Nano-fibrillation of pulp fibers for the processing of transparent nanocomposites

Pulp fibers were fibrillated uniformly into nano-sized fibers using a grinder with a specially designed set of grinding disks. To investigate the effect of the fibrillation through the grinder on the physical properties of the composites, dissolved pulp fibers were subjected to various passes through the grinder, and the resulting fibrillated pulp fibers were used to make fibrillated pulp fibers/acrylic resin composites. Scanning electron microscopy observations showed that at above five passes, the structure of the fibrillated pulp fibers did not change significantly. The light transmittances of the composites were increased to 80% up to five passes through the grinder, and did not change after further passes. However, the tensile test and thermal expansion analysis indicated that a degradation of the fibrillated pulp occurred during the grinding treatment. To evaluate the fiber degradation, the degree of crystallinity and degree of polymerization of cellulose were measured. Both decreased as the number of passes through the grinder increased. In addition, to reduce the thermal expansion of composites, the fibrillated pulp fibers were additionally treated by sulfuric acid. The thermal expansion of composites was decreased, because the amorphous region of cellulose was removed. PACS 81.05.Lg; 81.05.Qk; 81.07.-b     

The effect of morphological changes from pulp fiber towards nano-scale fibrillated cellulose on the mechanical properties of high-strength plant fiber based composites

Fibrillated kraft pulp impregnated with phenolic resin was compressed under an extremely high pressure of 100 MPa to produce high strength cellulose nanocomposites. To evaluate how the degree of fibrillation of pulp fiber affects the mechanical properties of the final composites, kraft pulp subjected to various levels of refining and high pressure homogenization treatments was used as raw material with different phenolic resin contents. It was found that fibrillation solely of the surface of the fibers is not effective in improving composite strength, though there is a distinct point in the fibrillation stage at which an abrupt increase in the mechanical properties of composites occurs. In the range between 16 and 30 passes through refiner treatments, pulp fibers underwent a degree of fibrillation that resulted in a stepwise increment of mechanical properties, most strikingly in bending strength. This increase was attributed to the complete fibrillation of the bulk of the fibers. For additional high pressure homogenization-treated pulps, composite strength increased linearly against water retention values, which characterize the celluloses exposed surface area, and reached maximum value at 14 passes through the homogenizer. PACS 81.05.Lg; 81.05.Qk     

Bacterial cellulose: the ultimate nano-scalar cellulose morphology for the production of high-strength composites

High-strength composites were produced using bacterial cellulose (BC) sheets impregnated with phenolic resin and compressed at 100 MPa. By utilizing this unique material synthesized by bacteria, it was possible to improve the mechanical properties over the previously reported high-strength composites based on fibrillated kraft pulp of plant origin. BC-based composites were stronger, and in particular the Youngs modulus was significantly higher, attaining 28 GPa versus 19 GPa of fibrillated pulp composites. The superior modulus value was attributed to the uniform, continuous, and straight nano-scalar network of cellulosic elements oriented in-plane via the compression of BC pellicles. PACS 81.05.Lg; 81.05.Qk     

Carbon nanotube synthesis in a flame using laser ablation for in situ catalyst generation

Laser ablation of either Ni or Fe is used to create nanoparticles within a reactive flame environment for catalysis of carbon nanotubes (CNTs). Ablation of Fe in a CO-enriched flame produces single-walled nanotubes, whereas, ablation of Ni in an acetylene-enriched flame produces carbon nanofibers. These results illustrate that the materials for catalyst particle formation and CNT, SWNT or nanofiber, inception and growth in the aerosol phase can be supplied from separate sources; a metal-carbon mixture produced by condensation is not necessary. Both particle formation and CNT inception can begin from molecular species in a laser-ablation approach within the complex chemical environment of a flame. Moreover, SWNTs and nanofibers can be synthesized within very short timescales, of the order of tens of milliseconds. Finally, high-intensity pulsed laser light can destroy CNTs through either vaporization or coalescence induced by melting. PACS 42.62 Fi; 81.05.Tp; 82.80.Ch; 81.15 Fg     

Formation of high aspect ratio polyamide-6 nanofibers via electrically induced double layer during electrospinning

