Development of surface-engineering strategies, which are facile, versatile, and mild, are highly desirable in tailor-made functionalization of high-performance bioinspired nanocomposites. We herein disclose for the first time a general organocatalytic strategy for the functionalization and hydrophobization of nacre-mimetic nanocomposites, which includes vide supra key aspects of surface engineering. The merging of metal-free catalysis and the design of nacre-mimetic nanocomposite materials were demonstrated by the organocatalytic surface engineering of cellulose nanofibrils/clay nanocomposites providing the corresponding bioinspired nanocomposites with good mechanical properties, hydrophobicity, and useful thia-, amino, and olefinic functionalities.
Residual stresses in glass-fiber composites were studied on the micro and meso scales by computational and experimental methods. Transmitted polarized light images of thin sections were compared with 3D finite-element solutions of a sample containing 1410 fibers. Calculated point-wise stresses were derived from a linear thermoelastic model with negligibly small numerical errors. Regions with calculated maximum compressive stresses showed good agreement with experimentally observed optical bands. A material with poor interfacial adhesion showed weaker optical effects indicating fiber/matrix debonding. On the basis of these results it stems likely that irreversible matrix deformation and debonding can take place in the curing phase.
A template transfer method (TTM) and a fiber fixation technique were established for fiber handling and micro tensile stage mounting of aligned and non-aligned electrospun fiber mats. The custom-made template had been precut to be mounted on a variety of collectors, including a rapidly rotating collector used to align the fibers. The method eliminated need for direct physical interaction with the fiber mats before or during the tensile testing since the fiber mats were never directly clamped or removed from the original substrate. By using the TTM it was possible to measure the tensile properties of aligned poly(methyl methacrylate) (PMMA) fiber mats, which showed a 250 % increase in strength and 450 % increase in modulus as compared to a non-aligned system. The method was further evaluated for aligned PMMA fibers reinforced with cellulose (4 wt%) prepared as enzymatically derived nanofibrillated cellulose (NFC). These fibers showed an additional increase of 30 % in both tensile strength and modulus, resulting in a toughness increase of 25 %. The fracture interfaces of the PMMA-NFC fibers showed a low amount of NFC pull-outs, indicating favorable phase compatibility. The presented fiber handling technique is universal and may be applied where conservative estimates of mechanical properties need to be assessed for very thin fibers.
In solid foams, most physical properties are determined by the pore size and shape distributions and the organisation of the pores. For this reason, it is important to control the structure of porous materials. We recently tackled this issue with the help of microfluidic-aided foam templating, which allowed us to generate mono-disperse and highly ordered chitosan foams. However, the properties of foams also depend on the properties of the pore wall constituents. In case of chitosan-based foams, the foams have poor absolute mechanical properties, simply due to the fact that the solubility of chitosan in water is very low, so that the relative density of the freeze-dried foams becomes very small. Drawing inspiration from the field of nanocomposites, we incorporated cellulose nanofibres into the foamed chitosan solutions, with a view to strengthening the pore walls in the foam and thus the mechanical properties of the final foam. We report here how the cellulose nanofibres affect the structure of both the liquid foam template and the solid foam. The resulting nanocomposite foams have improved mechanical properties, which, however, are not proportional to the amount of cellulose nanofibres in the composites. One reason for this observation is the disturbance of the porous structure of the solid foams by the cellulose nanofibres.
The nanocellulose fibril is the major load-bearing component in the wood cell wall. It is readily disintegrated from wood pulp, and of great interest as a component in new materials. It can be used to form 100% cellulose nanofiber (CNF) nanopaper films or polymer matrix nanocomposite films of high cellulose content, where the CNF network controls most physical properties. Here, the uniaxial tensile properties of CNF nanopaper and composite films are discussed, together with the deformation mechanisms. The CNF network and most types of nanocomposite films are prepared by a scalable filtration process akin to paper-making. The effects of intrinsic CNF properties, degree of CNF dispersion, CNF-CNF adhesion, CNF-polymer matrix interaction, CNF orientation, and humidity are also discussed.
