Temperature and stress effects in the creep of aramid fibers under transient moisture conditions and discussions on the mechanisms

In a previous study, a mechanosorptive phenomenon in poly(p-phenylene terephthalamide) fibers was reported. In this article, the mechanosorptive creep mechanism of aramid fibers and the temperature and stress influences on the mechanosorptive creep behavior of aramid fibers are addressed. Test results indicate that logarithmic creep rates and the mechanosorptive effects increase with temperature. The creep activation energies of the fibers tested are: 20 kJ/mole for the cyclic moisture condition, 4.4 kJ/mole for a high equilibrium moisture condition (RH = 95%), and 7.8 kJ/mole for a low equilibrium moisture condition (RH = 5%). Increase in stress may increase the logarithmic creep rates but may reduce the mechanosorptive effect. Aramid fibers contain hydrogen bonds between rodlike crystallites oriented at small angles relative to the fiber axis. Transient moisture conditions may cause slippage of hydrogen bonded elements and result in accelerated crystallite rotations due to breakage of hydrogen bonds, thus causing increases in logarithmic creep rate. The obtained activation energies and the reduction in fiber elastic compliance due to creep deformation support the proposed mechanisms. © 1992 John Wiley & Sons, Inc.     

Influence of humidity cycling parameters on the moisture‐accelerated creep of polymeric fibers

Accelerated creep is a curious and poorly understood transient moisture effect. The creep rates of most hydrophilic materials increase greatly with moisture content. However, when these same materials are subjected to creep loads in cyclic humidity environments, they often exhibit much higher creep rates than in a constantly humid state. This is called accelerated creep. Previous experimenters reported that accelerated creep was less likely to occur in polymeric fibers. We demonstrate experimentally that this happened only because of their choice of humidity cycling parameters. New results are given for Kevlar, lyocell, nylon‐6,6, and ramie fibers. Other paper scientists have argued that the absence of accelerated creep in single fibers supports a explanation based on fiber network effects for accelerated creep in paper. We argue here that accelerated creep is a more general phenomenon consistent with sorption‐induced stress‐gradient explanations. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2048–2062, 2001     

Comparison of nano- and microfibrillated cellulose films

Nanocellulose is an interesting building block for functional materials and has gained considerable interest due to its mechanical robustness, large surface area and biodegradability. It can be formed into various structures such as solids, films and gels such as hydrogels and aerogels and combined with polymers or other materials to form composites. Mechanical, optical and barrier properties of nanofibrillated cellulose (NFC) and microfibrillated cellulose (MFC) films were studied in order to understand their potential for packaging and functional printing applications. Impact of raw material choice and nanocellulose production process on these properties was evaluated. MFC and NFC were produced following two different routes. NFC was produced using a chemical pretreatment followed by a high pressure homogenization, whereas MFC was produced using a mechanical treatment only. TEMPO-mediated oxidation followed by one step of high pressure (2,000 bar) homogenization seems to produce a similar type of NFC from both hardwood and softwood. NFC films showed superior mechanical and optical properties compared with MFC films; however, MFC films demonstrated better barrier properties against oxygen and water vapor. Both the MFC and NFC films were excellent barriers against mineral oil used in ordinary printing inks and dichlorobenzene, a common solvent used in functional printing inks. Barrier properties against vegetable oil were also found to be exceptionally good for both the NFC and MFC films.     

Ultra porous nanocellulose aerogels as separation medium for mixtures of oil/water liquids

A novel type of sponge-like material for the separation of mixed oil and water liquids has been prepared by the vapour deposition of hydrophobic silanes on ultra-porous nanocellulose aerogels. To achieve this, a highly porous (>99%) nanocellulose aerogel with high structural flexibility and robustness is first formed by freeze-drying an aqueous dispersion of the nanocellulose. The density, pore size distribution and wetting properties of the aerogel can be tuned by selecting the concentration of the nanocellulose dispersion before freeze-drying. The hydrophobic light- weight aerogels are almost instantly filled with the oil phase when selectively absorbing oil from water, with a capacity to absorb up to 45 times their own weight in oil. The oil can also be drained from the aerogel and the aerogel can then be reused for a second absorption cycle.     

Two modes of transformation of amorphous calcium carbonate films in air

Large-area amorphous calcium carbonate (ACC) films in air are shown to be transformed into crystalline calcium carbonate (CaCO(3)) films via two modes-dissolution-recrystallization and solid-solid phase transition-depending on the relative humidity of the air and the temperature. Moisture in the air promotes the transformation of ACC into crystalline forms via a dissolution-recrystallization process. Increasing the humidity increases the rate of ACC crystallization and gives rise to films with numerous large pores. As the temperature is increased, the effect of moisture in the air is reduced and solid-solid transition by thermal activation becomes the dominant transformation mechanism. At 100 and 120 degrees C, ACC films are transformed into predominantly (110) oriented crystalline films. Collectively, the results show that calcium carbonate films with different morphologies, crystal phases, and structures can be obtained by controlling the humidity and temperature. This ability to control the transformation of ACC should assist in clarifying the role of ACC in the biomineralization of CaCO(3) and should open new avenues for preparing CaCO(3) films with oriented and fine structure.     

