Adhesion of modified epoxy matrices to reinforcing fibers

The adhesive strength of joints between fibers and epoxy matrices modified with three types of modifiers—active diluents, thermostable rigid-chain thermoplasts, and dispersed fillers—is studied. It is shown that the introduction of modifiers increases interface strength in several cases in a particular concentration interval. The introduction of thermostable thermoplasts into epoxides is more effective. Possible mechanisms of adhesive-strength synergism for each of the modification types are discussed.     

Nanopore generation in hybrid polycyanurate/poly(ε-caprolactone) thermostable networks

Novel nanoporous thermosetting films were obtained from thermostable polycyanurate (PCN)-based hybrid networks synthesized by polycyclotrimerization of cyanate ester of bisphenol E in the presence of a modifier reactive toward cyanate groups, i.e. dihydroxy-telechelic poly(ε-caprolactone) (PCL). The nanoporous structure was generated in PCN/PCL hybrid networks after extraction of unreacted free PCL sub-chains which were not chemically incorporated into the PCN cross-linked framework. Structure–property relationships for precursory and porous PCN/PCL hybrid networks were investigated using a large array of physico-chemical techniques. The porosity associated with the networks after extraction was more particularly evaluated by SEM and DSC-based thermoporometry: pore sizes around 10–90 nm were determined along with pore volumes as high as about 0.3 cm³ g⁻¹. Density and dielectric measurements strongly suggested the occurrence of closed pore structures. Due to their high thermal stability as investigated by TGA, nanoporous PCN/PCL hybrid cross-linked films could be considered as promising materials for potential applications as thermostable membranes.     

Progress in cellulose shaping: 20 years industrial case studies at Fraunhofer IAP

Cellulose, the most abundant renewable organic material on earth, exhibits outstanding properties and useful applications, but also presents a tremendous challenge with regard to economical and environmentally friendly chemical processing. The viscose process, more than 100 year old is still the most widely utilized technology to manufacture regenerated cellulose fibers and films. Viscose fibers are produced today worldwide on a 5 million ton scale with various fiber types ranging from high performance tire yarn to textile filaments and staple fibers with excellent properties close to those of cotton. At Fraunhofer IAP, the technical equipment for viscose preparation, wet spinning of fibers, hollow fibers, and tube-like films is available on a min-plant scale. Research focused on raw materials testing, process optimization with regard to economic and ecological aspects, structural analysis of cellulose during processing, and structure–property relations of fibers and films. Similar to the viscose process, cellulosic fibers can be produced via cellulose carbamate as an environmentally friendly route. In a close cooperation of Fraunhofer IAP with industrial partners, a specific process based on cellulose carbamate was developed on a pilot plant scale, giving fiber properties close to those of conventional viscose fibers. In recent decades the N-methylmorpholine-N-oxide (NMMO)-technology turned out to be a nonderivatizing commercial alternative to the still dominant viscose route. From the very beginning, Fraunhofer IAP has been engaged in investigating the structure formation of cellulose fibers precipitated from NMMO-water solution, revealing structural reasons for the fibrillation tendency of these fibers and means to overcome them. Starting from fiber formation via dry-jet wet spinning, for the first time the blown film formation and the meltblown nonwovens technology were developed for cellulosics on a pilot plant scale at Fraunhofer IAP. Based on the elastic behavior of the dope at elevated temperatures, cellulose can be processed like a melt in the air-gap, offering new possibilities of shaping cellulose like meltable mass polymers. Combining cellulose carbamate with NMMO-monohydrate as a solvent, higher polymer concentrations in the dope and outstanding mechanical properties of the resulting fibers were achieved.     

Probing the Effects of Antimicrobial-Lysozyme Derivatization on Enzymatic Degradation of Poly(ε-caprolactone) Film and Fiber

Surface derivatization is essential for incorporating unique functionalities into biodegradable polymers. Nonetheless, its precise effects on enzymatic biodegradation still lack comprehensive understanding. In this study, a facile solution-based method is employed to surface derivatize poly(ε-caprolactone) films and electrospun fibers with lysozyme, aiming to impart antimicrobial properties and examine the impact on enzymatic degradation. The derivatized films and fibers have shown high antibacterial efficacy against Escherichia coli and Staphylococcus aureus. Through gravimetric analysis, it is observed that the degradation rate experiences a slight decrease upon lysozyme derivatization. However, this reduction is effectively countered by the inclusion of Tween-20, as affirmed by isothermal titration calorimetry. Comparing films and fibers, the latter undergoes degradation at a more accelerated pace, coupled with a rapid decline in molecular weight. This study provides valuable insights into the factors influencing the degradation of surface-derivatized biopolymers through electrospinning, offering a simple strategy to mitigate biomaterial-associated infections.     

