Central nervous system (CNS) injuries such as stroke or trauma can lead to long-lasting disability, and there is no currently accepted treatment to regenerate functional CNS tissue after injury. Hydrogels can mimic the neural extracellular matrix by providing a suitable 3D structure and mechanical properties and have shown great promise in CNS tissue regeneration. Here we present successful synthesis of a thermosensitive hyaluronic acid-RADA 16 (Puramatrix (TM)) peptide interpenetrating network (IPN) that can be applied in situ by injection. Thermosensitive hyaluronic acid (HA) was first synthesized by combining HA with poly(N-isopropylacrylamide). Then, the Puramatrix (TM) self-assembled peptide was combined with the thermosensitive HA to produce a series of injectable thermoresponsive IPNs. The HA-Puramatrix (TM) IPNs formed hydrogels successfully at physiological temperature. Characterization by SEM, rheological measurements, enzymatic degradation and swelling tests was performed to select the IPN optimized for neurologic use. SEM images of the optimized dry IPNs demonstrated an aligned porous structure, and the rheological measurements showed that the hydrogels were elastic, with an elastic modulus of approximately 500 Pa, similar to that of brain tissue. An evaluation of the cell-material interactions also showed that the IPN had biological characteristics required for tissue engineering, strongly suggesting that the IPN hydrogel possessed properties beneficial for regeneration of brain tissue.
The influence of heterogeneous semiconductors on the photodegradation of phenol in water was investigated using doped tin dioxide (SnO2) nanoparticles. Photocatalysts of SnO2 were synthesized with lanthanum (La), cerium (Ce), and neodymium (Nd) dopants. These photocatalysts were synthesized from tin tetrachloride by sol-gel method with different dopant concentrations, and its photocatalytic degradation was investigated up to 0.8 % under UV-A light in aqueous suspensions. The photocatalytic oxidation reactions were studied by varying photocatalyst composition, light intensity, reaction time, pH of the reaction medium, and phenol concentration. It was found that the photocatalytic activity of rare earth-doped SnO2 for phenol decomposition under UV light irradiation was considerably higher than that of pure SnO2 nanoparticles. The experimental results also indicate that more than 95 % phenol was effectively oxidized in the presence of an aqueous suspension of La: SnO2 nanoparticles within 120 min of UV light irradiation.
Phase transformation studies in ZnO-SnO2 system from zinc metastannate (ZnSnO3) to zinc orthostannate (Zn2SnO4) with annealing temperature are reported. Non-centrosymmetric oxides show unique symmetry dependent and spontaneous polarization properties, which are technologically important. ZnSnO3 particles were synthesized by a simple aqueous synthesis at low temperatures designed with the assistance of potential-pH diagrams. ZnSnO3 particles synthesized at 4 A degrees C are more porous losing the ilmenite structure upon annealing at 200 A degrees C, while the other samples prepared at higher temperatures (25-65 A degrees C) becomes amorphous at 300 A degrees C. The phase transformation into the inverse spinel orthostannate phase occurs around 750 A degrees C in all the samples.
A thermodynamic assessment of the Ni-Te system has been performed using the Calphad method, based on experimental data available in the literature. The proposed description has been developed for use in the modeling of fission-product-induced internal corrosion of stainless steel cladding in Generation IV nuclear reactors. DFT calculations were performed to obtain 0 K properties of solid phases to assist the thermodynamic optimization. The ionic liquid two-sublattice model was used, and most solution phases were modeled using interstitial metal sub-lattices. With a strict number of parameters, the resulting description satisfactorily reproduces all thermodynamic properties and high-temperature phase transitions. The metastable miscibility gap in the Ni-rich liquid that is experimentally suggested is not present in the final description. The phase exhibits a metastable order-disorder transition between the CdI2 and NiAs types of interstitial nickel distribution. The CdI2 prototype is the stable space group at room temperature. Low-temperature ordering phase transitions have been disregarded in this description, since they are not of interest to the application of corrosion in nuclear reactors.
Thermodynamic description of phase diagram and diffusion data are required to model microsegregation during solidification of metallic alloys. Knowledge about non-equilibrium phase diagrams is essential for modeling of microsegregation in practical situations. Therefore, the aim of this study is to theoretically analyze phase diagram and diffusion data for calculation of microsegregation. For this purpose, aluminum-rich part of the Al-Cu phase diagram was recalculated under non-equilibrium conditions. Effect of excess vacancies formed during solidification was considered on both the phase diagram and diffusion coefficient. The results show that by modifying the phase diagram, the calculated results have better consistency with the experimental results, but there is still room for improvement. When the effect of excess vacancies on diffusion coefficient is considered, the modeling results show a much better correlation with the experimental results. The origin of discrepancies between the calculations and experiments are deeply discussed using current theories in solidification.
A technique based on Fourier Transform Infrared Spectroscopy-Attenuated Total Reflectance (FTIR-ATR) was developed and used to study movement of water into bitumen/substrate interfaces, as well as to characterize stripping. Bitumens from different sources were used and applied on various substrates (silicon, germanium and zinc selenide) as thin films. The influence of bitumen type, substrate type, temperature, film thickness and modification with amines, on water damage was studied. The technique gave information on water flow into interfaces and how stripping possibly occurs. It distinguished between stripping and non-stripping bitumens. At least one of three processes occurred, namely water diffusion, film fracture, and bitumen displacement by water, respectively. The diffusion of water did not obey Fick's law. Stripping was influenced by bitumen source when silicon and germanium substrates were used. Notching the films made the process of water entry almost occur immediately. Additives significantly reduced stripping in the moisture-sensitive bitumen on silicon and germanium substrates, even after film notching. Although, good agreement was observed between tests for the bitumens that did not strip, the tests on stripping bitumens showed poor agreement.
