Short-rotation woody crop plantations of fast-growing trees, such as willow and poplar, can be grown as alternative sources of clean, renewable energy. These intensive culture systems have high nutrient demands. Application of N at three rates, (100, 200, and 300 kg N/ha) as slow-release urea and a control were used to evaluate the impact of fertilization on second-year yields of five willow clones and one poplar clone in three plantations across New York State. Regression equations were developed to estimate standing biomass. Willow clone SV1 and poplar clone NM6 benefited from fertilization, reaching yields as high as 20.3 and 21.6 o.d. Mg/ha by the second year of the rotation, respectively. The responses of the other four willow clones were confounded greatly by weeds and unmeasured site factors, though there was some benefit from fertilization. Tree biomass response to fertilization differed by site and was a function of survival, weeds, and the interactions with site and microsite variations. Fertilizing at rates above 100 kg N/ha for a three-year rotation are recommended only when additional site data indicate a need.

Progress in the Development of Surface Modified Cellulose Nanocrystals to Be Used as Reinforcing Fillers in Engineering Thermoplastics
Deepanjan Bhattacharya and William T Winter- Cellulose Research Institute, College of Environmental Science and Forestry, State University of New York , Syracuse, NY-13210

Cellulose was obtained from bagasse after mercerization and bleaching. It was then broken down into nanoparticles through a process of homogenization. The surface of these nanocrystals was chemically modified with maleic anhydride. This was confirmed by infra red spectroscopy that revealed the presence of a carbonyl peak at 1730 cm^-1. The degree of surface modification was obtained by determining the acid number. The extent of reaction was found to be greater in case of the commercial grade microcrytalline cellulose as compared to the nanocrystals obtained from bagasse. These surface modified nanocrystals serve as an excellent source of reinforcing fillers in composites based on engineering thermoplastics. Studies on the extent of improvement in the mechanical properties of the composites, on addition of these surface modified fillers are currently in progress.

Issues Facing the Wood-Using Industries
Hugh O. Canham, Professor- Faculty of Forestry, SUNY College of Environmental Science & Forestry, Syracuse, NY 13210[email: hocanham@esf.edu]

The wood-using industries face serious issues concerning fiber supply, environmental regulations, public pressures, policies and laws. A study undertaken by the author, during the fall of 1999, with funding from the Joachim Foundation, has produced current information on what industry people feel are the important issues and dimensions of them. Knowledge of these issues will enable researchers, academicians, and policy makers, and industry personnel to better direct their efforts to improve the economic health of some of the nation’s leading economic sectors. Results will be displayed in poster format with the author available for discussion and comment.

Chemicals and Biofuels from Hardwood, Fuel Crops and Agricultural Wastes
Janis Gravitis- United Nations University Institute of Advanced Studies. 53-67 Jingumae 5-chome, Shibuya-ku, Tokyo 150-8304. [email: gravitis@ias.unu.edu];
Nikolay Vedernikov, Janis Zandersons and Arnis Kokorevics- Latvian State Institute of Wood Chemistry. Dzerbenes 27, Riga, LV1006, Latvia

It would be important to produce furfural and levoglucosan (LG) as monomers for organic synthesis in one two-step process. But the simultaneous obtaining of these two products till nowadays was considered as theoretically impossible because of near values of kinetical parameters of furfural formation and cellulose destruction. This results in the 40-50% cellulose destruction during the furfural obtaining process.

The other problem which has not been solved during 77 years of the industrial furfural production was a comparatively low yield of furfural not exceeding 55% from theoretical.   The mechanism of the process was to be changed in order to solve both problems simultaneously. It was done on the basis of a new non-traditional approach – theory of differentiated catalysis.  The fast pyrolysis of lignocellulose to obtain LG was carried out. LG derivatives, synthesized according to reactive hydroxyl groups, have been used in a variety of applications (polyethers, polyuretanes and reactive oligomers).

Plant biomass conversion into chemicals as well as their combination with carbonization technologies and steam explosion will be discussed. These integrated technologies are orientated to achieve Zero Emissions target (no waste in air, water and land), the program was launched in 1994 by the United Nations University.

