SIMS Profiling and TEM of CVD Films on Multi-Filament Samples

 A suitable fibre coating is essential to obtain optimal fibre-matrix interaction in fibre-strengthened composite materials. Thin films (∼100 nm) of silicon carbide, turbostratic carbon, and boron nitride were deposited by CVD as single or double layers on commercial multi-filament fibres in a continuous process. The fibre material itself may be carbon, alumina, silicon carbide, or a quaternary ceramic of SiCBN. The application of MCs⁺-SIMS enables one to determine the composition (including impurities of H and O) of various fibre coating materials with an accuracy of at least 20% relative. Due to the special geometry of the multi-filament samples the depth resolution of the SIMS depth profiles is limited, nevertheless, layered structures and some details of the interface between coating and fibre can be studied. The depth calibration of the SIMS depth profiles is derived from sputter rates established on flat samples with a composition similar to that of the fibre coating material. However, the obtained film thicknesses are not extremely different from the values derived from TEM on cross sections of coated fibres.     

A New Method to Examine Interfacial Reactions of a Multilayered System NiAl–Hf–hBN on a Sapphire Fibre

Fibre reinforced NiAl offers new possibilities for the development of high strength structural materials of low density applicable in gas turbines at high operating temperatures. The properties of composite materials are strongly influenced by the strength of the fibre–matrix interface. In addition, if fibre and matrix differ in their thermal expansion coefficients, a well controlled interface reaction at high temperature changes is demanded. Therefore, two layers consisting of BN and Hf were embedded between a sapphire fibre and NiAl and heated at 1350 °C to find a compromise between adhesion and ductility. The control and characterization of the reaction zone is essential for the development of these new materials. Especially, the characterization of the fibre-coating interface is a challenge. The different hardness of fibre and coating makes it nearly impossible to use a conventional cross-section preparation. Further, the small dimension of the reaction zone requires the use of analytical techniques providing high lateral resolution. In order to accomplish these requirements, a newly developed technique FIB (Focused Ion Beam)-EPMA (Electron Probe Microanalysis) was combined with XRD (X-ray diffraction). XRD was performed for the identification of the phases. The reaction zone was exposed by a special FIB preparation technique and examined by surface-sensitive EPMA. This allowed to determine the spatial distribution of the different phases.     

Diffusion-induced dimensional changes in papers and fibrillar films: influence of hydrophobicity and fibre-wall cross-linking

The initial dimensional stability of paper measured as hydroexpansion, i.e. when paper is exposed to liquid water, has been considerably improved by combining a periodate-oxidation-induced cross-linking of the fibre wall with the subsequent adsorption of a hydrophobic polyelectrolyte multilayer consisting of three layers of poly(allylamine hydrochloride) and two layers of poly(acrylic acid). This reduced the rate of diffusion of water into the fibre wall at the same time as the diffusion distance was increased, i.e. the water has to diffuse all the way from the top of the sheet and not only from the individual fibre surfaces since capillary absorption was prevented. However, as a consequence, the hydrophobic sheets present a greater expansion maximum before contraction. It is suggested that this may be due to a higher moisture content in the top fibre layers of the hydrophobically modified papers than in the hydrophilic sheets, since all the water is concentrated to the top fibre layers of the hydrophobic papers. Sheets made from bleached kraft pulp or thermo-mechanical pulp as well as model sheets made from microfibrillated cellulose (MFC) were studied. The MFC-sheets were intended as a model of the fibre wall, i.e. a sheet without any fibre joints. The behaviour of the MFC-sheets was similar to that of ordinary sheets when subjected to water, which indicates that the properties of the fibre joints do not affect the hydroexpansion to any great content and that the expansion of the paper is directly linked to the expansion of the fibre wall.     