This study demonstrates how multi-alloying the Fe-Si–B–P–Cu (Nanomet®) can avoid the strict requirements on the annealing scheme in terms of high heating rate and narrow annealing temperature range in order to grow a homogeneous ultrafine nanocrystalline structure. The rather restricted amorphization capability sets a low limit of the maximum thickness of the amorphous precursor. These shortcomings have their origin in the existence of detrimental pre-existing nuclei in the amorphous precursors, which in turn potentially lead to a heterogeneous crystallization. Here, we have multialloyed Nanomet with CoCNi- and CoCMo- to avoid the creation of these pre-existing nuclei. This leads to improved amorphization capability and changes a potentially heterogeneous crystallization to a homogeneous nanocrystallization over a much broader temperature range than for unalloyed Nanomet. Thus, the requirements for the annealing are much relaxed. This work encompasses quenching the amorphous precursors using melt-spinning, investigating the crystallization temperatures by calorimetry, showing the depletion of pre-existing nuclei by magneto-thermo-gravimetry, conceptualizing the crystallization dynamics using isothermal calorimetry, and finally revealing the excellent soft magnetic properties over a broad annealing temperature interval (390–490 °C for the substituted alloys compared to 410–470 °C for unalloyed Nanomet). The multi-elemental substitution of Fe with CoCMo and CoCNi in Nanomet alloy nearly maintains the saturation magnetization and the coercivity. We believe the substituted alloys provide a better alternative to Nanomet with improved amorphization capability and homogeneous nanocrystallization without any special heat treatment scheme. Graphical abstract: [Figure not available: see fulltext.]
This paper provides an overview of recent progress made in the area of cellulose nanofibre-based nanocomposites. An introduction into the methods used to isolate cellulose nanofibres (nanowhiskers, nanofibrils) is given, with details of their structure. Following this, the article is split into sections dealing with processing and characterisation of cellulose nanocomposites and new developments in the area, with particular emphasis on applications. The types of cellulose nanofibres covered are those extracted from plants by acid hydrolysis (nanowhiskers), mechanical treatment and those that occur naturally (tunicate nanowhiskers) or under culturing conditions (bacterial cellulose nanofibrils). Research highlighted in the article are the use of cellulose nanowhiskers for shape memory nanocomposites, analysis of the interfacial properties of cellulose nanowhisker and nanofibril-based composites using Raman spectroscopy, switchable interfaces that mimic sea cucumbers, polymerisation from the surface of cellulose nanowhiskers by atom transfer radical polymerisation and ring opening polymerisation, and methods to analyse the dispersion of nanowhiskers. The applications and new advances covered in this review are the use of cellulose nanofibres to reinforce adhesives, to make optically transparent paper for electronic displays, to create DNA-hybrid materials, to generate hierarchical composites and for use in foams, aerogels and starch nanocomposites and the use of all-cellulose nanocomposites for enhanced coupling between matrix and fibre. A comprehensive coverage of the literature is given and some suggestions on where the field is likely to advance in the future are discussed.
This review paper provides a recent overview of current international research that is being conducted into the functional properties of cellulose as a nanomaterial. A particular emphasis is placed on fundamental and applied research that is being undertaken to generate applications, which are now becoming a real prospect given the developments in the field over the last 20 years. A short introduction covers the context of the work, and definitions of the different forms of cellulose nanomaterials (CNMs) that are most widely studied. We also address the terminology used for CNMs, suggesting a standard way to classify these materials. The reviews are separated out into theme areas, namely healthcare, water purification, biocomposites, and energy. Each section contains a short review of the field within the theme and summarizes recent work being undertaken by the groups represented. Topics that are covered include cellulose nanocrystals for directed growth of tissues, bacterial cellulose in healthcare, nanocellulose for drug delivery, nanocellulose for water purification, nanocellulose for thermoplastic composites, nanocellulose for structurally colored materials, transparent wood biocomposites, supercapacitors and batteries.
Understanding the arrangement of wood polymers within the fiber wall is important for understanding the mechanical properties of the fibers themselves. Due to their high load bearing ability, the arrangement of cellulose fibrils within the cell wall are of special interest. In this work AFM-Atomic Force Microscopy-in combination with image processing has been used to obtain more information about the arrangement of cellulose aggregates (fibrils) in the secondary cell wall layer of spruce wood. The effects of chemical processing on the arrangement of these cellulose aggregates were also studied. Enlargement of cellulose aggregates was found in the initial phase of the kraft cook. This increase in cellulose aggregate dimensions depended mostly on temperature for treatment temperatures above 140degreesC, regardless of the amount of alkali present. Although hemicelluloses are lost to various degrees under alkaline conditions, the increase in cellulose aggregate size was mainly related to thermally induced rearrangement of the cellulose molecules. The mean side length of cellulose aggregates was found to be around 18 nm in unprocessed wood and 23 nm in processed wood. The cellulose aggregates were assumed to be square shaped in cross section in both cases.
High density cellulose-based materials have been widely used for electrical insulation and (interior) construction or structural material. Similar to typical paper/board materials, the microstructure of high-density fibre mats consists of a porous network of cellulose fibres, which contributes to its highly non-linear mechanical response. Such fibre mats exhibit strong anisotropic material behaviour as well as significant transient (time-or rate-dependent) behaviour. The present investigation is aimed at studying the transient behaviour of high-density cellulose fibre mats, particularly during out-of-plane compression. A viscoelastic-viscoplastic constitutive model dedicated for high-density cellulose-based materials has been used to simulate the responses of the high-density cellulose-based fibre mats upon two types of transient loading, i.e. compressive creep and stress relaxation. The predictions of the model are then compared to the corresponding experimental characterization results, which indicate that material densification mechanism plays a more critical role during out-of-plane compression creep than in stress relaxation.