Cellulose nanocomposites can be considered for semistructural load-bearing applications where modulus and strength requirements exceed 10 GPa and 100 MPa, respectively. Such properties are higher than for most neat polymers but typical for molded short glass fiber composites. The research challenge for polymer matrix biocomposites is to develop processing concepts that allow high cellulose nanofibril (CNF) content, nanostructural control in the form of well-dispersed CNF, the use of suitable polymer matrices, as well as molecular scale interface tailoring to address moisture effects. From a practical point of view, the processing concept needs to be scalable so that large-scale industrial processing is feasible. The vast majority of cellulose nanocomposite studies elaborate on materials with low nanocellulose content. An important reason is the challenge to prevent CNF agglomeration at high CNF content. Research activities are therefore needed on concepts with the potential for rapid processing with controlled nanostructure, including well-dispersed fibrils at high CNF content so that favorable properties are obtained. This perspective discusses processing strategies, agglomeration problems, opportunities, and effects from interface tailoring. Specifically, preformed CNF mats can be used to design nanostructured biocomposites with high CNF content. Because very few composite materials combine functional and structural properties, CNF materials are an exception in this sense. The suggested processing concept could include functional components (inorganic clays, carbon nanotubes, magnetic nanoparticles, among others). In functional three-phase systems, CNF networks are combined with functional components (nanoparticles or fibril coatings) together with a ductile polymer matrix. Such materials can have functional properties (optical, magnetic, electric, etc.) in combination with mechanical performance, and the comparably low cost of nanocellulose may facilitate the use of large nanocomposite structures in industrial applications.
We report on a sustainable route to protective nanocomposite coatings, where one of the components, nanocellulose fibrils, is derived from trees and the glass matrix is an inexpensive sol-gel organic-inorganic hybrid of zirconium alkoxide and an epoxy-functionalized silane. The hydrophilic nature of the colloidal nanocellulose fibrils is exploited to obtain a homogeneous one-pot suspension of the nanocellulose in the aqueous sol-gel matrix precursors solution. The mixture is then sprayed to form nano composite coatings of a well-dispersed, random in-plane nano cellulose fibril network in a continuous organic inorganic glass matrix phase. The nanocellulose incorporation in the sol-gel matrix resulted in nanostructured composites with marked effects on salient coating properties including optical transmittance, hardness, fracture energy, and water contact angle. The particular role of the nanocellulose fibrils on coating fracture properties, important for coating reliability, was analyzed and discussed in terms of fibril morphology, molecular matrix, and nanocellulose/matrix interactions.
Wide-spread use of cellulose nanofibril (CNF) biocomposites and nanomaterials is limited by CNF moisture sensitivity due to surface hydration. We report on a versatile and scalable interface tailoring route for CNF to address this, based on technically important epoxide chemistry. Bulk impregnation of epoxide-amine containing liquids is used to show that CNF hydroxyls can react with epoxides at high rates and high degree of conversion to form covalent bonds. Reactions take place inside nanostructured CNF networks under benign conditions, and are verified by solid state NMR. Epoxide modified CNF nanopaper shows significantly improved mechanical properties under moist and wet conditions. High resolution microscopy is used in fractography studies to relate the property differences to structural change. The cellulose-epoxide interface tailoring concept is versatile in that the functionality of molecules with epoxide end-groups can be varied over a wide range. Furthermore, epoxide reactions with nanocellulose can be readily implemented for processing of moisture-stable, tailored interface biocomposites in the form of coatings, adhesives and molded composites.
Nanocomposites with high volume fractions (15-50 vol%) of nanofibrillated cellulose (NFC) were prepared by impregnation of a wet porous NFC network with acetone/epoxy/amine solution. Infrared spectroscopy studies revealed a significant increase in curing rate of epoxy (EP) in the presence of NFC. The NFC provided extremely efficient reinforcement (at 15 vol%: 3-fold increase in stiffness and strength to 5.9 GPa and 109 MPa, respectively), and ductility was preserved. Besides, the glass transition temperature increased with increasing NFC content (from 68 degrees C in neat epoxy to 86 degrees C in 50 vol% composite). Most interestingly, the moisture sorption values were low and even comparable to neat epoxy for the 15 vol% NFC/EP. This material did not change mechanical properties at increased relative humidity (90% RH). Thus, NFC/EP provides a unique combination of high strength, modulus, ductility, and moisture stability for a cellulose-based biocomposite. Effects from nanostructural and interfacial tailoring are discussed.