固相微萃取的涂层进展

 对固相微萃取 (SPME)的固定相涂层的发展进行了综述。阐述了商品化和非商品化涂层的各自特点 ,并对涂层的选择性和SPME技术作了简单的介绍。     

Large Photoinduced Refractive Index Change in a Polyimide Film by Charge‐Transfer Complex Formation with a Polymer‐Bound Phenylazide Fragment

A large photo‐induced refractive index change as large as 0.014 at 632.8 nm in thermostable transparent polymer films has been realized for the first time by using photoirradiation of polyimide precursor films containing a phenylazide and successive imidization. The phenylazide fragment forms a charge‐transfer complex with imide moiety. The films maintained high transmittance in a wide visible region in contrast to usual polyimide films. This value of refractive index change is sufficient to make thermostable channel waveguides and other optical devices.     

Introducing carboxyl and aldehyde groups to softwood-derived cellulosic fibers by laccase/TEMPO-catalyzed oxidation

For more cost-effective and/or value-added utilization of cellulosic fibers in pulp and paper industry, fiber engineering is an important concept. Essentially, fibers can be engineered via various mechanical, chemical, and biological processes. In the current study, the combined use of laccase and TEMPO was applied to introduce carboxyl and aldehyde groups to softwood-derived cellulosic fibers (bleached softwood kraft pulp). The process conditions in preparation of the engineered fibers were optimized. Under the conditions studied, the maximum increases in carboxyl and aldehyde contents were 360 % and 225 %, respectively. The effectiveness of the laccase/TEMPO system could be well explained by the reaction cycles in catalytic oxidation pathways. The findings of the current work may provide useful insights into the enzymatic modification of cellulosic fibers for papermaking applications.     

Comparison of formats for the development of fiber-optic biosensors utilizing sol-gel derived materials entrapping fluorescently-labelled protein

The development of fiber-optic biosensors requires that a biorecognition element and a fluorescent reporter group be immobilized at or near the surface of an optical element such as a planar waveguide or optical fiber. In this study, we examined a model biorecognition element-reporter group couple consisting of human serum albumin that was site-selectively labelled at Cys 34 with iodoacetoxy-nitrobenzoxadiazole (HSA-NBD). The labelled protein was encapsulated into sol-gel derived materials that were prepared either as monoliths, as beads that were formed at the distal tip of a fused silica optical fiber, or as thin films that were dipcast along the length of a glass slide or optical fiber. For fiber-based studies, the entrapped protein was excited using a helium-cadmium laser that was launched into a single optical fiber, and emission was separated from the incident radiation using a perforated mirror beam-splitter, and detected using a monochromator-photomultiplier tube assembly. Changes in fluorescence intensity were generated by denaturant-induced conformational changes in the protein or by iodide quenching. The analytical parameters of merit for the different encapsulation formats, including minimum protein loading level, response time and limit-of-detection, were examined, as were factors such as protein accessibility, leaching and photobleaching. Overall, the results indicated that both beads and films were suitable for biosensor development. In both formats, a substantial fraction of the entrapped protein remained accessible, and the entrapped protein retained a large degree of conformational flexibility. Thin films showed the most rapid response times, and provided good detection limits for a model analyte. However, the entrapment of proteins into beads at the distal tip of fibers provided better signal-to-noise and signal-to-background ratios, and required less protein for preparation. Hence, beads appear to be the most viable method for interfacing of proteins to optical fibers.     

纳米碳材料在可穿戴柔性导电材料中的应用研究进展

可穿戴设备的兴起使得对柔性器件的需求日益提高,柔性导电材料作为可穿戴器件的重要组成部分而成为研究的热点。传统的电极材料主要是金属,因金属材料本身不具有柔性,一般通过降低金属层厚度以及设计波纹结构等策略实现其在柔性器件中的应用,其加工程序复杂,成本较高。以碳纳米管和石墨烯为代表的纳米碳材料兼具良好的柔性和优异的导电性,且具有化学稳定、热稳定、光学透明性等优点,在柔性导电材料领域展现了极大的应用潜力。本文简要综述了近年来纳米碳材料在柔性导电材料领域的研究进展,首先介绍了碳纳米管基柔性导电材料,分别包括基于碳纳米管水平阵列、碳纳米管垂直阵列、碳纳米管薄膜、碳纳米管纤维的柔性导电材料;继而介绍了石墨烯基柔性导电材料,包括基于剥离法制备的石墨烯和化学气相沉积法制备的石墨烯以及石墨烯纤维基柔性导电材料;并简述了碳纳米管/石墨烯复合柔性导电材料;最后论述了纳米碳材料基柔性导电材料所面临的挑战并展望了其未来发展方向。     