The graft copolymerization of lignocellulosic fibers with glycidyl methacrylate (GMA) using a Fe2+-thiourea dioxide-H(2)O(2)redox system (Fe2+-TD-H2O2) was studied to overcome the problems of poor compatibility and low surface strength when cellulosic fibers are composited with synthetic polymers. The results show that cellulose-poly(GMA) (CPGMA) was successfully synthesized from GMA and bleachedEucalyptuscellulosic fibers by Fe2+-TD-H(2)O(2)in a mild aqueous solution. CPGMA had high graft rate (244%), high content of epoxy group, and high stability in water. X-ray diffraction patterns and(13)C cross-polarization magic angle spinning nuclear magnetic resonance spectra analyses showed that graft copolymerization did not change the crystalline structure of the CPGMA fiber backbone cellulose, but the crystallinity of the CPGMA fiber decreased with an increase in amorphous PGMA grafting. Scanning electron microscopy confirmed that the grafting reaction occurred both inside and outside the fiber. The specific surface area and pore diameter of the grafted fibers were significantly affected by the grafting. The hydrophobicity of the fibers was significantly enhanced by graft copolymerization. PGMA grafting can enhance the compatibility between the modified fiber and synthetic polymer matrix, improving the processing runnability and product properties of composite materials. A high intensity focused ultrasound method was used to analyze the fiber surface strength. It was confirmed that graft copolymerization significantly improved the surface strength of the grafted fibers. Graft copolymerization can significantly improve the dimensional stability of cellulosic fibers.
The Ti-Cr-C system has been studied by producing samples within the MC-M3C2-M7C3 (M=Ti, Cr) and MC-M3C2-graphite equilibria. The main purpose was to determine the solubility of Cr in MC; however, the solubility of Ti in M3C2 and M7C3 was also of interest, as well as the C content in MC. Heat treatments have been performed at 1673 and 1773 K for 300 h. Thereafter, the phase compositions have been measured with energy-dispersive X-ray spectroscopy (EDS) and wavelength-dispersive X-ray spectroscopy (WDS). X-ray diffraction (XRD), in combination with Rietveld refinement, has been used to determine the lattice parameter for MC. Density functional theory (DFT) calculations were performed to estimate the lattice parameter for MC as a function of composition, and the Rietveld refined lattice parameters for MC have then been recalculated to compositions in order to verify the EDS measurements. The results show that the EDS and XRD measurements give equal results. One conclusion is that, with the current conditions, 300 h is a sufficient heat treatment time in order to reach thermodynamic equilibrium. The other main conclusion is that the solubility of Cr in MC, in general, was overestimated by previous studies due to too short heat treatment times, but also that the solubility is very temperature dependent, especially for the MC-M3C2-graphite equilibrium. This clear temperature dependence was not taken into account in the existing thermodynamic description found in the literature.
Foam bitumen is highly efficient in wetting and coating the surface of mineral aggregate at lower temperature. In order to improve understanding and characterization of the bitumen foam, X-ray radiography was used to study the formation and decay of bitumen foam in 2D representation. Image segmentation analysis was used to determine the foam bubble size distribution. In addition, the main parameters influencing foam bitumen formation, water content, and temperature were also investigated. The results demonstrate the influence of the water content on morphology and expansion of foam bitumen bubbles. Adding more water in the foaming process leads to quick collapse of bubbles and intensifies coalescence of foam bitumen. Higher temperatures produces larger bubbles at early foaming stage compared to lower temperature. Moreover the morphology of bubble formation depends on the types of bitumen used. An exponential function has been implemented to represent the bubble area distribution.
The possibility of creep cavity formation at subboundaries in austenitic stainless steels is analysed. It is demonstrated that such nucleation is thermodynamically feasible. A minimum stress must be exceeded in order to create cavities. The nucleation is assumed to take place where subboundaries on one side of a sliding grain boundary meet subgrain corners on the other side (double ledge models). Alternative cavitation positions can be found where particles meet subboundaries. The nucleation model can quantitatively predict the observed nucleation rate. The model gives a nucleation rate that is proportional to the creep rate in agreement with many experiments
Two models are presented for grain boundary sliding (GBS) displacement during creep. GBS is considered as crucial for the formation of creep cavities. In the first model, the shear sliding model, GBS is accommodated by grains freely sliding along the boundaries in a power-law creeping material. The GBS rate is proportional to the grain size. In the second model, the shear crack model, the sliding boundaries are represented by shear cracks. The GBS rate is controlled by particles in the boundaries. In both models, the GBS displacement rate is proportional to the creep strain rate. Both models are consistent with existing experimental observations for GBS during creep of austenitic stainless steels. For cavity nucleation at particles, Harris’ model (1965) for the relationship between GBS and a critical particle size has been analysed and found to be in agreement with observations.
Biodegradable coatings and films of cellulose nanofibers (CNFs) or a combination of CNFs and inorganic fillers, such as clay or calcium carbonate (CaCO3), can provide a replacement for non-biodegradable plastic coatings as barrier layers in packaging boards. In this work, transparent composite films were prepared from CNFs of Pinus radiata and Eucalyptus using different amounts of clay and CaCO3 as fillers. The impact of raw material (softwood vs. hardwood), TEMPO oxidation levels and filler type (clay vs. CaCO3) on film properties was studied. Pinus radiata CNF films had superior mechanical properties to Eucalyptus CNF films, but no significant differences were observed in the barrier and optical properties. Clay seemed to work better as filler compared to CaCO3, in terms of its impact on film properties. Composite films with CaCO3 as filler were highly brittle with inferior properties to clay-CNF films, and an uneven distribution and agglomeration of the CaCO3 mineral particles was evident in SEM images. Based on the results, clay as filler in CNF coatings is preferred for targeting packaging board applications. Rheological characterisation of the CNF suspensions revealed shear-thinning behaviour, with the CNF from Eucalyptus having higher viscosities and lower power-law indices when compared to the CNF from P. radiata.