Although the anisotropy of wood fibers is reasonably well established, the anisotropy of injection molded wood fiber composites is not well understood. This work focuses on chemo-thermomechanical pulp (CTMP) reinforced polypropylene (PP) composites. A kinetic mixer (Gelimat) is used for compounding CTMP/PP composites, followed by injection molding. Effects from processing induced orientation on mechanical properties are investigated. For this purpose, a film gate mold was designed to inject composites in the shape of plates so that specimens in different directions to the flow could be evaluated. Observations from tensile tests were complemented by performing flexural tests (in different directions) on discs cut from the injected plates. SEM was used to qualitatively observe the fiber orientation in the composites. At high fiber content, both modulus and tensile strength could differ by as much as 40% along the flow and transverse to the flow. The fiber orientation was strongly increased at the highest fiber content, as concluded from theoretical analysis.
The use of cellulosic nanofibers as reinforcement in polymer composites offers great advantages over their petroleum counterparts. Apart from being strong, stiff and low density; they are obtained from naturally occurring resources and as such are favorable from an environmental point of view. A major problem while studying nanomaterials is their tendency to agglomerate, thus leading to inhomogeneous distribution within the polymer matrix. This often results in stress concentrations in the matrix rich regions when the material is subjected to load and therefore, limits the potential application of these materials. A common approach to circumvent this is by surface modification, which facilitates the dispersion in non-polar matrices. An environmental friendly approach, inspired by clay chemistry, was used to functionalize the CNC surface. It was shown that the CNC could be modified in a rather convenient way to attach a variety of functional groups on the surface. Primarily, the problem of cellulose nanocrystal (CNC) distribution in a hydrophobic polymer matrix is investigated. Composites prepared from modified CNC were studied and compared with unmodified CNC. The distribution of the CNC is carefully monitored at different stages via UV-Vis spectroscopy and scanning electron microscopy (SEM). The mechanical properties of the resulting materials were characterized by dynamic mechanical as well as uniaxial tensile tests. It was shown that a homogeneous distribution of the CNC exposes a tremendous amount of surface area to interact with the matrix. In such a case, the stress transfer is much more efficient and perhaps, the matrix behavior is modified, which leads to significant improvements in the mechanical properties.
In this work, the problem to disperse cellulose nanocrystals (CNC) in hydrophobic polymer matrices has been addressed through application of an environmentally friendly chemical modification approach inspired by clay chemistry. The objective is to compare the effects of unmodified CNC and modified CNC (modCNC) reinforcement, where degree of CNC dispersion is of interest. Hydrophobic functionalization made it possible to disperse wood-based modCNC in organic solvent and cast well-dispersed nanocomposite films of poly(vinyl acetate) (PVAc) with 1-20 wt % CNC. Composite films were studied by infrared spectroscopy (FT-IR), UV-vis spectroscopy, dynamic mechanical thermal analysis (DMTA), tensile testing, and field-emission scanning electron microscopy (FE-SEM). Strongly increased mechanical properties were observed for modCNC nanocomposites. The reinforcement efficiency was much lower in unmodified CNC composites, and specific mechanisms causing the differences are discussed.
Delignified chemical wood pulp fibers can be designed to have a controlled structure of cellulose fibril aggregates to serve as porous templates in biocomposites with unique properties. The potential of these fibers as reinforcement for an epoxy matrix (EP) was investigated in this work. Networks of porous wood fibers were impregnated with monomeric epoxy and cured. Microscopy images from ultramicrotomed cross sections and tensile fractured surfaces were used to study the distribution of matrix inside and around the fibers - at two different length scales. Mechanical characterization at different relative humidity showed much improved mechanical properties of biocomposites based on epoxy-impregnated fibers and they were rather insensitive to surrounding humidity. Furthermore, the mechanical properties of cellulose-fiber biocomposites were compared with those of cellulose-nanofibril (CNF) composites; strong similarities were found between the two materials. The reasons for this, some limitations and the role of specific surface area of the fiber are discussed.