Aerogels with 3D Ordered Nanofiber Skeletons of Liquid‐Crystalline Nanocellulose Derivatives as Tough and Transparent Insulators

Aerogels of high porosity and with a large internal surface area exhibit outstanding performances as thermal, acoustic, or electrical insulators. However, most aerogels are mechanically brittle and optically opaque, and the structural and physical properties of aerogels strongly depend on their densities. The unfavorable characteristics of aerogels are intrinsic to their skeletal structures consisting of randomly interconnected spherical nanoparticles. A structurally new type of aerogel with a three‐dimensionally ordered nanofiber skeleton of liquid‐crystalline nanocellulose (LC‐NCell) is now reported. This LC‐NCell material is composed of mechanically strong, surface‐carboxylated cellulose nanofibers dispersed in a nematic LC order. The LC‐NCell aerogels are transparent and combine mechanical toughness and good insulation properties. These properties of the LC‐NCell aerogels could also be readily controlled.     

Nanocellulose properties and applications in colloids and interfaces

In this review we introduce recent advances in the development of cellulose nanomaterials and the construction of high order structures by applying some principles of colloid and interface science. These efforts take advantage of natural assemblies in the form of fibers that nature constructs by a biogenetic bottom-up process that results in hierarchical systems encompassing a wide range of characteristic sizes. Following the reverse process, a top-down deconstruction, cellulose materials can be cleaved from fiber cell walls. The resulting nanocelluloses, mainly cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC, i.e., defect-free, rod-like crystalline residues after acid hydrolysis of fibers), have been the subject of recent interest. This originates from the appealing intrinsic properties of nanocelluloses: nanoscale dimensions, high surface area, morphology, low density, chirality and thermo-mechanical performance. Directing their assembly into multiphase structures is a quest that can yield useful outcomes in many revolutionary applications. As such, we discuss the use of non-specific forces to create thin films of nanocellulose at the air–solid interface for applications in nano-coatings, sensors, etc. Assemblies at the liquid–liquid and air–liquid interfaces will be highlighted as means to produce Pickering emulsions, foams and aerogels. Finally, the prospects of a wide range of hybrid materials and other systems that can be manufactured via self and directed assembly will be introduced in light of the unique properties of nanocelluloses.     

Method for combinatorial screening of moisture vapor transmission rate

A high-throughput method for screening the moisture vapor transmission rate of barrier films was developed. This moisture high-throughput screening (MHTS) technique is based upon a Nafion-crystal violet (CVN) sensor that changes color from yellow to green upon absorption of water. Using an appropriate set of known standards, the slope of absorbance (at 630 nm) as a function of time can be converted into moisture vapor transmission rate (MVTR) values that agree with those obtained using ASTM F1290. High-throughput screening was demonstrated by depositing 20 emulsion-based poly(vinylidene chloride) films, using a 48-well template, of varying thicknesses onto the CVN sensor film and aging at 40 degrees C and 90% relative humidity for 72 h. MVTR values were accurately determined to a level of 0.9 g/m(2).day, at which point side-diffusion of moisture between the barrier and sensor films prevented observation of lower values. Larger sample size and edge-sealing are two proposed methods for improving the sensitivity of MHTS.     

Cholesteric-type cellulosic structures: from plants to applications

ABSTRACT

The structural support of plant cells is provided by the cell wall, which major load-bearing component is an array of hierarchical orientedhierarchical-oriented cellulose nano-, micro- and meso-structures of cellulose microfibrils. Cellulosic structures can respond to humidity changes by expanding or shrinking and this allows, for example, the dispersion of seeds. Previous studies have shown that nanorods, extracted from cell walls, can generate lyotropic liquid crystals that are at the origin of solid cholesteric-like arrangements. Not only photonic films, but also right and left helical filaments, anisotropic films with the ability to bend back and forth under the action of a moisture gradient at room temperature, are some of the materials that were produced from cellulose liquid crystal systems. This work is a review that focus on liquid crystalline-based structures obtained from cellulosic materials and how small perturbations on their structures affect significantly the response to external stimulus and interactions with the environment. Special emphasis is given to cholesteric-like organization of cellulose structures existing in plants, which are an inspiration for the production of the next generation of soft interactive materials.     