The precipitation of cementite (M3C) from as-quenched martensite during tempering at 500 and 700 degrees C was investigated in a Fe-1C-1Cr (wt%) alloy. Tempering for a short duration at 700 degrees C results in a Cr/Fe ratio in the core region of M3C precipitates which is equal to the bulk alloy composition, while a shell on the surface of the precipitates exhibits a higher Cr concentration. With a prolonged tempering up to 5h, the shell concentration gradually increases toward the equilibrium value, but the core region has not yet reached the equilibrium value. After tempering for 5s at 500 degrees C, there is no Cr enrichment found at the M3C-matrix interface, while a transition to partitioning of Cr is found during the first 5min of tempering at 500 degrees C. These experimental results indicate that M3C grows without significant partitioning of substitutional elements at both temperatures initially, i.e., growth is carbon diffusion controlled. This stage is, however, very short, and soon after 5s at 700 degrees C and 5min at 500 degrees C, Cr diffusion becomes important. Calculations using the diffusion simulation software DICTRA and precipitation simulation software TC-PRISMA were performed. The diffusion simulations using the local equilibrium interface condition show excellent agreement with experiments concerning Cr enrichment of the particles, but the size evolution is overestimated. On the other hand, the precipitation simulations underestimate the size evolution. It is suggested that a major improvement in the precipitation model could be achieved by implementing a modified nucleation model that considers nucleation far from the equilibrium composition.
The microstructure evolution of two martensitic alloys Fe-0.15C-(1.0 and 4.0) Cr (wt%) was investigated, using X-ray diffraction, electron backscatter diffraction, electron channeling contrast imaging and transmission electron microscopy, after interrupted tempering at 700 A degrees C. It was found that quenching of 1-mm-thick samples in brine was sufficient to keep most of the carbon in solid solution in the martensite constituent. The high dislocation density of the martensite decreased rapidly during the initial tempering but continued tempering beyond a few minutes did not further reduce the dislocation density significantly. The initial martensitic microstructure with both coarse and fine laths coarsened slowly during tempering for both alloys. However, a clear difference between the two alloys was distinguished by studying units separated by high-angle boundaries (HABs). In the low-Cr alloy, M3C precipitates formed and coarsened rapidly, thus they caused little hindrance for migration of HABs, i.e., coarsening of the HAB units. On the other hand, in the high-Cr alloy, M7C3 precipitates formed and coarsened slowly, thus they were more effective in pinning the HABs than M3C in the low-Cr alloy, i.e., coarsening of HAB units was minute in the high-Cr alloy.
Interfiber friction in paper exists in fiber suspensions, fiber flocs, and fiber networks. The interfiber friction force is, therefore, important both in papermaking and in the use of paper. The objective of this research is to develop a methodology using atomic force microscopy (AFM) for the direct measurement of the friction force between pulp fibers. Different factors such as AFM scanning velocity, contact area, and fiber surface roughness were investigated. The results show that AFM is an effective tool for measuring micro-scale interfiber friction forces. Both AFM scanning velocity and fiber surface roughness affect the measured results. The coefficient of friction increases, but the initial adhesion force decreases, with increasing fiber surface roughness.
The pinning effect of particles on grain boundary migration was studied in a Fe-20 mass % Cr alloy deoxidised with Ti and Zr. The different nitrogen contents (65, 248 and 490 ppm) were used to vary the number of precipitated inclusions. The specimens from equiaxed zones of metal samples with different particle densities were examined by in situ observations during a 60-min holding time at 1200 and 1400 degrees C in a Confocal Scanning Laser Microscope. The change of particles pinning effect on the grain growth was described by an average grain size, (D) over bar (A), and the ratio between the perimeter and area of grains, P-GB/A(G). It was found that the pinning effect of particles (mostly complex Ti-Zr oxynitrides) on grain growth decreased with a decreased nitrogen content in the metal. Furthermore, the effect of particles decreased with an increased temperature of treatment, due to the reduction of the number of particles on the grain boundaries.
As part of refractory erosion studies, the wetting behaviour of molten iron containing varying amounts of oxygen on refractory oxides was investigated by the sessile drop method. The oxides investigated in the present work were alumina, silica and mullite. The reactions were followed in static as well as dynamic modes, under isothermal conditions, through contact angle measurements. Other parameters investigated in the present study were temperature and oxygen partial pressure. For all substrates, the contact angles started decreasing due to the lowering of the surface tension of iron, as oxygen at constant partial pressure, came into contact with the surface of the drop. At a critical level of oxygen in the metal drop, a reaction product started forming at the drop/substrate interface and at this stage the contact angle dropped suddenly. In all cases there was a tendency for the contact angle to increase after this minimum. In the alumina case, the iron drop moved away from the reaction site, once the product layer had been formed at the interface, probably due to the imbalance in the surface forces. In the case Of SiO2 and mullite, liquid slags were formed. The substrates were analysed through SEM and EDS. The reaction products identified were in agreement with thermodynamic predictions. In the case Of SiO2, deep erosions were formed along the periphery of the drops, probably due to Marangoni flow. The possible mechanisms of the reactions and their impact on refractory erosion are discussed in the light of the present experimental results.
Diffusion is considered important in the process of mixing old and new binders during asphalt recycling. The degree of mixing is presumed to greatly influence the final properties of recycled asphalt concrete. Previously, studies have been undertaken to investigate diffusion using FTIR-ATR (Fourier Transform Infrared Spectroscopy using Attenuated Total Reflectance). A need was identified to verify, if the rates of diffusion detected using FTIR-ATR were accompanied by changes in rheological properties. In this paper, a dynamic shear rheometer (DSR) with parallel plates is used for monitoring diffusion. Diffusion coefficients obtained at 60, 80 and 100 degrees C from tests of a soft bitumen (rejuvenator) diffusing into a stiff one are presented. The diffusion coefficients determined are compared with the corresponding diffusion coefficients obtained using FTIR-ATR. The comparison shows that the rates of diffusion detected by the DSR are of the same magnitude, but somewhat higher than the ones detected by FTIR-ATR.