In the present study, the formation of high aspect ratio nanofibers in polyamide-6 was investigated as a function of applied voltage ranging from 15 to 25 kV using electrospinning technique. All other experimental parameters were kept constant. The electrospun polyamide-6 nanofibers were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF). FE-SEM images of polyamide-6 nanofibers showed that the diameter of the electrospun fiber was decreased with increasing applied voltage. At the critical applied voltage, the polymer solution was completely ionized to form the dense high aspect ratio nanofibers in between the main nanofibers. The diameter of the polyamide-6 nanofibers was observed to be in the range of 75-110 nm, whereas the high aspect ratio structures consisted of regularly distributed very fine nanofibers with diameters of about 9-28 nm. Trends in fiber diameter and diameter distribution were discussed for the high aspect ratio nanofibers. TEM results revealed that the formation of double layers in polyamide-6 nanofibers and then split-up into ultrafine fibers. The electrically induced double layer in combination with the polyelectrolytic nature of solution is proposed as the suitable mechanisms for the formation of high aspect ratio nanofibers in polyamide-6.     

Novel high-strength biocomposites based on microfibrillated cellulose having nano-order-unit web-like network structure

A completely new kind of high-strength composite was manufactured using microfibrillated cellulose (MFC) derived from kraft pulp. Because of the unique structure of nano-order-scale interconnected fibrils and microfibrils greatly expanded in the surface area that characterizes MFC, it was possible to produce composites that exploit the extremely high strength of microfibrils. The Youngs modulus (E) and bending strength (_b) of composites using phenolic resin as binder achieved values up to 19 GPa and 370 MPa, respectively, with a density of 1.45 g/cm², exhibiting outstanding mechanical properties for a plant-fiber-based composite. PACS 81.05.Lg; 81.05.Qk     

Production and Characterization of Zirconia (ZrO2) Ceramic Nanofibers by Using Electrospun Poly(Vinyl Alcohol)/Zirconium Acetate Nanofibers as a Precursor

Zirconia (ZrO₂) inorganic ceramic nanofibers were produced using electrospinning of the poly(vinyl alcohol)/zirconium acetate as a precursor followed by calcinating and sintering to decompose the polymer and turn the metal salt (zirconium acetate) into the metal oxide. Characterization of the nanofibers, including polymer thermal decomposition, chemical and crystal structure, phase transformations, and fiber morphology were investigated by simultaneous thermal analysis (STA), thermomechanical analysis (TMA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and field emission scanning electron microscopy (FESEM). The results showed that the polymer decomposition started at 250°C and zirconia nanofibers with different phases (tetragonal and monoclinic) were obtained by the calcination of the precursor nanofibers at various temperatures between 500°C and 1100°C. The initially crystallized zirconia phase, which formed at 500°C, was tetragonal and with increasing calcination temperature, zirconia nanofibers with increasing amount of monoclinic phase were formed. Consequently, at 1100°C, the tetragonal phase disappeared and was transformed to the monoclinic phase of the zirconia completely. Increasing the calcination temperature caused the fiber average diameter decrease and grain growth took place due to the removal of the polymer and organic groups; neighboring grains sintered to each other and formed fibers with a high aspect ratio. At 1100°C the grains size was about the same as the fiber diameter.     

Growth of normally-immiscible materials (NIMs), binary alloys, and metallic fibers by hyperbaric laser chemical vapor deposition

This work demonstrates that two or more elements of negligible solubility (and no known phase diagram) can be co-deposited in fiber form by hyperbaric-pressure laser chemical vapor deposition (HP-LCVD). For the first time, Hg-W alloys were grown as fibers from mixtures of tungsten hexafluoride, mercury vapor, and hydrogen. This new class of materials is termed normally-immiscible materials (NIMs), and includes not only immiscible materials, but also those elemental combinations that have liquid states at exclusive temperatures. This work also demonstrates that a wide variety of other binary and ternary alloys, intermetallics, and mixtures can be grown as fibers, e.g. silicon-tungsten, aluminum-silicon, boron-carbon-silicon, and titanium-carbon-nitride. In addition, pure metallic fibers of aluminum, titanium, and tungsten were deposited, demonstrating that materials of high thermal conductivity can indeed be grown in three-dimensions, provided sufficient vapor pressures are employed. A wide variety of fiber properties and microstructures resulted depending on process conditions; for example, single crystals, fine-grained alloys, and glassy metals could be deposited. PACS 81.15.Fg; 81.05.Bx; 81.05.Je; 81.15.Gh     

