Forest Products Laboratory

This critical review provides a processing-structure-property perspective on recent advances in cellulose nanoparticles and composites produced from them. It summarizes cellulose nanoparticles in terms of particle morphology, crystal structure, and properties. Also described are the self-assembly and rheological properties of cellulose nanoparticle suspensions. The methodology of composite processing and resulting properties are fully covered, with an emphasis on neat and high fraction cellulose composites. Additionally, advances in predictive modeling from molecular dynamic simulations of crystalline cellulose to the continuum modeling of composites made with such particles are reviewed (392 references).

Summarizes information on wood as an engineering material. Presents properties of wood and wood-based products of particular concern to the architect and engineer. Includes discussion of designing with wood and wood-based products along with some pertinent uses.

Wood is a major pool of organic carbon that is highly resistant to decay, owing largely to the presence of lignin. The only organisms capable of substantial lignin decay are white rot fungi in the Agaricomycetes, which also contains non-lignin-degrading brown rot and ectomycorrhizal species. Comparative analyses of 31 fungal genomes (12 generated for this study) suggest that lignin-degrading peroxidases expanded in the lineage leading to the ancestor of the Agaricomycetes, which is reconstructed as a white rot species, and then contracted in parallel lineages leading to brown rot and mycorrhizal species. Molecular clock analyses suggest that the origin of lignin degradation might have coincided with the sharp decrease in the rate of organic carbon burial around the end of the Carboniferous period.

This revision of the classification of unicellular eukaryotes updates that of Levine et al. (1980) for the protozoa and expands it to include other protists. Whereas the previous revision was primarily to incorporate the results of ultrastructural studies, this revision incorporates results from both ultrastructural research since 1980 and molecular phylogenetic studies. We propose a scheme that is based on nameless ranked systematics. The vocabulary of the taxonomy is updated, particularly to clarify the naming of groups that have been repositioned. We recognize six clusters of eukaryotes that may represent the basic groupings similar to traditional "kingdoms." The multicellular lineages emerged from within monophyletic protist lineages: animals and fungi from Opisthokonta, plants from Archaeplastida, and brown algae from Stramenopiles.

With the arising of global climate change and resource shortage, in recent years, increased attention has been paid to environmentally friendly materials. Trees are sustainable and renewable materials, which give us shelter and oxygen and remove carbon dioxide from the atmosphere. Trees are a primary resource that human society depends upon every day, for example, homes, heating, furniture, and aircraft. Wood from trees gives us paper, cardboard, and medical supplies, thus impacting our homes, school, work, and play. All of the above-mentioned applications have been well developed over the past thousands of years. However, trees and wood have much more to offer us as advanced materials, impacting emerging high-tech fields, such as bioengineering, flexible electronics, and clean energy. Wood naturally has a hierarchical structure, composed of well-oriented microfibers and tracheids for water, ion, and oxygen transportation during metabolism. At higher magnification, the walls of fiber cells have an interesting morphology-a distinctly mesoporous structure. Moreover, the walls of fiber cells are composed of thousands of fibers (or macrofibrils) oriented in a similar angle. Nanofibrils and nanocrystals can be further liberated from macrofibrils by mechanical, chemical, and enzymatic methods. The obtained nanocellulose has unique optical, mechanical, and barrier properties and is an excellent candidate for chemical modification and reconfiguration. Wood is naturally a composite material, comprised of cellulose, hemicellulose, and lignin. Wood is sustainable, earth abundant, strong, biodegradable, biocompatible, and chemically accessible for modification; more importantly, multiscale natural fibers from wood have unique optical properties applicable to different kinds of optoelectronics and photonic devices. Today, the materials derived from wood are ready to be explored for applications in new technology areas, such as electronics, biomedical devices, and energy. The goal of this study is to review the fundamental structures and chemistries of wood and wood-derived materials, which are essential for a wide range of existing and new enabling technologies. The scope of the review covers multiscale materials and assemblies of cellulose, hemicellulose, and lignin as well as other biomaterials derived from wood, in regard to their major emerging applications. Structure-properties-application relationships will be investigated in detail. Understanding the fundamental properties of these structures is crucial for designing and manufacturing products for emerging applications. Today, a more holistic understanding of the interplay between the structure, chemistry, and performance of wood and wood-derived materials is advancing historical applications of these materials. This new level of understanding also enables a myriad of new and exciting applications, which motivate this review. There are excellent reviews already on the classical topic of woody materials, and some recent reviews also cover new understanding of these materials as well as potential applications. This review will focus on the uniqueness of woody materials for three critical applications: green electronics, biological devices, and energy storage and bioenergy.