Effects of electrochemical and plasma treatments on carbon fibre surfaces

This paper summarizes the chemical changes induced on carbon fibre surfaces (examined by X-ray photoelectron spectroscopy, XPS) by a variety of electrochemical treatment in aqueous electrolytes together with the improvements in fibre/resin bonding in the corresponding composite materials. It was found that there was no correlation between the amount of chemical functionality introduced onto the fibre surface and the fibre/resin bond strength, i.e. chemical bonding does not play a major role in fibre resin adhesion. This does not rule out the possibility of chemical bonding between the fibre and resin—it simply implies that it is not the governing factor. It is suggested that the immediate surface concentration of chemical groups is too low to make a significant contribution. To tailor interfacial properties it would be desirable to promote chemical bonding between fibre and matrix. The use of a specially designed plasma treatment cell has led to an increase in the surface concentration of chemical groups ( C OH, hydroxyl) that have the potential to react chemically with the resin. By exploiting grazing angle data taken from XPS analysis, it is shown that changes in the chemical nature of the fibres only occurs in the outermost layers, whereas the electrochemical reaction proceeds well into the fibre sublayers. Selective introduction of nitrogen-containing functionality (such as amines,  NH₂) has been achieved. The reactivity towards a particular plasma is shown to be largely dependent on the structure of the fibre surface. The number of C/N groups produced on higher modulus fibres was undesirably low. Their concentration was increased by biasing the fibres to a negative potential (10–30 V) during plasma exposure.     

Measurement of thermal radiative properties of penguin down and other fibrous materials using FTIR

Penguins live in the extremely cold Antarctic. Understanding the thermal radiative properties of penguin down may help us to develop super insulating materials. In this study, Fourier transform infrared spectroscopy (FTIR) was applied to measure the thermal radiative properties of penguin down and compare them with those of other fibrous materials. It was found that penguin and duck down are superior to other fibrous materials, such as polyester, Thinsulate and wool, at the same fibre volume fraction, in shielding the radiative heat transmission, largely due to their fine fibre diameter. There is an optimum fibre diameter at which the fibrous materials are at their best in blocking thermal radiation. The fibre diameter of penguin down is very close to this optimum value. The study further found that the relationship between the effective thermal radiative conductivity and fibre fineness may be better fitted with a quadratic curve.     

Nanocellulose characteristics from the inner and outer layer of banana pseudo-stem prepared by TEMPO-mediated oxidation

Many tonnes of agricultural wastes are generated annually, which contains a relatively high amount of cellulose; banana pseudo-stem is one waste type that is a promising material for nanocellulose production. This research characterised nanocellulose from inner and outer layers of banana pseudo-stem as a preliminary research strategy for designing biodegradable packaging material from banana pseudo-stem nanocellulose. Nanocellulose was successfully prepared through TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl)-mediated oxidation. The extracted nanocellulose from both the inner and outer layers had observed widths of approximately 7–35 nm and long fibrillated fibre. They had high negative zeta potential (lower than ?33.6) that provided good colloidal stability. The purity of the nanocellulose was high as demonstrated by ¹³C solid-state NMR and Fourier transform infrared spectroscopy. Nanocellulose from both layers was significantly more crystalline than the raw materials. Thermal stability of nanocellulose sourced from inner and outer layers was relatively similar, with degradation temperature of approximately 220 °C, which was slightly lower than the degradation temperature of its native form (232 °C for inner layer and 261 °C for outer layer).     

Preparation of electrically conducting cellulose fibres utilizing polyelectrolyte multilayers of poly(3,4-ethylenedioxythiophene):poly(styrene sulphonate) and poly(allyl amine)