Biocomposites reinforced by natural plant fibers tend to be brittle, moisture sensitive and have limited strength. Wood cellulose nanofibers (CNF) were therefore used to reinforce an unsaturated polyester matrix (UP) without the need of coupling agents or CNF surface modification. The nanostructured CNF network reinforcement strongly improves modulus and strength of UP but also ductility and toughness. A template-based prepreg processing approach of industrial potential is adopted, which combines high CNF content (up to 45 vol%) with nanoscale CNF dispersion. The CNF/UP composites are subjected to moisture sorption, dynamic thermal analysis, tensile tests at different humidities, fracture toughness tests and fractography. The glass transition temperature (T-g) increases substantially with CNF content. Modulus and strength of UP increase about 3 times at 45 vol% CNF whereas ductility and apparent fracture toughness are doubled. Tensile properties at high humidity are compared with other bio-composites and interpreted based on differences in molecular interactions at the interface.
TW transparent wood/polymer biocomposite laminates are of interest as multifunctional materials with good longitudinal modulus, tensile strength and optical transmittance. The effect of filling the pore space in wood with a polymer matrix on fracture toughness and crack growth is not well understood. Here, we carried out in-situ fracture tests on neat birch wood and laminates made of four layers of delignified birch veneers impregnated with poly(methyl methacrylate) (PMMA) and investigated crack growth in the tangential-radial (TR) fracture system. Fracture toughness KIc and JIc at crack initiation were estimated, including FEM analysis. SEM microscopy revealed that cracks primarily propagate along the ray cells, but cell wall peeling and separation between the PMMA and wood phases also take place. A combination of in-situ tests and strain field measured by digital image correlation (DIC) showed twice as long fracture process zone of TW laminates compared with neat birch.
We report the mechanical strength of native chitin nanofibrils. Highly crystalline alpha-chitiri nanofibrils Were purified from filaments produced by a microalgae Phaeocystis globosa, and two types of beta-chitin nariofibrils were purified from pens of a squid Loligo bleekeri and tubes of a tubeworm Lamellibrachia satsuma, with relatively low and high crystallinity, respectively. These chitin nanofibrils were fully dispersed in water. The strength of individualized nanofibrils was estimated using cavitation induced tensile fracture of nanoscale filaments in a liquid medium. Both types of beta-chitin nanofibrils exhibited similar strength values of approximately 3 GP; in contrast, the alpha-chitin nanofibrils exhibited a much lower strength value of 1.6 GPa. These strength estimates suggest that the tensile strength of chitin nanofibrils is governed by the molecular packing modes of chitin rather than their crystallinity.
The influence of temperature on structure and properties of the cellulose Iβ crystal was studied by molecular dynamics simulations with the GROMOS 45a4 force-field. At 300 K, the modeled crystal agreed reasonably with several sets of experimental data, including crystal density, corresponding packing and crystal unit cell dimensions, chain conformation parameters, hydrogen bonds, Young's modulus, and thermal expansion coefficient at room temperature. At high-temperature (500 K), the cellulose chains remained in sheets, despite differences in the fine details compared to the room-temperature structure. The density decreased while the a and b cell parameters expanded by 7.4% and 6%, respectively, and the c parameter (chain axis) slightly contracted by 0.5%. Cell angles α and β divided into two populations. The hydroxymethyl groups mainly adopted the gt orientation, and the hydrogen-bonding pattern thereby changed. One intrachain hydrogen bond, O2'H2'···O6, disappeared and consequently the Young's modulus decreased by 25%. A transition pathway between the low- and high-temperature structures has been proposed, with an initial step being an increased intersheet separation, which allowed every second cellulose chain to rotate around its helix axis by about 30°. Second, all hydroxymethyl groups changed their orientations, from tg to gg (rotated chains) and from tg to gt (non-rotated chains). When temperature was further increased, the rotated chains returned to their original orientation and their hydroxymethyl groups again changed their conformation, from gg to gt. A transition temperature of about 450 K was suggested; however, the transition seems to be more gradual than sudden. The simulated data on temperature-induced changes in crystal unit cell dimensions and the hydrogen-bonding pattern also compared well with experimental results.