Trichoderma reesei is the main industrial source of cellulases and hemicellulases used to depolymerize biomass to simple sugars that are converted to chemical intermediates and biofuels, such as ethanol. We assembled 89 scaffolds (sets of ordered and oriented contigs) to generate 34 Mbp of nearly contiguous T. reesei genome sequence comprising 9,129 predicted gene models. Unexpectedly, considering the industrial utility and effectiveness of the carbohydrate-active enzymes of T. reesei, its genome encodes fewer cellulases and hemicellulases than any other sequenced fungus able to hydrolyze plant cell wall polysaccharides. Many T. reesei genes encoding carbohydrate-active enzymes are distributed nonrandomly in clusters that lie between regions of synteny with other Sordariomycetes. Numerous genes encoding biosynthetic pathways for secondary metabolites may promote survival of T. reesei in its competitive soil habitat, but genome analysis provided little mechanistic insight into its extraordinary capacity for protein secretion. Our analysis, coupled with the genome sequence data, provides a roadmap for constructing enhanced T. reesei strains for industrial applications such as biofuel production.

An extracellular lignin-degrading enzyme from the basidiomycete Phanerochaete chrysosporium Burdsall was purified to homogeneity by ion-exchange chromatography. The 42,000-dalton ligninase contains one protoheme IX per molecule. It catalyzes, nonstereospecifically, several oxidations in the alkyl side chains of lignin-related compounds: C(alpha)-C(beta) cleavage in lignin-related compounds of the type aryl-C(alpha)HOH-C(beta)HR-C(gamma)H(2)OH (R = -aryl or -O-aryl), oxidation of benzyl alcohols to aldehydes or ketones, intradiol cleavage in phenylglycol structures, and hydroxylation of benzylic methylene groups. It also catalyzes oxidative coupling of phenols, perhaps explaining the long-recognized association between phenol oxidation and lignin degradation. All reactions require H(2)O(2). The C(alpha)-C(beta) cleavage and methylene hydroxylation reactions involve substrate oxygenation; the oxygen atom is from O(2) and not H(2)O(2). Thus the enzyme is an oxygenase, unique in its requirement for H(2)O(2).

The extracellular fluid of ligninolytic cultures of the wood-decomposing basidiomycete Phanerochaete chrysosporium Burds. contains an enzyme that degrades lignin substructure model compounds as well as spruce and birch lignins. It has a molecular size of 42,000 daltons and requires hydrogen peroxide for activity.

A new family of materials comprised of cellulose, cellulose nanomaterials (CNMs), having properties and functionalities distinct from molecular cellulose and wood pulp, is being developed for applications that were once thought impossible for cellulosic materials. Commercialization, paralleled by research in this field, is fueled by the unique combination of characteristics, such as high on-axis stiffness, sustainability, scalability, and mechanical reinforcement of a wide variety of materials, leading to their utility across a broad spectrum of high-performance material applications. However, with this exponential growth in interest/activity, the development of measurement protocols necessary for consistent, reliable and accurate materials characterization has been outpaced. These protocols, developed in the broader research community, are critical for the advancement in understanding, process optimization, and utilization of CNMs in materials development. This review establishes detailed best practices, methods and techniques for characterizing CNM particle morphology, surface chemistry, surface charge, purity, crystallinity, rheological properties, mechanical properties, and toxicity for two distinct forms of CNMs: cellulose nanocrystals and cellulose nanofibrils.