A novel strategy to increase performance of solid‐phase microextraction fibers: Electrodeposition of sol‐gel films on highly porous substrate

In the present work, the effect of substrate porosity for preparation of solid‐phase microextraction (SPME) fibers was investigated. The fibers were prepared by electrodeposition of sol‐gel coatings using negative potentials on porous Cu wire and compared with previous reported technique for preparation of SPME fibers using positive potentials on smooth gold wire. Porous substrate was prepared by electrodeposition of a thin layer of Cu on a Cu wire. The extraction capability of prepared fibers was evaluated through extraction of some aromatic hydrocarbons from the headspace of aqueous samples. The effect of substrate porosity and some operating parameters on extraction efficiency was optimized. The results showed that extraction efficiency of SPME fibers highly depends on porosity of the substrate. The LOD ranged from 0.005 to 0.010 ng/mL and repeatability at the 1 ng/mL was below 12%. Electrodeposited films were characterized for their surface morphology and thermal stability using SEM and thermogravimetric analysis, respectively. SEM analysis revealed formation of porous substrate and subsequently porous coating on the wire surface and thermogravimetric analysis showed high thermal stability of the prepared fiber.     

Finetuning hierarchical energy material microstructure via high temperature material synthesis route

Hierarchical energy materials such as graphite are a backbone of various scientifically and commercially important emerging technologies including high-energy density energy storage systems with fast charging capability, multifunctional catalyst systems, selective membrane separation systems, and next-generation nuclear material systems. Consequently, it is extremely crucial to develop an efficient and cost-effective route of bulk hierarchical material synthesis (e.g., carbonaceous materials with a well-controlled fraction of the graphitic content) to cater the extraordinary operational and energy material requirements in a very complex coupled thermophysicochemical environment. Here we present a fabrication of Polyacrylonitrile (PAN) derived carbon films and fibers (~with linear dimension ~100 nm) via electrospinning and spin coating methods ensued by a heat-treatment in the range of 1000–3000 °C under inert atmospheric conditions. Intriguingly, we observed at least a two orders of magnitude enhancement (~134%) in length of graphitic plane accompanied by 36% more graphitization when the carbonization temperature increased from 1000 °C to 3000 °C. Such significant enhancements were attributed to the differences in the fundamental nanomorphology of initial carbonaceous materials and their subsequent kinetic evolution as it was more favorable for underlying graphene layers in films to stack and bond to the adjacent ones without strong rotations as compared to fibers, which were further evident from fewer voids and cracks in the films. The covalent cross-links, substrate effect and physical entanglements of carbon domains in PAN-derived carbon films contributed to a higher graphitic length owing to more shear stress between the graphene layers, compared to fibers and undergoes an enormous transformation from turbostratic structures to ordered state along with nitrogen removing over high temperature heating. This morphology dependent graphitization was also investigated from computational approach and concluded in the similar thoughts. The outcomes from this systematic study can be beneficial to the carbon research community focusing in the morphology dependent applications, for instance catalysis, energy storage, sensors etc.     

Plasma polymerization of mixed monomer gases

In this paper, plasma polymerization of mixed monomer gases was studied. In the films, the elements derived from each monomer are contained, and they are distributed homogeneously at a certain depth. The films are made up by the copolymers in which both monomers are combined. The chemical compositions of the copolymers can be controlled by changing the proportions of the two monomer gases. The films having gradual compositional change toward depth can be prepared by using a mixture of two monomer gases and changing their proportions during the plasma polymerization. These copolymeric and gradient copolymeric films were formed on porous glass hollow fibers, and gas permeability of these composite membranes was measured. The gradient copolymerization methods are available for the preparation of the membranes for gas separation.     

Aromatic Copolyimides Containing Perylene Units

Perylene-containing copolyimides have been synthesized by one-step polycondensation reaction under high temperature of two different aromatic diamines with a mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) and 4,4'-hexafluoroisopropylidene diphthalic anhydride (6FDA). The copolyimides were soluble in polar amidic solvents and their solutions gave flexible thin films when spread onto glass plates. Very thin films obtained by spin coating had smooth surfaces and were self-organized into vertically segregated structures. The polymers were highly thermostable, their decompositions being above 470 °C and displayed reasonable high glass transition temperature values. After being excited with UV light, the polymers emitted light in the bluish and green-yellow domains.     