A technical problem in cellulosic nanocomposite materials is the weak interaction between hydrophilic cellulose and hydrophobic polymer matrices. One approach to solve this difficulty is to chemically graft monomers of the matrix polymer onto the cellulose surface. An important question is to understand the effect such surface modification has on the interfacial properties. Semi-empirical approaches to estimate work of adhesion based on surface energies do not provide information on specific molecular interactions. Details about these interactions were obtained using molecular dynamics (MD) simulation. Cellulose interfaces with water and caprolactone medium were modeled with different amounts of grafted caprolactone. The modification lead to an increased work of adhesion between the surface and its surrounding medium. Furthermore, the MD simulations showed that the interaction between cellulose, both modified and non-modified, and surrounding medium is dominated by Coulomb interactions, predominantly as hydrogen bonds.
Pulling single cellulose molecules from a crystalline cellulose surface has been modeled by molecular dynamics (MD) simulations of the experimental procedure used in atomic force microscopy (AFM). Specifically, the aim of the study was to investigate cellulose interactions at desorption. Simulations were performed in both water and the organic solvent cyclohexane. Moreover, the effects of initial octamer conformation and orientation with respect to the surface chains were studied. A strong effect from the solvent was observed. In cyclohexane, normal forces of 200-500 pN and energies of 43.5 +/- 6.0 kJ/mol glucose unit were required to pull off the octamer. The normal forces in water were substantially lower, around 58 pN, and the energies were 18.2 +/- 3.6 kJ/mol glucose unit. In addition, the lateral components of the pull-off force were shown to provide information on initial conformation and orientation. Hydrogen bonds between the octamer and surface were analyzed and found to be an important factor in the pull-off behavior. Altogether, it was shown that MD provides detailed information on the desorption processes that may be useful for the interpretation of AFM experiments.
Solid-state nuclear magnetic resonance (CP/MAS 13C NMR) spectroscopy has often been used to study cellulose structure, but some features of the cellulose NMR spectrum are not yet fully understood. One such feature is a doublet around 84 ppm, a signal that has been proposed to originate from C4 atoms at cellulose fibril surfaces. The two peaks yield different T1, differing by approximately a factor of 2 at 75 MHz. In this study, we calculate T1 from C4-H4 vector dynamics obtained from molecular dynamics computer simulations of cellulose Iβ-water interfacial systems. Calculated and experimentally obtained T1 values for C4 atoms in surface chains fell within the same order of magnitude, 3-20 s. This means that the applied force field reproduces relevant surface dynamics for the cellulose-water interface sufficiently well. Furthermore, a difference in T1 of about a factor of 2 in the range of Larmor frequencies 25-150 MHz was found for C4 atoms in chains located on top of two different crystallographic planes, namely, (110) and (10). A previously proposed explanation that the C4 peak doublet could derive from surfaces parallel to different crystallographic planes is herewith strengthened by computationally obtained evidence. Another suggested basis for this difference is that the doublet originates from C4 atoms located in surface anhydro-glucose units with hydroxymethyl groups pointing either inward or outward. This was also tested within this study but was found to yield no difference in calculated T1.
A combined solid-state NMR and Molecular Dynamics simulation study of cellulose in urea aqueous solution and in pure water was conducted. It was found that the local concentration of urea is significantly enhanced at the cellulose/solution interface. There, urea molecules interact directly with the cellulose through both hydrogen bonds and favorable dispersion interactions, which seem to be the driving force behind the aggregation. The CP/MAS (13)C spectra was affected by the presence of urea at high concentrations, most notably the signal at 83.4 ppm, which has previously been assigned to C4 atoms in cellulose chains located at surfaces parallel to the (110) crystallographic plane of the cellulose I beta crystal. Also dynamic properties of the cellulose surfaces, probed by spin-lattice relaxation time (13)CT (1) measurements of C4 atoms, are affected by the addition of urea. Molecular Dynamics simulations reproduce the trends of the T (1) measurements and lends new support to the assignment of signals from individual surfaces. That urea in solution is interacting directly with cellulose may have implications on our understanding of the mechanisms behind cellulose dissolution in alkali/urea aqueous solutions.