A novel fabrication method for optical thin film filters based on the self-organization of alternating layers of colloidal gold and silica nanoparticles (NP) is reported. The filter is designed to work in the deep-UV to visible spectral range. The spectral absorption peaks are tuned by three parameters: the organic capping ligand of the gold NPs (citrate, chitosan, poly (diallyl-dimethylammonium)- chloride or PDDA); the capping environment (bare, chitosan, or PDDA) of the silica NPs and the thickness of the film. Precise control of the transmission color (less than 1% color distance per layer), is achieved by changing the film thickness. Exploitation of the self-assembly process should lead to the facile production of highly reliable large area thin film optical filters at considerably lower costs.
Nanofibrillated cellulose (NFC)-Norway spruce O-acetyl-galactoglucomannan (GGM) composite films were coated either with a novel succinic ester of GGM or with native GGM. NFC films were made for reference. The succinic ester of GGM was synthesised at low (GGM-Su1) and high (GGM-Su2) degree of substitution to obtain different level of water repellence. GGM and its succinic esters had good affinity with NFC substrate. This made it possible to implement the barrier functionality on the NFC network with the adequate mechanical properties. The coatings further enhanced the already excellent oxygen permeability properties, achieving 0.1 [(cm(3) A mu m)(m(2) kPa d)] as the lowest value with the NFC-GGM film double-coated with GGM-Su2. The films demonstrated pronounced stiffness by adding GGM to the NFC, as well as coating of GGM-Su2 on the NFC-GGM films at 0-90 % relative humidity. The films turned out to be impenetrable with grease even at high temperatures. NFC-GGM film with GGM-Su2 coating exhibited hydrophobic characteristics according to the water contact angle measurements. It was shown that adding 5.5 wt% of GGM to a NFC film and further 5.4 wt% of coating of GGM-Su or GGM on the film may highly enhance the feasibility of the biocomposites to be used for food packaging to replace typical oil-based non-biodegradable plastics currently used.
A new remodeling theory accounting for mechanically driven collagen fiber reorientation in cardiovascular tissues is proposed. The constitutive equations for the living tissues are motivated by phenomenologically based microstructural considerations on the collagen fiber level. Homogenization from this molecular microscale to the macroscale of the cardiovascular tissue is performed via the concept of chain network models. In contrast to purely invariant-based macroscopic approaches, the present approach is thus governed by a limited set of physically motivated material parameters. Its particular feature is the underlying orthotropic unit cell which inherently incorporates transverse isotropy and standard isotropy as special cases. To account for mechanically induced remodeling, the unit cell dimensions are postulated to change gradually in response to mechanical loading. From an algorithmic point of view, rather than updating vector-valued microstructural directions, as in previously suggested models, we update the scalar-valued dimensions of this orthotropic unit cell with respect to the positive eigenvalues of a tensorial driving force. This update is straightforward, experiences no singularities and leads to a stable and robust remodeling algorithm. Embedded in a finite element framework, the algorithm is applied to simulate the uniaxial loading of a cylindrical tendon and the complex multiaxial loading situation in a model artery. After investigating different material and spatial stress and strain measures as potential driving forces, we conclude that the Cauchy stress, i.e., the true stress acting on the deformed configuration, seems to be a reasonable candidate to drive the remodeling process.
Most wooden structures for outdoor applications require repetitive maintenance operations to protect the surfaces from adverse effects of weathering. One-sided surface modification of boards with a relatively fast charring process has the potential to increase the durability and service life of wooden claddings. To assess some weathering-related effects on surface charred wood, spruce and pine sapwood were subjected to a series of long charring processes (30-120 min) at a moderate temperature of 250 A degrees C and to a short one (30 s) at a high temperature of 400 A degrees C. The wettability and contact angles of treated samples were investigated, and the heat transfer was measured along with the micromorphological changes taking place in the material. The result revealed an increased moisture resistance of charred spruce sapwood and an increased water uptake of pine sapwood. The contact angles of both wood species improved compared to references. Heat conduction measurement revealed that only a thin section of the wood was thermally modified. Some micromorphological changes were recorded, especially on the inside walls of the lumina. The results show that spruce sapwood has an improved resistance towards moisture-induced weathering, but more studies are needed to unlock the potential of surface charred wood.
Scots pine (Pinus sylvestris L.) wood was surface densified in its radial direction in an open press with one heated plate to obtain a higher density on the wood surface whilst retaining the overall thickness of the sample. This study investigated the effect of temperature (100, 150 and 200 A degrees C) and press closing speed (5, 10 and 30 mm/min, giving closing times of 60, 30 and 10 s, respectively) on the micromorphology of the cell-wall, as well as changes occurring during set-recovery of the densified wood. The micromorphology was analysed using scanning electron microscopy (SEM) combined with a sample preparation technique based on ultraviolet-excimer laser ablation. Furthermore, the density profiles of the samples were measured. Low press temperature (100 A degrees C) and short closing time (10 s) resulted in more deformation through the whole thickness, whilst increasing the temperature (150 and 200 A degrees C) and prolonging the closing time (30 and 60 s) enabled more targeted deformation closer to the heated plate. The deformation occurred in the earlywood regions as curling and twisting of the radial cell-walls, however, no apparent cell-wall disruption or internal fracture was observed, even at low temperatures and fast press closing speed, nor after soaking and drying of the samples. In the SEM-analysis after soaking and drying, it was noticed that the cells did not completely recover their original form. Thus, part of the deformation was considered permanent perhaps due to viscoelastic flow and plastic deformation of the cell-wall components.