Mapping of the cationic starch adsorbed on pulp fibers by ToF-SIMS

Cationic starch (CS) is routinely used in the papermaking process to improve the dry strength or printability of paper. The effectiveness depends on the distribution of the starch on the pulp fiber, and in this study, time-of-flight secondary ion mass spectrometry was used to investigate this distribution. The characteristic peak at 58m/z was applied to map the CS. Based on the imaging analysis of the handsheets with the CS as an internal additive, the distribution of CS became more uniform with decreasing freeness. The amount of adsorbed CS increased with increasing fiber length and was lower on vessels than on other fibers. These results were related to fibrillation. From the analysis of handsheets with CS as an external additive, the penetration depth of the starch into base paper increased with decreases in the sizing degree of the base paper.     

Some aspects of the characterization of decorations on ceramic glazes

From antiquity, glazes have been one of the techniques used for decorating ceramics. Potters took advantage of the optical properties of these glazes to improve the quality of the object, especially to obtain an appearance or some characteristics that had commercial success. This is why it is important to know the reasons of the visual appearance of glazes. In this paper we present some aspects of the characterization of lustre, one of the on-glaze decorations that results in a more spectacular visual effect, as a microstructure, its composition, its raw materials and some technological aspects of its production. Lustre is a three-dimensional heterogeneous structure, where copper and silver nanoparticles play the most important role, but also alkali elements in the glaze and other components of raw lustre pigments. Lustre properties are determined by copper and silver composition and by distribution and dimension of these metallic nanocrystals in the decoration layer. PACS 61.46.+w; 68.37.Hk; 68.37.Lp; 81.05.-t; 79.60.-i; 81.07.-b ; 78.67.Bf; 81.05.Kf; 81.05.Je     

Electrospun precursor carbon nanofibers optimization by using response surface methodology

Ultrafine fibers were electrospun from Polyacrylonitrile and N,N-dimethylformamide solution to be used as a precursor for carbon nanofibers. An electrospinning set-up was used to collect fibers with diameter ranging from 104 nm to 434 nm. Morphology of fibers and its distribution were investigated by varying Berry's number, charge density, spinning angle, spinneret diameter and collector area. A more systematic understanding of process parameters was obtained and a quantitative relationship between electrospinning parameters and average fiber diameter was established by using response surface methodology. It was concluded that; Berry's number, charge density and spinneret diameters played an important role to the diameter of nanofibers and its standard deviation. Spinning angle and collector area had no significant impact. Based on response surface methodology the optimum Polyacrylonitrile average fiber diameter of 280 nm and 28 nm standard deviation, were collected at 1.6 kV/cm charge density, 8 Berry's number and 0.9 mm spinneret diameter.     

Microanalytical study of a ferrous agricultural tool recovered from a historical site in Rio de Janeiro

The present work has as its objective a microanalytical study of a metallic archeological artifact using methods of optical microscopy (MO), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The object of the study corresponds to an agricultural tool (a hoe) from the Brazilian colonial period, dating from the late XVIII century, removed from an archeological site (Sítio Rochedo) in excavations conducted by researchers of the Brazilian Archeological Institute. Sample preparation required a meticulous procedure in view of the fragility of the object. The hoe has been suffering the action of oxidation-corrosion over the years, thereby making the impregnation of mineral sediments possible. A detailed metallographic analysis, coupled with spectroscopic SEM and TEM measurements, allows one to conclude that the hoe was made of puddle iron, retaining significant amount of slag. The hoe was probably made by African slaves who had metallurgical knowledge acquired from their ancestors under Portuguese colonization. The equi-axial microstructure of ferrite grains, together with the alignment of slag inclusions, strongly suggest a metal forming procedure conducted on low-carbon puddled iron, followed by heat treatment and then cooling at a slow rate. PACS 81.05.bx; 81.70.-q; 01.65.tg; 81.05.t     