The primary goal with this work is to create electrically conductive cellulose fibres, this has been done to explore possible new applications for fibre based material. This research uses various methods to create polyelectrolyte multilayers (PEMs) on bleached softwood fibres and on SiO₂ model surfaces, by sequentially treating these materials with poly(3,4-ethylenedioxythiophene):poly(styrene sulphonate) (PEDOT:PSS) and poly(allyl amine) (PAH). Paper sheets were then produced from the PEM-modified pulp and evaluated in terms of tensile strength, adsorbed amount of polymer, and electrical conductivity. To evaluate the influence of fibre charge on the measured paper properties, pulps of two different initial fibre charge densities were prepared via carboxymethylation. Because of the bluish colour of PEDOT:PSS, the build-up of PEM could be easily followed, since the fibres grew increasingly darker blue throughout the modification sequence. The conductivity of the fibre network increased by 2−3 orders of magnitude when the pulp of a higher fibre charge density was used. This suggests that it is more important to create a fibrous network with a high fibre-fibre joint strength and a large total joined area in the sheet rather than to maximize the adsorbed amount of PEDOT:PSS. A difference in conductivity could also be noted depending on the polyelectrolyte adsorbed in the outer layer, PAH lowered the conductivity compared to PEDOT:PSS. Evaluating the mechanical properties revealed that the use of PEDOT:PSS reduces the tensile strength of the paper. When five double layers had been adsorbed onto the carboxymethylated sample in which PEDOT:PSS formed the outer layer, calculations indicated a 25% decrease in tensile strength compared to that of reference material without PEMs. ESEM studies indicate that PEM treatment produces a significantly changed and somewhat smoother fibre surface.     

Surface phenomena at polymers

Polymers with advanced properties can be achieved among other measures by reinforcing with fibrous materials, by polymer blending and surface modification. Using the surface treatment of PP-EPDM injection moulding specimens (washing, flaming, plasma-treatment) an overview on progress in surface analytics is given. It is shown that XPS, contact angle and zeta-potential measurements give corresponding results concerning the composition of the surface region. Additional to the kind of interaction forces at interfaces the mechanical properties of reinforced polymers are governed by sorption layers and electrical phenomena at interfaces. Corresponding results were obtained at chalk filled PE-HD and glass fibre reinforced polyamide.     

Mechanical and biodegradation performance of short natural fibre polyhydroxybutyrate composites

The work outlined in this paper describes the evaluation of polyhydroxybutyrate (PHB) based natural fibre composites via an extrusion – injection moulding process. Virgin PHB was compounded with two different naturally occuring plant fibres, hemp and jute, and a third, regenerated cellulose fibre, lyocell. Composite materials containing 10–30 wt% of each type of fibre were obtained by twin screw extrusion and the resultant material was injection moulded to produce tensile samples suitable for mechanical characterisation. Mechanical properties were determined using tensile, impact and flexural testing. Melt flow index and water absorption studies were also carried out on the biocomposite materials, and Fourier transform infrared spectroscopy was used to examine the bonding between the polymer and each fibre type. The rate of biodegradation was also observed by placing composite samples in compost and measuring weight loss weekly. The biocomposites produced using this method were shown to have increased rates of biodegradation whilst exhibiting significantly improved flexural properties.     

Flame retardant activity of SiO2-coated regenerated cellulose fibres

An alternative route to lower the flammability of viscose fibres is presented. Instead of adding a flame retardant to the viscose dope chemically, we have grown a layer of silica (SiO₂) on the surface of a regenerated cellulose fibre via a sol-gel process. One set of samples was used as-received, while the other was pre-treated in an 18% NaOH solution, giving a rough, etched surface to the fibre. The different surface morphology of both fibre types triggered a different growth of silica layers. On an untreated fibre, silica formed a 300-400 nm thick surface layer containing a high density of cracks and holes. Conversely, on a NaOH pre-treated fibre, the silica layer intruded into fibre interior, adhered more tightly to the fibre structure and formed an almost defect-free, thin (100 nm) layer on the outer fibre surface. This type of silica layer increased the temperature at which the fibre started to decompose by 20 °C. It also hindered significantly the flow of oxygen to the generated volatiles during the thermal decomposition, and increased the temperature of glowing combustion of the residual char; the temperature of the corresponding exothermic peaks increased by ca. 20 °C and 40 °C. In contrast, the thermal effects of silica coatings that grew on an untreated fibre were much smaller.     

Propriétés rhéologiques à l'état fondu de polyesters thermoplastiques chargés de fibres de verre

A study of rheological properties in the molten state of two short glass fibre reinforced polyesters (polyethylene terephthalate and polybutylene terephthalate) was carried out, both in steady and dynamic flow. The results lead to information on the flow behaviour of these composite materials. Moreover, this study confirms the presence of fibre tied entanglements and shows the influence of the matrix.     

