good chemical specificity. SIMS is inherently an ultrahigh vacuum technique which requires flat specimens. Some means must be employed to eliminate charge accumulation (e.g., electron flood gun or conductive screen over the specimen). 86 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 87

Appendix G: Nanoscience User Facilities

This is a listing of facilities where uncommon National Renewable Energy Laboratory tools may be available. Rather than attempt (NREL) descriptions of these laboratories, the URLs Surface Analysis for their web sites are provided. www.nrel.gov/measurements/surface.html Pacific Northwest National Laboratory In addition to this list, most universities have Environmental Molecular Sciences centers where major instruments are shared Laboratory among different departments. Often, non- www.emsl.pnl.gov/ university users can also use these facilities which usually include electron and optical Universities and Research Centers microscopes, as well as surface analysis instrumentation. These centers may also Lehigh University provide contact with university specialists who www.lehigh.edu/nano/ may be potential collaborators; who are • 13 electron microscopes more significant help than instruments. • Scienta high resolution x-ray • photoelectron spectrometer National Laboratories University of Pennsylvania www.seas.upenn.edu/nanotechfacility/ Argonne National Laboratory Advanced Photon Source • facilities for corporate users www.aps.anl.gov University of Albany Brookhaven National Laboratory www.albanynanotech.org/Programs/ National Synchrotron Light Source (NSLS) metrology/index.cfm www.nsls.bnl.gov/ • six electron microscopes Lawrence-Berkley National LaboratoLaboratory • two x-ray photoelectron Advanced Light Source spectrometers www-als.lbl.gov/als/microscopes/ • focused ion beam index.html • three scanning probe microscopes • Fourier transform infrared • visible, infrared microspectroscopy spectroscopy • PEEM (Photoelectron emission spectrometer) University of Notre Dame • imaging x-ray microscopy www.nd.edu/~ndnano/title.htm • x-ray photoelectron • mostly electronics fabrication microspectroscopy • four electron microscopes National Institute for Standards and • atomic force microscope Technology (NIST) • near-field scanning optical SURF III synchrotron microscope Physics.nist.gov/MajResFac/SURF/ • Fourier transform infrared SURF.html spectroscopy High-Resolution UV and Optical Spectroscopy Facility 88 Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap

University of Illinois University of Saskatchewan Center for Microanalysis of Materials Canadian Light Source, Inc. cmm.mrl.uiuc.edu/techniques/sims.htm www.lightsource.ca/experimental/ • Cameca ims 5f • x-ray microscopy • Fourier transform infrared University of Wisconsin spectroscopy Material Science Center www.msae.wisc.edu/mscweb/ Duke University Free Electron Laser Laboratory • electron microscopes www.fel.duke.edu/ • preparation facilities • atomic force microscope • infrared FEL • x-ray photoelectron spectrometers • ultraviolet FEL • focused ion beam Louisiana State University Synchrotron Radiation Center—Aladdin Center for Advanced Microstructures and www.src.wisc.edu Devices www.camd.lsu.edu/ • Scienta 200 high resolution x-ray photoelectron spectrometers • synchrotron for x-ray microscopy and • Infrared microscope spectroscopy • PEEM Photoelectron emission Cornell University spectrometer Cornell High Energy Synchrotron Source Nanoscale Science and Engineering (CHESS) Center www.chess.cornell.edu/ www.nsec.wisc.edu North Carolina State University Northeastern University Harold Ade research group Center for High-rate Nanomanufacturing www.physics.ncsu.edu/stxm/stxm.html www.nano.neu.edu/ • near edge x-ray fluorescence • electron microscopy spectroscopy (NEXAFS) • atomic force microscopy • scanning transmission x-ray microscopy (STXM) Pennsylvania State University • photoelectron emission spectrometer National Nanotechnology Infrastructure (PEEM) Network www.nanofab.psu.edu University of Dayton University of Dayton Research Institute • electron beam, optical and probe (UDRI) lithography www.udri.udayton.edu/ • novel materials deposition and etching • x-ray photoelectron spectroscopy • electron and optical microscopy • electron microscopy • scanning probe microscopy Purdue University • focused ion beam Birck Nanotechnology Center • near-field scanning optical http://www.nano.purdue.edu/wps/portal/ microscopy .cmd/cs/.ce/155/.s/4271/_s.155/4271 Colorado State University NSF Engineering Research Center for Extreme Ultraviolet Science euverc.colostate.edu/ Nanotechnology for the Forest Products Industry—Vision and Technology Roadmap 89

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