Progress in the Development of Cellulose Reinforced Nanocomposites
Maren Grunert and William T. Winter- Cellulose Research Institute and Department of Chemistry, SUNY-ESF, 121 Edwin C. Jahn Laboratory, Syracuse, NY 13210 [email: mgrunert@mailbox.syr.edu]

Cellulose nanocrystals and topochemically trimethylsilylated cellulose nanocrystals were prepared from bacterial cellulose. The crystals were characterized by FTIR and CP/MAS NMR spectroscopy, x-ray diffraction and transmission electron microscopy. The surface derivatization was investigated as a function of reaction time. The trimethylsilylation appeared to be completed after 18 hours. Nanocomposites were prepared with crosslinked polydimethylsiloxane as matrix and unreacted or surface trimethylsilylated cellulose crystals as particulate phase. The nanocomposites were characterized by dynamic mechanical analysis. A reinforcement with respect to the pure matrix was observed for both the composite with unreacted and the composite with trimethylsilylated crystals. The extent of reinforcement depended strongly on temperature, oscillation frequency and surface chemistry of the particulate phase.

Expression of white-rot fungi manganese peroxidase (MnP) in the yeast Pichia pastoris
Lina Gu, Christine Kelly and Curtis Lajoie- Chemical Engineering and Material Science, Syracuse University, Syracuse, NY 13244-1190 [e-mail: ckelly@syr.edu]

Lignin polymers are a major obstacle to efficient utilization of lignocellulose in industrial processes. White-rot fungi are the most effective lignin degrading organisms known. Whereas some organisms can access cellulose by oxidizing, depolymerizing and solubilizing lignin, white-rot fungi, such as Phanerochaete chrysosporium, are also capable of mineralizing lignin. P. chrysosporium produces two types of extracellular ligninolytic enzymes; lignin peroxidase (LiP) and manganese peroxidase (MnP). LiP and MnP are heme-containing enzymes that catalyze the H₂O₂-dependent degradation of lignin. Production of commercially viable yields of these enzymes has not been achieved, precluding their evaluation and subsequent use in bio-manufacturing processes.

Research is being conducted on the heterologous production of ligninolytic enzymes from P. chrysosporium using the Pichia pastoris (methylotrophic yeast) expression system. The gene encoding MnP2 has been cloned from induced cultures of P. chrysosporium via RT-PCR, and inserted with the endogenous signal sequence downstream of the strong methanol promoter AOXI in the P. pastoris vector pHIL-D2. To increase yields important variables being studied include alternative secretion signals, P. pastoris phenotypes (Mut⁺, Mut^s), pH, and heme concentration. It is hypothesized that high yields of ligninolytic enzymes can be achieved by maintaining adequate levels of intracellular heme during enzyme biosynthesis.

Microparticle Dispensers for the Controlled Release of Insect Pheromones
Patrick J. Hennessy, Arthur J. Stipanovic and Francis X. Webster- Department of Chemistry, SUNY - College of Environmental Science and Forestry, Jahn Laboratory, One Forestry Drive, Syracuse, NY 13210 [email: pahennes@syr.edu]

Pheromones play a very important role in the world of insects. In most cases, females will emit pheromones to attract a male to mate. For many insects, the specific mating pheromone has been characterized and can now be synthesized in large quantities in the laboratory. This allows us to use these synthetic pheromones in monitoring pest population, mass trapping, and in mating disruption. The main focus of this project is to improve upon existing controlled release technology used for mating disruption. Currently, dispensers used in this application are relatively large, non-biodegradable, and are manpower intensive to implement in the field. In this project, micron-sized biodegradable pheromone dispensers have been fabricated which could, potentially, be broadly applied via conventional spraying. Preliminary work with microcrystalline cellulose (MCC) particles has shown that the evaporation rate for the gypsy and codling moth pheromones, as determined by an "aeration" procedure and Thermal Analysis (TGA, DSC), can be modified through adsorption of these compounds onto a cellulosic substrate. To further control evaporation rate, MCC particles can be coated with biodegradable polymers, including cellulose derivatives and other polysaccharides.

Influence of Dehydrating Agents on Carbonization of Cellulose and Wood
Dae-Young Kim, Yoshiharu Nishiyama, Masahisa Wada, and Shigenori Kuga- Department of Biomaterials Science, Graduate School of Agricultural and Life Sciences, The University of Tokyo, Yayoi 1-1-1, Bunkyo-ku, Tokyo 113-8657, Japan [email: d-kim@sbp.fp.a.u-tokyo.ac.jp]

Some inorganic agents are known to be effective in developing large surface area in production of activated carbon from cellulosic materials. We notice that these additives also significantly affects mass yield and properties of resulting chars due to their action as dehydrating agents. We chose sulfuric acid as additive and examined its influences on carbonization of cellulose and wood. The addition of sulfuric acid resulted in lowered decomposition temperature, significant improvement in mass yield, smaller shrinkage, and higher rigidity of the resulting char. These effects are interpreted to result from facilitated extraction of water from cellulose accompanied by development of extended carbon networks. The same features were observed for wood meal with somewhat decreased degrees as a result of presence of non-cellulose substances. Since sulfuric acid is evaporated in the course of carbonization, resulting carbon does not need washing as in the case of zinc chloride or other inorganic salts, and this can be advantageous in preparing block-shaped materials.