纳米碳纤维红外消光数值计算

为探讨纳米碳纤维作为烟幕粒子的红外消光特性,基于电磁场理论建立了细直的纳米碳纤维感应电流积分方程,并利用矩量法进行了求解,导出了纳米碳纤维散射场及吸收、散射和消光截面的计算式.通过与变分法的计算结果相比较,表明了该方法的有效性.利用该方法数值分析了纳米碳纤维红外消光截面与入射场波长、入射角、纤维长度和半径的关系,计算结果为纳米碳纤维用于红外烟幕干扰提供了理论依据.     

Comparison of two different ultrasound reactors for the treatment of cellulose fibers

The pulp and paper industry is in continuous need for energy-efficient production processes. In the refining process of mechanical pulp, fibrillation is one of the essential unit operations that count for up to 80% of the total energy use. This initial study explores the potential and development of new type of scalable ultrasound reactor for energy efficient mechanical pulping. The developed reactor is of continuous flow type and based on both hydrodynamic and acoustic cavitation in order to modify the mechanical properties of cellulose fibers. A comparison of the prototype tube reactor is made with a batch reactor type where the ultrasonic horn is inserted in the fluid. The pulp samples were sonicated by high-intensity ultrasound, using tuned sonotrodes enhancing the sound pressure and cavitation intensity by a controlled resonance in the contained fluid. The resonant frequency of the batch reactor is 20.8 kHz and for the tube reactor it is 22.8 kHz. The power conversion efficiency for the beaker setup is 25% and 36% in case of the tube reactor in stationary mode. The objective is to verify the benefit of resonance enhanced cavitation intensity when avoiding the effect of Bjerkenes forces. The setup used enables to keep the fibers in the pressure antinodes of the contained fluid. In case of the continuous flow reactor the effect of hydrodynamic cavitation is also induced. The intensity of the ultrasound in both reactors was found to be high enough to produce cavitation in the fluid suspension to enhance the fiber wall treatment. Results show that the mechanical properties of the fibers were changed by the sonification in all tests. The continuous flow type was approximately 50% more efficient than the beaker. The effect of keeping fibers in the antinode of the resonant mode shape of the irradiation frequency was also significant. The effect on fiber properties for the tested mass fraction was determined by a low-intensity ultrasound pulse-echo based measurement method, and by a standard pulp analyzer.     

Sorption characteristics of water,oil and diesel in cellulose nanofiber reinforced corn starch resin/ramie fabric composites

Nowadays, utilisation of biodegradable materials has become necessary in order to maintain global environmental and ecological balance. Fully biodegradable nano 'Green' textile composites have been prepared from cellulose nanofibers reinforced corn starch resin and ramie fabric. Nanofibers having dimensions of approximately 1 μm long and 20–30 nm in diameter are used in the study. The nanofibers were incorporated in corn starch resin via ball mill mixing using ceramic balls. Textile composites were fabricated by pasting the reinforced resin onto the ramie fabric and by hot compression molding technique. Interactions at the fiber–matrix interface and the compatibility between cellulose and corn starch resin molecules will affect the properties of the system. The well dispersed cellulose nanofibers contribute higher interfacial area and good fiber networking within the matrix resin. This will lead to better barrier properties. Sorption characteristics of water, oil and diesel in the textile composites were analysed and the influence of nano fibers and macro fibers on the transport phenomena was investigated. The kinetics of sorption-diffusion process was investigated. Kinetic parameters such as n, k, diffusion coefficient, permeability, solubility parameter, % swelling index, etc., were analysed. The presence of cellulose nanofibers influences the sorption mechanism. The water sorption mechanism in the nanocomposites was found to exhibit slight deviation from Fickian mode. Structure–property relationships of the nanocomposites were evaluated.     