Ferroelectric Materials by the Sol-Gel Method

The sol-gel method is ideally suitable for the preparation of ferroelectric thin films such as LiNbO₃, BaTiO₃, KNbO₃ and PZT. The preparation and properties of polycrystalline, amorphous and single crystal films of these ferroelectric oxides are summarized. The origin of “amorphous ferroelectricity” is discussed. Single crystal KNbO₃ films have been successfully fabricated into planar waveguides and their ability to convert infrared laser into green light demonstrated.     

Improving the detection limit of silicon, magnesium and aluminum in neutron activation analysis of polymers using a TRIGA? reactor

The measurement of impurities, specifically; the combination of magnesium, silicon and aluminum, in polymers and in mixed additives is a common problem for industrial application of neutron activation analysis (NAA). Typically this problem can be addressed using XRF and ICP. However, in some cases, the available sample size, desired detection limit and the desired accuracy prohibit the use of XRF or ICP. Therefore under these requirements, as in the measurement of talc in milligram size polymer fibers, using NAA has become a niche for nuclear analytical applications. Other important advantages, apart from high precision and lower detection limit, are the non-destructive nature of the analysis and the minimal sample preparation necessary to carry out the measurement. Therefore, polymers such as polyethylene, polystyrene or poly-carbonate can be analyzed for these metals as organic solutions, beads, films, pellets or powders. This paper highlights some of the recent improvements made to the Dow NAA measurement facility to accomplish this task.     

Enhancement of mechanical and barrier properties of LLDPE composite film via PET fiber incorporation for agricultural application

A study was conducted to determine the potential of linear low‐density polyethylene (LLDPE)‐PET fiber composite films to be used as an agricultural mulching film. Incorporation of 1 wt% PET fiber into the LLDPE matrix improved the tensile strength and percent elongation. The water vapor transmission rate was significantly lowered because of the presence of PET fibers. Also, the effect of continuous exposure of films to pesticide and UV light has been reported in terms of deterioration of mechanical and optical properties of the films. Differential scanning calorimetry shows that there is no effect of the presence of PET fibers on processing temperature of LLDPE at optimized loading; however, it was found that it lowers the latent heat of fusion and crystallization.     

Plasma polymerization of cyano compounds

Plasma polymerizations of three cyano compounds—acrylonitrile (AN), 1,2-dicyanoethylene (FN), and tetracyanoethylene (TCE)—were investigated by FT IR and XPS, and the transforamtion of cyano groups during the plasma polymerization was discussed. The results pointed out an aspect of the preparation of plasma films with cyano groups. Plasma polymerizations of AN, FN, and TCE deposited brown or dark brown films that contained carbon, nitrogen, and oxygen. The elemental composition of the plasma films, especially N/C atomic ratio, showed a monomer dependence but no rf power dependence. The plasma films contained amide and amino groups, and ketene-imine and conjugated — C = N — structures as well as cyano groups as nitrogen functionalities, and carbonyl and carboxyl groups as oxygen functionalities. For the preparation of plasma films with cyano groups, compounds with more than two cyano groups themselves are not suitable as monomers. The operation of plasma polymerization under mild plasma conditions at low rf power and in no oxygen atmosphere is favorable for the preparation of plasma films with cyano groups. © 1992 John Wiley & Sons, Inc.     

Pd/Al2O3催化剂的高温热烧结研究

以汽车尾气净化催化剂为背景，用溶胶－凝胶法和浸渍法制备了低负载量贵金属单钯燃烧催化剂。通过ＸＲＤ宽化法检测了在１２７３Ｋ的模拟反应气流中烧结２４ｈ后催化剂上Ｐｄ晶粒大小的变化。     

Incorporation into paper of cellulose triacetate films containing semiconductor nanoparticles

CdSe/ZnS quantum dots (QDs) were embedded in films of cellulose triacetate (CTA) to give clear films with the broad absorbance and well-defined, size-tunable fluorescence characteristic of QDs. The relative quantum yields of the QDs in polymer were compared to that of the initial QDs dispersed in toluene. Alkaline hydrolysis of the film surfaces to regenerated cellulose rendered the previously hydrophobic CTA film surfaces hydrophilic and compatible with aqueous papermaking. Films containing combinations of different sized QDs gave more complex emission patterns. Small pieces of fluorescent films were added to pulp slurries and incorporated into laboratory paper sheets through hydrogen bonding between the regenerated cellulose film surfaces and cellulosic pulp fibers. The film system (cellulose ester bulk/cellulose surface) can be used to incorporate hydrophobic particles or molecules compatible with solutions of cellulosic polymers into paper products at both high and low loadings. QDs in paper may prove useful for security applications, such as sheets with unique optical signatures.