The so called "bee phenomenon" in bitumen has been investigated by means of AFM quantitative nanomechanical property mapping. Bees are a phenomenon that can be observed by topography measurements using AFM. The characteristic "bee" appearance comes from regions with alternating higher and lower bands in the surface topography of bitumen, which are surrounded by a flat area. The proposed mechanism for bee formation is phase separation and differential contraction during cooling from melt temperatures leading to wrinkling due to differences in the elastic modulus of the material phases. Using a laminate wrinkling model, the thickness of the bee laminate was calculated from the wavelengths and Young's moduli of the bee laminate and the matrix. It was found to vary between 70 and 140 nm for the five bitumen samples that contained significant amounts of wax.
In this paper, the N back-migration and restoration behavior of duplex stainless steels (DSSs) 2101 and 2205 (DSS2205) were studied. Experimental findings indicated that the Cr2N in the ferrite (α) persistently decreased for both steels during the cooling process from 1200 °C to 1000 °C, and the disappearance rate of Cr2N in DSS2205 was significantly faster than that of lean duplex stainless steel 2101 (LDX2101). On the one hand, due to the severe partitioning behavior of N atoms in α migrating back to austenite (γ), on the other hand, the enriched Mn in LDX2101 and the enriched Ni in DSS2205 exerted an impact on N migration. Also, the cumulative thermal deformation at 1200 °C contributed to the N migration back into γ with the assistance of high-density dislocations and thermal deformation energy. Furthermore, the softening mechanism of constituent phases was dominated by discontinuous dynamic recrystallization (DDRX) mechanism in both steels at a strain rate of 10 s−1, which was characterized by strain-induced boundaries migration from low-density dislocations to high ones.
A modeling approach was applied to study elastic properties and volume change in dental composites. Mechanics modeling results were compared with experimental data in model materials of known composition where the filler content was varied. Composite behavior was predicted based on polymer and filler properties in order to improve basic understanding. Model predictions agree well with data. The models were used to discuss effects of resin properties, filler volume fraction and microstructure (particle shape and filler size distribution).
In several European countries, dental composites are replacing mercury-containing amalgams as the most common restorative materials. One problem with dental composites is residual stresses which may lead to poor performance of the restoration. In the present study, a combined modeling and materials characterization approach is presented and predictions compare well with experimental data on residual stresses. The model takes stress relaxation into account through the complete relaxation time spectrum of the resin. The approach allows for detailed parametric studies where resin and composite composition as well as cure conditions may be tailored with respect to residual stress generation.
The effects of high magnetic fields on the solidification microstructure of Al-Si alloys were investigated. Al-7.2 wt%Si and Al-11.8 wt%Si alloys were solidified in various high magnetic fields at different cooling rates. The secondary dendrite arm spacing (SDAS) of the primary Al dendrites and the lamellar spacing (LS) of the eutectics were measured. It was found that the application of a high magnetic field could decrease the SDAS of the primary Al dendrites in Al-7.2 wt% Si alloys and the LS of the eutectics in Al-11.8 wt% Si alloys. The effects of the high magnetic field on the SDAS decreased with increasing cooling rate. The decrease in the SDAS and LS can be attributed to the decrease of the solute diffusivity in the liquid ahead of the solid/liquid interface during the growth of the dendrite and eutectic. This decrease is caused by the high magnetic field which can damp the convection and avoid its contributions to the diffusion.
The effect of hydrogen on the physical-chemical properties of copper is directly dependent on the types of chemical bonding between H and lattice defects in Cu. In this work, we performed a systematic study of the bonding of H-atoms with crystal lattice defects of copper. This included three types of symmetric tilt grain boundaries (GBs), sigma 3, sigma 5 and sigma 11, and the low Miller index surfaces, (111), (110) and (100). A comparison with literature data for the bonding of H-atoms with point defects such as vacancies was done. From the defects investigated and analyzed, we conclude that the bond strength with H-atoms varies in the decreasing order: surfaces [(111), (110) and (100)] > vacancy > sigma 5 GB > sigma 11 GB > bulk approximate to sigma 3 GB. A study on the effects of the fcc lattice expansion on the binding energies of H-atoms shows that the main driving force behind the segregation of H-atoms at some GBs is the larger volume at those interstitial GB sites when compared to the interstitial bulk sites.
A series of solidification experiments using a mirror furnace and a levitation technique were performed on different Cu-Sn alloys. Cooling curves during solidification were registered using a thermocouple of type K connected to a data acquisition system. The undercooling, cooling rates of the liquid and of the solid state, solidification times and temperatures were evaluated from the curves. The samples were found to solidify far below the liquidus temperature. The cooling curves for different samples and alloys were simulated using a FEM solidification program. The heat transfer coefficient, heat of fusion and specific heat were evaluated. It was found that the calculated values of the heat of fusion were much lower than the tabulated ones. The calculated values of the specific heat in the solid state were also found to be much higher than those quoted in the literature, especially for the mirror furnace experiments. The effect of rapid cooling on the thermodynamic state and the solidification process of the alloys has been evaluated. The effect of cooling rate on the formation and condensation of vacancies is discussed. It is proposed that a large number of vacancies form during rapid solidification and that they condense during and after the solidification. The influence of these defects on the thermodynamics and solidification of the alloys has been evaluated.