Genetic Improvement of Salix at the State University of New York College of Environmental Science and Forestry
Richard F. Kopp, Lawrence B. Smart, Lawrence P. Abrahamson and Charles A. Maynard- SUNY- College of Environmental Science and Forestry, 1 Forestry Drive, Syracuse, NY 13210 [email: rfkopp@syr.edu]

Shrub willow is rapidly coming to the forefront as a biomass crop when grown under short-rotation intensive culture in the temperate regions of the world. SUNY-ESF has been a leader in North American research aimed at dedicated willow crop systems. Significant increases in yield and wood quality are likely to be attained through the development of genetically superior clones. SUNY-ESF has assembled and tested a large diverse collection of willow germplasm from across the Northeast United States and Southeast Canada and began using the material in controlled intra- and interspecific crosses in 1998. S. eriocephala and S. purpurea are well represented in the collection, with small numbers of clones of ten other willow species. F1 full-sib progeny produced during 1998 and 1999 are currently being field-tested. Controlled crosses to produce F2 full-sib progeny will be completed during February-April 2000. Molecular fingerprinting by amplified fragment length polymorphism (AFLP) is in progress to facilitate clone selection and confirm clone identity. This poster will present the status of willow genetics research for bioenergy crops in the United States.

Kraft Pulp from Plantation-Grown Bio-mass Willow
Hannu P. Makkonen, Stephen G. Granzow, and Emmett S. Cheshire- Empire State Paper Research Institute/SUNY-ESF, 1 Forestry Drive, Syracuse, NY 13210 [email: espri@syr.edu]

A short experimental evaluation was done on the papermaking potential of willow grown on an ESF plantation for biomass energy. The growth rate for willow was 5-7 (max. 13) o.d. gross tons/acre/year (~25-35 m³/ha/a, max. 65 m³/ha/) rendering it competent in growth with the fast-growing eucalyptus.

It was resolved that both barked and debarked chips (after 3 years of growth) pulped fully with screened yields between 47.2 % and 53.9 %, at kappa numbers 16.2 to 26.6, and that the unbleached kraft pulps from debarked wood contained better sheet properties than those from raw material containing bark. Both were compared to a commercial ECF-bleached eucalyptus pulp and it was shown that the willow samples contained good strength properties despite of short fibers (~.54 mm). Willow was proven to be a viable commercial fiber source.

The preliminary results call for a further study on more mature wood (5-6 years), and on processing alternatives for debarking (15%), and fiber fractionation.

Keywords: Bark, biomass, eucalyptus, fiber length, kraft pulp, willow.

Industrial Benefits: The favorable growth rate of willow and its homogeneous fiber length distribution along with easy delignification and beating might attract the industry's interest in willow as raw material source for pulping instead of energy.

Synthesis of Poly(lignin-g-(1-chloroethylene)) Under a Partial Factorial, Experimental Design
John J. Meister and Vipul Shah- Center for Forest Products Research, Inc., Seven Technology Center, 2008 Hendola Drive, NE, Albuquerque, NM 87110-4808

A four-factor, one third factorial, Box Behnken experimental design of 27 reactions was chosen to determine yield of a graft copolymerization of lignin and 1-chloroethene. Yield as a function of lignin concentration (C_Lignin), 1-chloroethene concentration (C_CE), calcium chloride concentration (C_CaCl2), and hydrogen peroxide concentration (C_H2O2) in dimethylsulfoxide is:

Yield = 212.0 * C_Lignin -92. 19 * C_CE + 57.49 * C_CaCl2 +150.5 * C_H2O2 +523 * C_Lignin * C_Lignin -189 * C_CE * C_Lignin +84.5 * C_CE * C_CE -1150 * C_CaCl2 * C_Lignin -13.9 * C _CaCl2 * C_CE +296 * C _CaCl2 * C _CaCl2 -343 * C_H2O2 * C_Lignin -193 * C_H2O2 * C_CE +358 * C_H2O2 * C _CaCl2 -302 * C_H2O2 * C_H2O2 +33.85

The synthesis of poly(lignin-graft-vinyl chloride) requires pressure containment to allow the reaction of the gaseous monomer, steps to increase the kinetics of the polymerization, and an optimization of the ratios of the reactants. Pressure containment was achieved by using a set of inexpensive pipe reactors which allow bulk samples of the polymer to be produced. Increased kinetics and 48 hour production of product was achieved by tripling the monomer content of the reactor and increasing containment pressure to raise the rate of reaction. Rate is directly dependent on the pressure of monomer over the reaction solution and the Henry’s Law constant of 1-chloroethene in the reaction mixture.