Cellulose nanopaper in the form of nanofiber networks show superior mechanical performance and new functional characteristics compared with the brittle paper and fiberboard materials and thermoplastic biocomposites, which are commercially available. The chapter analyzes the potential to combine toughness and strength in polymer matrix nanocomposites based on cellulose nanofiber networks.
It is difficult to prepare clay nanocomposites of high volume fraction clay. Layer-by-layer methods have been successful, but are difficult to use in large-scale production. In the present study, papermaking techniques are used for fabrication of oriented clay platelet nanocomposites. Materials are characterized by TEM, SEM, XRD and mechanical and barrier properties are measured and fire retardance performance is demonstrated. High strength and stiffness is demonstrated and the potential for bionanocomposites is discussed, in particular with moisture durability in mind.
Cellulose biocomposites are widely used in industry as a low-cost engineering material with plant fiber reinforcement. However, chemical and microstructural heterogeneity causes low strength, low strain-to-failure, high moisture sensitivity, and odor and discoloration problems. Efforts toward improved performance through fiber orientation control, increased fiber lengths, and biopolymer use are reviewed. Interfacial strength control and moisture sensitivity are remaining challenges. As an attractive alternative reinforcement, high-quality cellulose nanofibers obtained by wood pulp fiber disintegration can be prepared at low cost. These nanofibers have high length/diameter ratios, diameters in the 5-15 nm range, and intrinsically superior physical properties. Wood cellulose nanofibers are interesting as an alternative reinforcement to more expensive nanoparticles, such as carbon nanotubes. Nanopaper and polymer matrix nanocomposites based on cellulose nanofiber networks show high strength, high work-of-fracture, low moisture adsorption, low thermal expansion, high thermal stability, high thermal conductivity, exceptional barrier properties, and high optical transparency. The favorable mechanical performance of bioinspired foams and low-density aerogels is reviewed. Future applications of cellulose biocomposites will be extended from the high-volume/low-cost end toward high-tech applications, where cellulose properties are fully exploited in nanostructured materials.
The limited ductility of plant fiber biocomposites is typically caused by interfacial debonding mechanisms at low strain. This leads to damage development and premature failure. The present paper discusses recent results on cellulose nanocomposites with thermoset and thermoplastic matrices, where substantial ductility is observed. The data are presented and reasons for the observed ductility are discussed.
It is a challenging task to realize the vision of hierarchically structured nanomaterials for large-scale applications. Herein, the biomaterial wood as a large-scale biotemplate for functionalization at multiple scales is discussed, to provide an increased property range to this renewable and CO2-storing bioresource, which is available at low cost and in large quantities. The Progress Report reviews the emerging field of functional wood materials in view of the specific features of the structural template and novel nanotechnological approaches for the development of wood-polymer composites and wood-mineral hybrids for advanced property profiles and new functions.
The present invention relates to cellulose-based materials comprising nanofibrillated cellulose (NFC) from native cellulose. exhibiting highly superior properties as compared to other cellulose-based materials, a method for preparing such cellulose-based material, and uses thereof are also disclosed.
The present invention relates to composite material of xyloglucan and clay for use as a coating material. The invention also relates to a method of producing the coating.
Tamarind seed xyloglucan is an interesting polysaccharide of high molar mass with excellent thermomechanical properties. Several plasticizers were studied in order to facilitate thermal processing and improve toughness (work to fracture) of xyloglucan film materials: sorbitol, urea, glycerol and polyethylene oxide. Films of different compositions were cast and studied by thermogravimetric analysis (TGA), calorimetry (DSC), dynamic mechanical thermal analysis (DMA) and tensile tests. Results are analysed and discussed based on mechanisms and practical considerations. Highly favourable characteristics were found with XG/sorbitol combinations, and the thermomechanical properties motivate further work on this material system, for instance as a matrix in biocomposite materials.