Investigation of Moisture Sorption,Permeability, Cytotoxicity and Drug Release Behavior of Carrageenan/Poly Vinyl Alcohol Films

This work describes moisture sorption behavior and water vapor permeability of glutaraldehyde-crosslinked carrageenan/polyvinyl alcohol (Carr/PVA) films. The moisture uptake has been studied under various relative humidity (RH) and the data obtained has been interpreted in the terms of various isotherm models such as GAB, Oswin and Halsey models. The moisture permeability through the films has been characterized in the terms of various parameters like water vapor transmission rate (WVTR), permeance (P) and water vapor permeability (WVP). It was found that these parameters are greatly affected by the degree of crosslinking of the films. Finally, the model drug Gentamycin Sulphate was loaded in to the films and its release was monitored kinetically in the physiological buffer (PF) at 37°C. The films exhibited diffusion controlled release mechanism. The films are non-cytotoxic.     

Soy protein–nanocellulose composite aerogels

Organic aerogels based on two important and widely abundant renewable resources, soy proteins (SP) and nanofibrillar cellulose (NFC) are developed from precursor aqueous dispersions and a facile method conducive of channel- and defect-free systems after cooling and freeze-drying cycles that yielded apparent densities on the order of 0.1 g/cm³. NFC loading drives the internal morphology of the composite aerogels to transition from network- to fibrillar-like, with high density of interconnected cells. Composite aerogels with SP loadings as high as ca. 70 % display a compression modulus of 4.4 MPa very close to that obtained from reference, pure NFC aerogels. Thus, the high compression modulus of the composite system is not compromised as long as a relatively low amount of reinforcing NFC is present. The composite materials gain moisture (up to 5 %) in equilibrium with 50 % RH air, independent of SP content. Furthermore, their physical integrity is unchanged upon immersion in polar and non-polar solvents. Fast liquid sorption rates are observed in the case of composite aerogels in contact with hexane. In contrast, water sorption is modulated by the chemical composition of the aerogel, with an important contribution from swelling. The potential functionalities of the newly developed SP–NFC composite green materials can benefit from the reduced material cost and the chemical features brought about the amino acids present in SPs.     

微纳米纤维素功能膜在能源与环境领域的应用

探寻绿色清洁的资源与材料以维持高效的社会经济增长是未来数十年人们面临的最大挑战之一. 可持续资源与绿色材料的开发是降低传统化石能源与材料比重的最有前途的方案. 纤维素作为一种可持续发展、 可生物再生、 储量丰富且低成本的天然高分子聚合物, 在众多领域中具有广泛的应用, 并且纤维素可以加工成各种构型, 包括气凝胶、 泡沫、 海绵和薄膜等. 本文介绍了不同形态的纤维素及其衍生物组装而成的功能膜在能源与环境中的应用, 综述了微纳米纤维素及其衍生物在先进功能化储能器件方面的最新进展和制备方案, 以及在用于水处理的膜分离技术中的应用, 其中重点讨论了微纳米纤维素及其衍生物功能膜在电池、 电容器及水处理等领域中的作用, 如隔膜、 柔性电极膜和分离膜等. 此外, 还对纤维素及其衍生物功能膜的未来发展进行了总结和展望.     

Phase transitions in calcium nitrate thin films

Calcium carbonate is a ubiquitous mineral and its reactivity with indoor and outdoor air pollutants will contribute to the deterioration of these materials through the formation of salts that deliquesce at low relative humidity (RH). As shown here for calcium nitrate thin films, deliquescence occurs at even lower relative humidity than expected from bulk thermodynamics and lower than the recommended humidity for the preservation of artifacts and antiques.     

Evaluation of the rate of abiotic degradation of biodegradable polyethylene in various environments

The rate of abiotic degradation of polyethylene (PE) films containing a manganese pro-degradant has been studied in various environments at 60 and 70 °C. The degradation was monitored from the change in molecular weight and the elongation at break after exposure to dry and humid air. It was observed that moisture had a strong accelerating effect on the rate of thermo-oxidation of PE films. However, despite the humidity level in the compost environment being similar to that in humid air, the rate of degradation in compost was much slower. It is proposed that ammonia and/or hydrogen peroxide generated by microorganisms in the compost can be responsible for the deactivating effect, as aqueous solutions of these compounds significantly retard the rate of degradation.     