Utilization of Liquefied Product from Cellulosic Materials Incorporated with Reactive Solvents for Adhesive Source
Hirokuni Ono- Graduate School of Agri. and Life Sci., The University of Tokyo. 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 Japan [email: ahono@mail.ecc.u-tokyo.ac.jp];
Tatuhiko Yamada- Forestry and Forest Product Research Institute, The Ministry of Agri., Fishery and Forestry. Box 16, Tsukuba Norin Danchi, Tsukuba, Ibaraki-ken, Japan [email: yamadat@ffpri.affrc.go.jp]

Cellulosic materials were liquefied in the presence of sulfuric acid under normal pressure by using either phenol or ethylene glycol. Both solvents provided complete liquefaction products which dissolve in some polar organic solvent. Fractionation was applied to the dissolving parts and the residues of the products along with reaction time course. The cellulosic component in wood was found to lose its pyranose ring structure and finally convert into liquefied product, suggesting that these liquefactions would provide decomposed substance by drastic solvolysis reaction. The product is confirmed to have phenolic moieties when phenol is used for liquefaction.

In the case of ethylene glycol liquefaction, glucosides were observed at the initial stage of liquefaction and levulinates after complete liquefaction. These findings indicate that the proper selection of liquefaction would make possible to prepare polymers of special use. The potential of the liquefied products for plastics including adhesives will be discussed on the basis of chemical characteristics of the products. The performance of adhesion from liquefied products will be also discussed.

De-inking of Recycled Pulps Using Column Flotation
Somporn Chaiarrekij, H. Gupta, W. Amato and B. V. Ramarao- Department of Paper Science and Engineering, SUNY-ESF, Syracuse, NY-13210.

Column flotation is a novel technique of separation of hydrophobic particles from a suspension. As such, it has been applied widely in the mineral processing industry to replace agitated cells in the separation of minerals. By avoiding the usage of an agitator inside a cell, a flotation column offers considerable energy benefits besides smaller capital outlays and operational costs. These factors have made it attractive compared to agitated flotation cells and hence column flotation has been applied widely in the mineral processing industry.

In this report, we provide details of two experimental column flotation set-ups in our laboratories. An experimental investigation of column flotation as applied to de-inking of a 50-50 mix of photocopier and laser-print waste paper is described. Experiments were conducted in both the batch and the continuous mode of operation. Hand-sheets were made from the de-inked pulp and the brightness and ink particle size distributions were measured.

The kinetic constants for de-inking were determined for the batch as well as the continuous modes. A preliminary investigation of the sub-processes involved in particle attachment to bubbles was made to provide details of the kinetic constants.

A Novel Fractionation Process Based on Very Dilute Sulfuric Acid Hydrolysis of Hardwood for The Improved Production of Fuels and Chemicals
Robert W. Torget and Richard T. Elander- Biotechnology Center for Fuels and Chemicals National Renewable Energy Laboratory, Golden, CO 80401[Phone: (303) 384-6178 Fax: (303) 384-6877 email: Robert_Torget@NREL.gov];
Bonnie R. Hames, Amie D. Havercamp and David K. Johnson- Chemistry for Bioenergy Systems National Renewable Energy Laboratory,Golden, CO 80401

A continuous two stage dilute sulfuric acid (0.07 wt%) fractionation of hardwood sawdust has been demonstrated at the bench scale and is now being scaled up to the pilot scale (200 Kg/day). The proposed plug-flow first stage and a countercurrent second stage should allow for hemicellulose sugar recoveries of about 95%, cellulose conversions between 60 and 93%, and Klason lignin solubilization of 60-70%. Glucose yields are near theoretical (independent of the desired conversion) in this reactor mode and defy most of the previous kinetic predictions, and will be discussed in light of novel cellulose hydrolysis kinetics. Three lignin fractions are obtained in approximately equal amounts: a high molecular weight fraction (40,000-80,000); a fraction containing monomeric to tetrameric phenolic oligomers which are soluble in methanol, ethanol, acetone, THF, and MIBK, and well suited for conversion to liquid fuels; and a fraction containing monomeric and dimeric phenolic units with an average MW of 410 which are very soluble in water and the above mentioned solvents, and well suited to conversions to simple phenols, quinones, and muconic acids.