Functional analysis of genes and proteins involved in wood formation and fiber properties often involves phenotyping saplings of transgenic trees. The objective of the present study was to develop a tensile test method for small green samples from saplings, and to compare mechanical properties of juvenile European aspen (Populus tremula) and hybrid aspen (Populus tremula × tremuloides). Small microtomed sections were manufactured and successfully tested in tension parallel to fiber orientation. Strain was determined by digital speckle photography. Results showed significantly lower values for juvenile hybrid aspen in both Young's modulus and tensile strength parallel to the grain. Average Young's moduli spanned the ranges of 5.9-6.6 and 4.8-6.0 GPa for European aspen and hybrid aspen, respectively. Tensile strength was in the range of 45-49 MPa for European aspen and 32-45 MPa for hybrid aspen. The average density (oven-dry) was 284 kg/m3 for European aspen and 221 kg/m3 for hybrid aspen. Differences in mechanical properties correlated with differences in density.
Yew (Taxus baccata L.) longbow was the preferred weapon in the Middle Ages until the emergence of guns. In this study, the tensile, compression, and bending properties of yew were investigated. The advantage of yew over the other species in the study was also confirmed by a simple beam model. The superior toughness of yew has the effect that a yew longbow has a higher range compared with bows made from other species. Unexpectedly, the mechanical performance of a bow made from yew is influenced by the juvenile-to-mature wood ratio rather than by the heartwood-to-sapwood ratio. A yew bow is predicted to have maximized performance at a juvenile wood content of 30-50%, and located at the concave side (the compressive side facing the bowyer). Here, the stiffness and yield stress in compression should be as high as possible.
In 1628, the Swedish warship Vasa capsized on her maiden voyage and sank in the Stockholm harbor. The ship was recovered in 1961 and, after polyethylene glycol (PEG) impregnation, it was displayed in the Vasa museum. Chemical investigations of the Vasa were undertaken in 2000, and extensive holocellulose degradation was reported at numerous locations in the hull. We have now studied the longitudinal tensile strength of Vasa oak as a function of distance from the surface. The PEG-content, wood density, and cellulose microfibril angle were determined. The molar mass distribution of holocellulose was determined as well as the acid and iron content. A good correlation was found between the tensile strength of the Vasa oak and the average molecular weight of the holocellulose, where the load-bearing cellulose microfibril is the critical constituent. The mean tensile strength is reduced by approximately 40%, and the most affected areas show a reduction of up to 80%. A methodology is developed where variations in density, cellulose microfibril angle, and PEG content are taken into account, so that cell wall effects can be evaluated in wood samples with different rate of impregnation and morphologies.
To prevent deformation and cracking of waterlogged archaeological wood, polyethylene glycol (PEG) as a bulk impregnation agent is commonly applied. PEG maintains the wood in a swollen state during drying. However, swelling of wood can reduce its mechanical properties. In this study, the cellular structure of oak and cell wall swelling was characterized by scanning electron microscopy (SEM) of transverse cross-sections, and the microfibril angle of oak fibers was determined by wide angle X-ray scattering (WAXS). Samples of recent European oak (Quercus robur L) impregnated with PEG (molecular weight of 600) were tested in axial tension and radial compression. Mechanical tests showed that axial tensile modulus and strength were only slightly affected by PEG, whereas radial compressive modulus and yield strength were reduced by up to 50%. This behavior can be explained by the microstructure and deformation mechanisms of the material. Microfibril angles in tensile test samples were close to zero. This implies tensile loading of cellulose microfibrils within the fiber cell walls without almost any shear in the adjacent amorphous matrix. These results are important because they can help separate the impact of PEG on mechanical properties from that of chemical degradation in archaeological artifacts, which display only small to moderate biological degradation.
Several key enzymes in lignin biosynthesis of Populus have been down-regulated by transgenie approaches to investigate their role in wood lignification and to explore their potential for lignin modification. Cinnamate 4-hydroxylase is an enzyme in the early phenylpropanoid pathway that has not yet been functionally analyzed in Populus. This study shows that down-regulation of cinnamate 4-hydroxylase reduced Klason lignin content by 30% with no significant change in syringyl to guaiacyl ratio. The lignin reduction resulted in ultrastructural differences of the wood and a 10% decrease in wood density. Mechanical properties investigated by tensile tests and dynamic mechanical analysis showed a decrease in stiffness, which could be explained by the lower density. The study demonstrates that a large modification in lignin content only has minor influences on tensile properties of wood in its axial direction and highlights the usefulness of wood modified beyond its natural variation by transgene technology in exploring the impact of wood biopolymer composition and ultrastructure on its material properties.