Rapid preparation of smooth nanocellulose films using spray coating

Spraying of nanocellulose (NC) on a solid surface to prepare films is an alternative technique to vacuum filtration, which requires a long drainage time and produces films which can sometimes be difficult to separate from the filter. This letter reports a rapid preparation technique for nano-cellulose films using a bench scale system spray coating nanocellulose suspension onto stainless steel plates. After spraying NC suspension onto a smooth steel plate travelling on a constant velocity conveyor, the films can be dried directly on the plates using standard laboratory procedures, saving processing time and effort. By adjusting the suspension consistency, we were able to reproducibly make films with a basis weight ranging from 52.8 ± 7.4 to 193.1 ± 3.4 g/m² when spraying on to a plate moving at a velocity of 0.32 cm/s. The operator preparation time for the nanocellulose film was 1 min, independent of the sample basis weight, which compares to production times reported in the literature of 10 min using filtration techniques. The films made by spray coating showed higher thickness, but comparable uniformity, to those made by vacuum filtration. Optical profilometry measurements showed that over a 1 cm × 1 cm inspection area that the surface roughness (RMS) of the NC film is only 389 nm on the spray coated side in contact with the steel plates, compared to 2087 nm on the outside surface. Thus, the reduction in preparation time for producing the nanocellulose film recommends this spray coating technique as a rapid and flexible method to produce NC films at the laboratory scale.     

Composite films from spruce galactoglucomannans with microfibrillated spruce wood cellulose

Two future wood biorefinery products, spruce galactoglucomannans (GGM) and microfibrillated spruce wood cellulose (MFC), were mixed to form composite films. The films were plasticized with different amounts of glycerol, and the preparation of films was successful even with low glycerol contents. The film properties were studied using optical microscopy and scanning electron microscopy, x-ray diffraction, water sorption, dielectric analysis, moisture scanning dynamic mechanical analysis, and tensile testing. The addition of MFC clearly affected the properties of the films by decreasing the moisture uptake and increasing the relative humidity of softening of the films and by increasing the glass transition temperature, tensile strength, and Young’s modulus of the films. The effect of MFC addition on the tensile properties of films was emphasized at low glycerol contents. The addition of MFC did not affect the degree of crystallinity of GGM in the films, which was between 20 and 25%. MFC can be efficiently used as reinforcement of GGM films to form wood-based composite materials and to prepare GGM-based films and coatings with low plasticizer content.     

Morphology of conducting organic polymers: Polythiophene and poly(3-methyl thiophene)

Polythiophene and substituted polythiophene can be electrochemically generated as very adhesive thin films or as thick powdery deposits. The homogeneity of the thin films is very high, but it decreases when the film thickness is increased. Scanning electron microscopy shows that the nature of the dopant strongly influences the film morphology. Transmission electron microscopy reveals mainly a fibrillar structure, with a fibril diameter of 200 Å in the undoped state, and 800 Å in the doped conducting state.     

Effect of moisture content on the heat-sealing property of starch films from different botanical sources

In this study, we investigated the differences in the crystallinity of starch films (mung bean, water chestnut, sweet potato, and cassava starches) with different moisture contents stored in different humidity conditions (11%, 22%, 33%, 43%, 54%, 75%, and 84%) and evaluated their thermal adhesion and sealing properties. X-ray diffraction analysis revealed an association between the degree of crystallinity and the moisture content in starch films: crystallinity decreased with an increase in the moisture content. Field Emission Scanning Electron Microscopy (FE-SEM) analysis showed that films with low moisture content failed to completely adhere, but films with a high moisture content and lower crystallinity showed good adherence, with two films perfectly adhered at the same temperature because water molecules acted as a mobility enhancer. The peeling test demonstrated the failure modes of the heat-bound films. The cassava starch film, which had a low amylose content and crystallinity, showed better adhesion compared to other starch films.     

Characterization of fibril reinforced membranes for fuel cells

Characteristics of fibril reinforced membranes developed by Asahi Glass Company are reviewed. PTFE-fibrils <1 μm in diameter are dispersed in ion-exchange membranes uniformly. Mechanical properties, such as tensile strength, tear strength, creep property and compressive property were examined and compared with non-reinforced membranes. Fibril reinforced membranes, even by the addition of a small amount of PTFE-fibrils (2.7 wt.%), show excellent mechanical strength, especially in creep and tear strength. Cell performance is nearly equal to the one using a non-reinforced membrane and cell voltage stays about the same during the cell operation at 80 °C for 3000 h.     

Flammability, microhardness and transparency of nanocomposites based on functionalized polyethylenes

The flammability, microhardness and transparency of nanocomposites based on poly(ethylene-co-acrylic acid) copolymers having different concentration of acrylic acid and different molar mass, their Zn ionomer and ethylene-glycidylmethacrylate copolymer as matrixes and on organically modified montmorillonite as a nanofiller have been investigated. The presence and the increase in the content of the clay lead to the increase in the limiting oxygen index and to significant reduction of the burning rate of all materials. The results from the Vickers microhardness measurements have shown that the addition of the clay to matrixes of polar functionalized polyethylenes leads to a significant increase in the microhardness of the materials, while the creep constant does not decrease significantly. The UV spectra show that the light transmittance of the materials does not change significantly in the presence of the clay, i.e., the nanocomposite films preserve the polymer transparency. The results have been interpreted by the intercalated structures of the nanocomposites investigated.