Cellulose Powder as a Component of Thermoset Resins: Characterization, Functionalization and Curing Studies
A.J.Varma- Chemical Engineering Division, National Chemical Laboratory, Pune-411008, India [e-mail: ajvarma@che.ncl.res.in]

Incorporation of cellulosic materials as major components of currently known plastics presents an attractive strategy to produce new polymeric materials which are likely to be more environment-friendly. In the current work being presented, cellulose powder (and starch) has been chemically modified to have some aldehyde, carboxyl, or amino functional groups on the cellulose chain, and these were blended with epoxy resin and cured. As a result of this chemical modification, the following advantages were noted, as compared to unmodified cellulose, in epoxy matrices : 1) No phase separation of the modified filler due to incompatibility with the matrix resin, since the cellulosic filler is also the curing agent as well as coupling agent 2) No additional curing agent is needed if sufficient reactive functional groups are created along the polymer chain, and a compounding step is avoided for separate addition of a curing agent 3) The curing rate is significantly enhanced.

Further, in order to get reproducible results from commercial cellulose powder, the starting commercial cellulose powder must be well characterized. The characterizations carried out in our laboratory were based on angular-dependent x-ray photoelectron spectroscopy, wide-angle x-ray diffraction, thermal analysis, solid-state CP-MAS C-13 NMR, and solvent extractions. The importance of these characterizations is also discussed.

Site-Directed Mutagenesis of Thermobifida Fusca Cellulases Cel6A and Cel6B
David B. Wilson, Sheng Zhang and Diana Irwin- Department of Molecular Biology & Genetics, Cornell University, 458 Biotechnology Building, Ithaca, NY 14853 [email: dbw3@cornell.edu]

Cel6A is an endocellulase with an open active site and Cel6B is a homologous exocellulase with its active site in a tunnel. The 3-dimentional structure of Cel6A has been determined by X-ray crystallography at 1.0 Å resolution and we have a model of the structure of Cel6B based on the structures of T. fusca Cel6A and T. reesei Cel6A, another exocellulase. Fifty mutations in twenty different Cel6A residues were prepared, expressed and the mutant enzymes were assayed for activity on four cellulosic substrates and their binding affinities to several ligands. Analysis of the data from these experiments showed that Cel6A utilized an Asp residue as an essential catalytic acid, but does not contain an essential catalytic base. The data also show that movement of one of the loops near the active site is required for activity. A similar study was carried out on Cel6B in which twenty-three mutations in eleven residues were produced and characterized.

Rapid Liquefaction of Lignocellulosic Waste in the Presence of Cyclic Carbonates for Preparing Levulinic Acid and Polyurethane Resins
Tatsuhiko Yamada- Wood Chemistry Division, FFPRI : Forestry and Forest Products Research Institute, P.O. Box16, Tsukuba, Ibaraki 305-8687, Japan [email: yamadat@ffpri.affrc.go.jp]
Hirokuni Ono- Graduate school of Agricultural and Life Sciences, The University of Tokyo, Tokyo 113-8657, Japan

Liquefaction of lignocellulosics is the technique that converted lignocellulosic waste into useful liquid materials. Through liquefaction, lignocellulosics can be easily and completely converted into substances soluble in widely used organic solvents such as dioxane, methyl alcohol and acetone by using phenols or polyhydric alcohols, in the presence of acid catalyst at temperatures of 130 to 150 ^oC under atmospheric pressure. We have found cyclic carbonates such as ethylene carbonate and propylene carbonate provide very rapid liquefaction of lignocellulosic materials. The rate of cellulose liquefaction in the presence of ethylene carbonate was approximately 10 times faster than that of current liquefaction using polyhydric alcohols. The liquefied lignocellulosics were used for preparing polyurethane resins in cooperation with isocyanates. Cyclic carbonates particularly accelerated the acid solvolysis of cellulose, and rapidly led cellulose to levulinates. Levulinic acid was easily produced from liquefied lignocellulosics through hydrolysis following the liquefying treatment. Levulinic acid is known as a key chemical intermediate in the production of other important compound. This technique could be applied to a synthesis method for levulinic acid from biomass.

Cellulose Based "Smart Fluids": Stimuli Responsive Materials for the New Millennium
Shengnin Zhang, Arthur J. Stipanovic and William T. Winter- Department of Chemistry and the Cellulose Research Institute, SUNY- College of Environmental Science and Forestry, Jahn Laboratory, Syracuse, New York 13210 [e-mail :astipano@esf.edu or wtwinter@syr.edu]