Both cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) are nanoscale cellulose fibers that have shown reinforcing effects in polymer nanocomposites. CNCs and CNFs are different in shape, size and composition. This study systematically compared their morphologies, crystalline structure, dispersion properties in polyethylene oxide (PEO) matrix, interactions with matrix, and the resulting reinforcing effects on the matrix polymer. Transparent PEO/CNC and PEO/CNF nanocomposites comprising up to 10 wt % nanofibers were obtained via solution casting. Scanning electron microscopy (SEM), wide-angle X-ray diffraction (WXRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analyzer (DMA), and tensile testing were used to examine the above-mentioned properties of nanocellulose fibers and composites. At the same nanocellulose concentration, CNFs led to higher strength and modulus than did CNCs due to CNFs' larger aspect ratio and fiber entanglement, but lower strain-at-failure because of their relatively large fiber agglomerates. The Halpin-Kardos and Ouali models were used to simulate the modulus of the composites and good agreements were found between the predicted and experimental values. This type of systematic comparative study can help to develop the criteria for selecting proper nanocellulose as a biobased nano-reinforcement material in polymer nanocomposites.

White rot fungi efficiently degrade lignin, a complex aromatic polymer in wood that is among the most abundant natural materials on earth. These fungi use extracellular oxidative enzymes that are also able to transform related aromatic compounds found in explosive contaminants, pesticides and toxic waste. We have sequenced the 30-million base-pair genome of Phanerochaete chrysosporium strain RP78 using a whole genome shotgun approach. The P. chrysosporium genome reveals an impressive array of genes encoding secreted oxidases, peroxidases and hydrolytic enzymes that cooperate in wood decay. Analysis of the genome data will enhance our understanding of lignocellulose degradation, a pivotal process in the global carbon cycle, and provide a framework for further development of bioprocesses for biomass utilization, organopollutant degradation and fiber bleaching. This genome provides a high quality draft sequence of a basidiomycete, a major fungal phylum that includes important plant and animal pathogens.

Today's consumer electronics, such as cell phones, tablets and other portable electronic devices, are typically made of non-renewable, non-biodegradable, and sometimes potentially toxic (for example, gallium arsenide) materials. These consumer electronics are frequently upgraded or discarded, leading to serious environmental contamination. Thus, electronic systems consisting of renewable and biodegradable materials and minimal amount of potentially toxic materials are desirable. Here we report high-performance flexible microwave and digital electronics that consume the smallest amount of potentially toxic materials on biobased, biodegradable and flexible cellulose nanofibril papers. Furthermore, we demonstrate gallium arsenide microwave devices, the consumer wireless workhorse, in a transferrable thin-film form. Successful fabrication of key electrical components on the flexible cellulose nanofibril paper with comparable performance to their rigid counterparts and clear demonstration of fungal biodegradation of the cellulose-nanofibril-based electronics suggest that it is feasible to fabricate high-performance flexible electronics using ecofriendly materials.

Solar steam generation with subsequent steam recondensation has been regarded as one of the most promising techniques to utilize the abundant solar energy and sea water or other unpurified water through water purification, desalination, and distillation. Although tremendous efforts have been dedicated to developing high‐efficiency solar steam generation devices, challenges remain in terms of the relatively low efficiency, complicated fabrications, high cost, and inability to scale up. Here, inspired by the water transpiration behavior of trees, the use of carbon nanotube (CNT)‐modified flexible wood membrane (F‐Wood/CNTs) is demonstrated as a flexible, portable, recyclable, and efficient solar steam generation device for low‐cost and scalable solar steam generation applications. Benefitting from the unique structural merits of the F‐Wood/CNTs membrane—a black CNT‐coated hair‐like surface with excellent light absorbability, wood matrix with low thermal conductivity, hierarchical micro‐ and nanochannels for water pumping and escaping, solar steam generation device based on the F‐Wood/CNTs membrane demonstrates a high efficiency of 81% at 10 kW cm −2 , representing one of the highest values ever‐reported. The nature‐inspired design concept in this study is straightforward and easily scalable, representing one of the most promising solutions for renewable and portable solar energy generation and other related phase‐change applications.