The engulfment and pushing (extrusion) of inclusions during solidification play an important role in the formation of a steel structure and, as a result, for the mechanical properties of the final steel product. The aim of this study is to gain knowledge about the behavior of non-metallic inclusions at the interface between a growing solid front and a liquid phase. The focus is on the effect of the titanium and titanium oxide content on the inclusions and the different phenomena, which occurs at the solid/liquid interface. This was studied in samples of low-carbon steels de-oxidized by different combinations of Al, Ca, and Ti. For this purpose, each metal sample of 0.19 g was melted at a temperature close to 1550 A degrees C in an argon atmosphere and solidified under different solidification rates. A direct observation of inclusion behavior during solidification was made using a confocal scanning laser microscope equipped with an infrared gold image furnace. The alloying elements in the sample varied between: C 0.002-0.044; Si 0.02-1.33; Mn 0.12-1.33; P 0.003-0.016; S 0.003-0.01; Al 0.002-0,033; Ni 0-0.28; Cr 0-0.25; Ti 0.008-0.065; Ca 0.0007-0.002; O 0.002-0.0114 and N 0.0028-0.0056 (mass%). Several types of inclusions with different morphologies were found within the sample. The morphology of the observed inclusions on the molten steel surface varied from round alumina and calcium-oxide-rich inclusion to needle-shaped titanium oxide-rich inclusions. The observed motions of the inclusions at the vicinity of the front of the solidifying steels were classified. At a low solidifying velocity and a small inclusion size, inclusions flowed away from the solidifying front. Furthermore, they also or got pushed a distance and thereafter flowed away from the interface. At a medium velocity and a slightly bigger size, inclusions tend to get pushed in front of the solidifying front. Another observation was that at a high velocity and a large particle size, inclusions tend to get engulfed or pushed and then engulfed by the progressing front. The relationship among the morphology, chemical composition of inclusions and the solidifying velocity is discussed in this article.
Cellulose nanopaper consists of a dense fibrous self-binding network composed of cellulose nanofibres connected by physical entanglements, hydrogen bonding, etc. Compared with conventional printing paper, cellulose nanopaper has higher strength and modulus because of stronger fibres and inter-fibre bonding. The aim of this paper is to investigate the fracture properties of cellulose nanopaper using double edge notch tensile tests on samples with different notch lengths. It was found that strength is insensitive to notch length. A cohesive zone model was used to describe the fracture behaviour of notched cellulose nanopaper. Fracture energy was extracted from the cohesive zone model and divided into an energy component consumed by damage in the material and a component related to pull-out or bridging of nanofibres between crack surfaces which was not facilitated due to the limited fibre lengths for the case of nanopapers. For comparison, printing paper which has longer fibres than nanopaper was tested and modelled to demonstrate the importance of fibre length. Buckypaper, a fibrous network made of carbon nanotubes connected through van der Waals forces and physical entanglements, was also investigated to elaborate on the influence of inter-fibre connections.
Spent nuclear fuel, in Sweden, is planned to be put in 50-mm thick copper canisters and placed in 500-m depth in the bedrock. Depending on the conditions in the repository, an uptake of hydrogen in the copper may occur. It is therefore necessary to establish how a hydrogen uptake affects the microstructure in both the surface and the bulk. Phosphorus-doped, oxygen-free copper has been cathodically charged with hydrogen for up to 3 weeks. The amount of hydrogen as a function of the distance from the surface was measured by two methods: glow discharge optical emission spectrometry and melt extraction. The penetration of the increased hydrogen content was about 50 mu m. Extensive bubble formation took place during the charging. A model has been formulated for the diffusion of hydrogen into the copper, the bubble formation and growth. The model can describe the total amount of hydrogen, the number of bubbles and their sizes as a function of the distance from the surface. Bubbles close to the surface caused the surface to bulge due to the high hydrogen pressure. From the shape of the deformed surface, the maximum hydrogen pressure could be estimated with the help of stress analysis. The maximum pressure was found to be about 400 MPa, which is almost an order of magnitude larger than previously recorded values for electroless deposited copper.
Steels containing nitrogen at levels which are at or above the 1 Bar saturation solubility limit in the liquid at the liquidus temperature offer considerable metallurgical property advantages in many respects. For example, when nitrogen is used as a substitute for carbon in stainless grades, the alloys have superior corrosion properties especially in biomedical applications: nitrogen as a strengthening element in tool steels offers advantages in freedom from carbide particles which affect the polishability. Most of the steels grade of interest require electroslag remelting to control segregation without loss of nitrogen and the behaviour of nitrogen during this process is the subject of this work. It is concluded that the required process pressures are closely related to the alloy composition and that to prevent porosity in the product the ESR step must be carried out at an appropriate overpressure of either nitrogen or argon. The addition of nitrogen during ESR is also discussed and it is shown that this is possible only through solid additives.
The effect of cooling rate on the microstructure and mechanical properties of equimolar NiCoFeCrGa high-entropy alloy (HEA) was studied by scanning electron microscopy, energy-dispersive X-ray spectroscopy and electron backscatter diffraction (EBSD), as well as by microhardness tests. Experimental results show that the cooling rate has a crucial impact on the developing microstructure which has a mixture of twoFCC and BCCphases, leading to a self-similarity of the solidified structure formed in the sample. Furthermore, the cooling rate influences both the composition of the two phase-components and the ratio of their volume fractions, determining the mechanical properties of the sample. The present results confirm the grouping of Co, Fe and Cr in the FCC phase and that of Ni and Ga in BCC phase in the NiCoFeCrGa high-entropy alloy system. An empirical rule is suggested to predict how the phase-components can be expected in this complex high-entropy alloy.
The current study presents a method to calculate the critical diameters of TiO, TiN, and VN inclusions for intragranular ferrite (IGF) nucleation in steels. Based on the calculation results, it was noted that the critical diameters of TiO, TiN, and VN inclusions for IGF nucleation were 0.192, 0.355, and 0.810 μm. The calculation results agreed with the experiment data of a minimum inclusion size for IGF nucleation in the actual steel samples. Moreover, the effects of Mn, C, and S contents on the critical diameters of inclusions were investigated. It was found that the critical diameters of TiO, TiN, and VN inclusions increased with the increasing Mn and C contents. In addition, it was found that S does not have a direct effect on the critical diameters of TiO, TiN, and VN inclusions. However, the increasing S content led to an increased amount of MnS precipitation in the actual steels. This is negative, since MnS is ineffective nucleation site for IGF nucleation. When the amount of MnS increases in steels, the area fraction of IGF slightly decreases. This fact has been investigated by in situ observation experiments.