Comparative study of textured diamond films by thermal conductivity measurements

Superior thermal conductivity, high resistance, high breakdown voltage and wide band gap make diamond an attractive material for a variety of applications in electronics. One of its most appealing applications is as a buried dielectric in silicon-on-diamond (SOD) technology. This paper presents thermal conductivity measurements conducted on a series of diamond films (grown by the microwave plasma chemical vapor deposition technique) as a function of the sample morphology and thickness, for eventual incorporation in the SOD structures. Results show that there is a significant difference in the measured thermal conductivity between samples with fiber texture and samples with sheet texture. Also, measurements performed on a 160-μm-thick diamond sample before and after reactive ion etching of approximately 10 μm of the nucleation layer show no significant change in the measured value of the thermal conductivity. PACS 81.05.Uw; 65.40.-b; 61.72.-y     

利用近红外光谱鉴别纺织用竹纤维和麻纤维

利用近红外光谱技术对竹原纤维、竹粘胶纤维和苎麻纤维进行了快速定性鉴别研究.首先扫描3种纤维的近红外光谱,利用化学计量学分析软件,对谱图进行一阶导数预处理,建立不同纤维的光谱数据库,并分别建立竹原纤维、竹粘胶纤维和苎麻纤维的判别模型.利用判别模型,对未知样品进行判别.结果表明,近红外光谱可以在不破坏样品的情况下,可以快速鉴别竹原纤维、竹粘胶纤维和苎麻纤维.     

Continuous dry dispersion of multi-walled carbon nanotubes to aerosols with high concentrations of individual fibers

The assessment of the toxicity of airborne nanofibers is an important task. It relies on toxicological inhalation studies and validated exposure measurement techniques. Both require nanofiber-containing aerosols of known morphological composition and controlled fraction of individual fibers. Here, a dry powder dispersion method is presented that operates with mixtures of nanofibers and microscale beads. Aerosolization experiments of mixtures of multi-walled carbon nanotubes (MWCNTs) and glass beads that were continuously fed into a Venturi nozzle enabled high generation rates of aerosols composed of individual and agglomerate nanofiber structures. The aerosol process achieved good stability over more than 2 h with respect to concentration and aerodynamic size distribution. Its operation duration is limited only by the reservoir volume of the cyclone used to separate the beads from the aerosol. The aerosol concentration can be controlled by changing the mass ratio of MWCNTs and glass beads or by adapting the mass feed rate to the nozzle. For two agglomerated MWCNT materials, aerosol concentrations ranged from 1700 to 64,000 nano-objects per cm³. Comprehensive scanning electron microscope analysis of filter samples was performed to categorize and determine the morphological composition of the aerosol, its fiber content as well as fiber length and diameter distributions. High fractions of individual fibers of up to 34% were obtained, which shows the setup to be capable of dispersing also highly tangled MWCNT agglomerates effectively.     

Electrospinning of complex oxide nanofibers

Electrospinning is a versatile process for drawing fibers of diverse materials including polymers, ceramics, and composites. We demonstrate here its application in the synthesis of complex ceramic oxide materials. The phase formation and morphology of BaTiO₃ nanofibers synthesized via electrospinning is investigated as a function of heat treatment conditions. Fully crystallized BaTiO₃ nanofibers with the perovskite structure are obtained after annealing at 750 °C and show an average grain size of about 30 nm. Tetragonal crystal structure of the fibers is indicated by XRD peak splitting (calculated c/a ratio=1.007), and confirmed by Raman spectroscopy. Furthermore, the advancement in heat treatment of the electrospun fibers yields single crystalline BaTiO₃ nanofibers with 50 nm in diameter and lengths up to 1 μm.     

Fiber laser micro-cutting of stainless steel sheets

The authors report on laser micro-cutting results for stainless steel foils with the aid of a 100 W fiber laser. This novel laser source combines a high output power in relation to conventional laser sources for micro-processing applications with an excellent beam quality (M²=1.1). Different material thicknesses were evaluated (100 μm to 300 μm). Processing was carried out with cw operation of the laser source, and with nitrogen and oxygen as assisting gases. Besides the high processing rate of oxygen assisted cutting, a better cutting performance in terms of a lower kerf width was obtained. PACS 42.82.Cr; 42.62.Cf; 81.05.Bx