This chapter includes overall chemical composition of wood, methods of analysis, structure of hemicellulose components and degree of polymerization of carbohydrates. Tables of data are compiled for woods of several countries. Components include: cellulose (Cross and Bevan, holo-, and alpha-), lignin, pentosans, and ash. Solubilities in 1% sodium hydroxide, hot water, ethanol/benzene, and ether are reported. The data were collected at Forest Products Laboratory (Madison, Wisconsin) from 1927-68 and were previously unpublished. These data include both United States and foreign woods. Previously published data include compositions of woods from Borneo, Brazil, Cambodia, Chile, Colombia, Costa Rica, Ghana, Japan, Mexico, Mozambique, Papua New Guinea, the Philippines, Puerto Rico, Taiwan, and the USSR. Data from more detailed analyses are presented for common temperate-zone woods and include the individual sugar composition (as glucan, xylan, galactan, arabinan, and mannan), uronic anhydride, acetyl, lignin, and ash.

We used eddy covariance; gas-exchange chambers; radiocarbon analysis; wood, moss, and soil inventories; and laboratory incubations to measure the carbon balance of a 120-year-old black spruce forest in Manitoba, Canada. The site lost 0.3 +/- 0.5 metric ton of carbon per hectare per year (ton C ha-1 year-1) from 1994 to 1997, with a gain of 0.6 +/- 0.2 ton C ha-1 year-1 in moss and wood offset by a loss of 0.8 +/- 0.5 ton C ha-1 year-1 from the soil. The soil remained frozen most of the year, and the decomposition of organic matter in the soil increased 10-fold upon thawing. The stability of the soil carbon pool ( approximately 150 tons C ha-1) appears sensitive to the depth and duration of thaw, and climatic changes that promote thaw are likely to cause a net efflux of carbon dioxide from the site.

Basidiomycota (basidiomycetes) make up 32% of the described fungi and include most wood-decaying species, as well as pathogens and mutualistic symbionts. Wood-decaying basidiomycetes have typically been classified as either white rot or brown rot, based on the ability (in white rot only) to degrade lignin along with cellulose and hemicellulose. Prior genomic comparisons suggested that the two decay modes can be distinguished based on the presence or absence of ligninolytic class II peroxidases (PODs), as well as the abundance of enzymes acting directly on crystalline cellulose (reduced in brown rot). To assess the generality of the white-rot/brown-rot classification paradigm, we compared the genomes of 33 basidiomycetes, including four newly sequenced wood decayers, and performed phylogenetically informed principal-components analysis (PCA) of a broad range of gene families encoding plant biomass-degrading enzymes. The newly sequenced Botryobasidium botryosum and Jaapia argillacea genomes lack PODs but possess diverse enzymes acting on crystalline cellulose, and they group close to the model white-rot species Phanerochaete chrysosporium in the PCA. Furthermore, laboratory assays showed that both B. botryosum and J. argillacea can degrade all polymeric components of woody plant cell walls, a characteristic of white rot. We also found expansions in reducing polyketide synthase genes specific to the brown-rot fungi. Our results suggest a continuum rather than a dichotomy between the white-rot and brown-rot modes of wood decay. A more nuanced categorization of rot types is needed, based on an improved understanding of the genomics and biochemistry of wood decay.

Applications of cellulose nanomaterials (CNMs) have attracted increasing attention in recent years. One conceivable path lies in their commercial applications for packaging, in which their barrier properties will play an important role in determining their competiveness with conventional materials. This review critically analyzes the performance of CNMs acting as a barrier against moisture and oxygen permeation in CNM films, CNM-coated polymers and papers, and CNM-reinforced polymer composites, gives some insights into remaining challenges, and brings an overall perspective of compositing CNMs with other materials to achieve balanced properties adequate for barrier packaging. In general, CNMs are a poor moisture barrier but excellent oxygen barrier in the dry state and are still good below 65% relative humidity. The addition of CNMs can improve the oxygen barrier of the resulting polymer composites; however, neat CNM coatings and films can afford better oxygen barrier properties than dispersed CNMs in coatings and nanocomposites. The morphology and surface functionality of CNMs can be tailored to maximize the barrier performance of materials comprising them. The higher the surface charge density is of CNMs, the better is the barrier performance of coated polymers. Like other oxygen barriers such as ethylene vinyl alcohol and cellophane, the moisture sensitivity and sealability of CNMs can be improved by sandwiching them with high moisture-resistant and sealable polymers such as a polyolefin. A multilayered structure with layers of CNMs providing oxygen resistance covered by other layers of polymers providing moisture resistance and sealability might be competitive in barrier packaging markets dominated by synthetic plastics.