Martensitic transformation of AISI D2 tool steel continuously cooled from 1303 K to the cryogenic temperature of 173 K is investigated by dilatometry using 10 or 50 K s(-1) cooling rates. A 'typical' expansion takes place from the temperature and reaches a maximum at 325 K. However, an atypical behavior is observed below this temperature implying the activation of further martensitic transformation. A modification to existing equations is proposed, which allows for more accurate description of the kinetics of martensitic transformation. Scanning electron microscopic studies indicated the presence of plate and lath martensite for both cooling rates. Carbide precipitation takes place at the rate of 10 K s(-1) before the start of martensitic transformation while it was not observed when the 50 K s(-1) rate was used. Transmission electron microscopic studies revealed that the microstructure also contains a significant amount of nano-twinned martensite.
Rice husks are amongst the typical agricultural residues, which are easily available in huge amounts. They have been considered as raw material for composites panels' production. However, the major hindrance in rice husks utilization for composite manufacture lies in the lack of direct interaction with most adhesive binders to form the anticipated interfacial bonds. Rice husks are highly siliceous and have poor resistance to alkaline and acidic conditions. Manufacture of rice husks composites panels having good interface bond is difficult and largely dependent on a proper understanding of the interaction between the husks and the binder. This paper presents and discusses results on the production of composites boards from a mixture of rice husks and wattle (Acacia mimosa) tannin based resin. The experimental results have shown that the 'as received rice husks' when blended with alkali-catalyzed tannin resin do not result in optimum composite panel properties. However, it was found that a slight physical modification of the rice husk particles by hammer-milling resulted in drastic improvements in the interfacial bond strength and stiffness of the composites panels from 0.041 MPa to 0.200 MPa and 1039 MPa to 1527 MPa, respectively.
Wood fibres constitute the structural framework of e.g. wood, paper, board and composites, where stiffness and dimensional stability are of importance. An analytical modelling approach has been used for prediction of hygroelastic response, and assessment of the stresses in thick-walled cylinder models of wood fibres. A wood fibre was idealised as a multilayered hollow cylinder made of orthotropic material with helical orientation. The hygroelastic response of the layered assembly due to axisymmetric loading and moisture content changes was obtained by solving the corresponding boundary value problem of elasticity. A simple solution scheme based on the state space approach and the transfer matrix method was employed. This was combined with an analytical ultrastructural homogenisation method, used to link hygroelastic properties of constituent wood polymers to properties of each layer. Predicted hygroelastic response captured experimentally measured behaviour. Fibres that were constrained not to twist showed a stiffer response than fibres allowed twisting under uniaxial loading. It was also shown that the ultrastructure, i.e. the microfibril angle, will control the hygroexpansion in the same way as it controls the compliance of the cell wall. Qualitative failure trends comparable with experimental observations could be established with stress analysis and a simple plane-stress failure criterion.
Softwood hemicelluloses could potentially be combined with cellulose and used in packaging materials. In the present study, galactoglucomannan (GGM) is adsorbed to wood cellulose nanofibers (CNF) and filtered and dried or hot-pressed to form nanocomposite films. The CNF/GGM fibril diameters are characterized by AFM, and the colloidal behavior by dynamic light scattering. Mechanical properties are measured in uniaxial tension for wet gels, dried films, and hot-pressed films. The role of GGM is particularly important for the wet gels. The wet gels of CNF/GGM exhibit remarkable improvement in mechanical properties. FE-SEM fractography and moisture sorption studies are carried out to interpret the results for hygromechanical properties. The present study shows that GGM may find use as a molecular scale cellulose binding agent, causing little sacrifice in mechanical properties and improving wet strength.
The rheological and dynamic mechanical properties of polymer-based composites of Sm2Co17 and polyamide-12 with different particle loadings, sizes, and surface treatments are reported. Sm2Co17 particles were surface-treated with three different silanes: 3-glycidoxy(propyl)trimethoxysilane, 3-amino(propyl)trimethoxysilane (APTMS), and methyltrimethoxysilane (MTMS). It was shown, for the composites with untreated particles, that the viscosity and storage modulus increased with increasing filler content (0-60 vol%) and decreasing filler particle size. In addition, the glass transition temperature increased significantly and the damping decreased with increasing filler content. Of the silanes, the MTMS, which yielded only a thin surface layer, had in general the least effect on the rheological properties of the composite. The composite containing the APTMS-coated filler showed the highest storage modulus. The results give new insights on how to prepare polymer-bonded magnets with optimal process conditions (rheology) and dynamic mechanical properties, by varying the amount of particles, their size, and surface treatment.
There is an increasing demand for polymer-bonded magnets (PBM) in high temperature applications. While most research deals with high temperature properties of NdFeB-PBM, only a few studies consider Sm-Co PBM. Therefore, this study, on the thermal and magnetic properties of Sm-Co alloy powders and blends of these with polyamide-12 (PA12), was undertaken. Since the Sm-Co powders were the product of ball milling, they contained a variety of shapes and sizes. Studies on size fractions of these showed that the thermal stability and magnetic properties were improved as the particle size increased. It was suggested that higher residual strains and smaller crystallite sizes in the small particles were responsible for a decrease in the thermal stability and magnetic properties. In addition, energy dispersive X-ray spectroscopy revealed that the oxygen content increased with decreasing particle size (larger specific surface area) and higher oxygen content was possibly also responsible for a decrease in the magnetic properties. It was shown that, in general, the surface modification by silanization, using (3-aminopropyl)trimethoxsilane, increased the saturation magnetization and remanence of both the particles and the Sm-Co/PA12 composite. The silanization also improved the thermal stability of the particles.