Abstract The energy used for regulating building temperatures accounts for 14% of the primary energy consumed in the U.S. One‐quarter of this energy is leaked through inefficient glass windows in cold weather. The development of transparent composites could potentially provide affordable window materials with enhanced energy efficiency. Transparent wood as a promising material has presented desirable performances in thermal and light management. In this work, the performance of transparent wood is optimized toward an energy efficient window material that possesses the following attributes: 1) high optical transmittance (≈91%), comparable to that of glass; 2) high clarity with low haze (≈15%); 3) high toughness (3.03 MJ m −3 ) that is 3 orders of magnitude higher than standard glass (0.003 MJ m −3 ); 4) low thermal conductivity (0.19 W m −1 K −1 ) that is more than 5 times lower than that of glass. Additionally, the transparent wood is a sustainable material, with low carbon emissions and scaling capabilities due to its compatibility with industry‐adopted rotary cutting methods. The scalable, high clarity, transparent wood demonstrated in current work can potentially be employed as energy efficient and sustainable windows for significant environmental and economic benefits.

Brown rot decay removes cellulose and hemicellulose from wood--residual lignin contributing up to 30% of forest soil carbon--and is derived from an ancestral white rot saprotrophy in which both lignin and cellulose are decomposed. Comparative and functional genomics of the "dry rot" fungus Serpula lacrymans, derived from forest ancestors, demonstrated that the evolution of both ectomycorrhizal biotrophy and brown rot saprotrophy were accompanied by reductions and losses in specific protein families, suggesting adaptation to an intercellular interaction with plant tissue. Transcriptome and proteome analysis also identified differences in wood decomposition in S. lacrymans relative to the brown rot Postia placenta. Furthermore, fungal nutritional mode diversification suggests that the boreal forest biome originated via genetic coevolution of above- and below-ground biota.

Brown-rot fungi such as Postia placenta are common inhabitants of forest ecosystems and are also largely responsible for the destructive decay of wooden structures. Rapid depolymerization of cellulose is a distinguishing feature of brown-rot, but the biochemical mechanisms and underlying genetics are poorly understood. Systematic examination of the P. placenta genome, transcriptome, and secretome revealed unique extracellular enzyme systems, including an unusual repertoire of extracellular glycoside hydrolases. Genes encoding exocellobiohydrolases and cellulose-binding domains, typical of cellulolytic microbes, are absent in this efficient cellulose-degrading fungus. When P. placenta was grown in medium containing cellulose as sole carbon source, transcripts corresponding to many hemicellulases and to a single putative beta-1-4 endoglucanase were expressed at high levels relative to glucose-grown cultures. These transcript profiles were confirmed by direct identification of peptides by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Also up-regulated during growth on cellulose medium were putative iron reductases, quinone reductase, and structurally divergent oxidases potentially involved in extracellular generation of Fe(II) and H(2)O(2). These observations are consistent with a biodegradative role for Fenton chemistry in which Fe(II) and H(2)O(2) react to form hydroxyl radicals, highly reactive oxidants capable of depolymerizing cellulose. The P. placenta genome resources provide unparalleled opportunities for investigating such unusual mechanisms of cellulose conversion. More broadly, the genome offers insight into the diversification of lignocellulose degrading mechanisms in fungi. Comparisons with the closely related white-rot fungus Phanerochaete chrysosporium support an evolutionary shift from white-rot to brown-rot during which the capacity for efficient depolymerization of lignin was lost.