Characterisation of boron nitride fibre coatings with different crystalline order by TEM and XPS

Reinforcement effects in composites are widely influenced by fibre coatings. A detailed understanding of their microstructure and chemical composition is of great interest. Boron nitride films were deposited continuously on fibre rovings of various ceramics in CVD reactors of vertical as well as horizontal position. XPS depth profilings show that the film compositions are close to stoichiometric BN with carbon and oxygen impurities in the range of 10 at%. Cross-sections of separated fibres were investigated by HREM and TEM diffraction. All BN films are hexagonal turbostratic. The (002) layers with an increased distance (about 0.36 nm) showed a mean stacking sequence near to graphite and a characteristic orientation to the fibre in the interface region. We assume the gas flow type and hence the exchange rate of matter and energy determines the film structure in this region. With increasing film thickness the (002) layers fold randomly in all directions or form nanocrystals at elevated temperatures. Received: 7 September 1998 / Revised: 13 January 1999 / Accepted: 5 February 1999     

Surface chemical analysis of raw cotton fibres and associated materials

The surface chemical composition of raw unscoured cotton was successfully investigated by the surface analytical techniques X-ray Photoelectron Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The presence of non-cellulosic material at the fibre surface was established and determined to be a complex mixture of fatty acids, alcohols, alkanes, esters and glycerides. The effect of scouring and bleaching was to reduce the surface concentration of these materials but even after aqueous processing some non-cellulosic material residue was still detected at the fibre surface.     

Characterizing wood polymers in the primary cell wall of Norway spruce (<Emphasis Type="Italic">Picea abies</Emphasis> (L.) Karst.) using dynamic FT-IR spectroscopy

Dynamic Fourier Transform Infra-Red (FT-IR) spectroscopy was used to examine the interactions among cellulose, xyloglucan, pectin, protein and lignin in the outer fibre wall layers of spruce wood tracheids. Knowledge regarding these interactions is fundamental for understanding the fibre separation in a mechanical pulping process. Sheets made from an enriched primary cell wall material were used for studying the viscoelastic response of the polymers. The results indicated that strong interactions exist among lignin, protein, pectin, xyloglucan and cellulose in the primary cell wall. This signified a closely linked network structure of the components on the fibre surface. This ultrastructural arrangement in the primary cell wall and the relatively high content of lignin, pectin and protein in it, means that the primary cell wall is more submissive to selective chemical attacks, when compared to the secondary cell wall. A low ratio of cellulose Iα to cellulose Iβ in the primary cell wall was also found.     

Effect of preparation of sol-gel coatings on the strength of optical fibres

SiO₂, TiO₂, ZrO₂, and TiO₂-ZrO₂ thin coatings were applied by sol-gel method on quartz fibres during the fibre drawing. Durable layers with the thicknesses up to 0.7 m were obtained. The layer smoothness and thickness were determined using electron microprobe analyzer and electron or optical microscopy. In order to investigate a decrease in the strength of sol-gel coated fibres a novel method employing silica capillaries was developed. The fibre strength decrease was explained by the influence of water penetrating as a result of the coating process into the flaws on the fibre surface.     

Why do we observe significant differences between measured and ‘back-calculated’ properties of natural fibres?

The drive towards sustainability, even in materials technologies, has fuelled an increasing interest in bio-based composites. Cellulosic fibres, such as flax and jute, are being considered as alternatives to technical synthetic fibres, such as glass, as reinforcements in fibre reinforced polymer composites for a wide range of applications. A critical bottleneck in the advancement of plant fibre composites (PFRPs) is our current inability to predict PFRP properties from data on fibre properties. This is highly desirable in the cost- and time-effective development and design of optimised PFRP materials with reliable behaviour. This study, alongside limited other studies in literature, have found that the experimentally determined (through single fibre tests) fibre properties are significantly different from the predicted (‘back-calculated’ using the popular rule-of-mixtures) fibre properties for plant fibres. In this note, we explore potential sources of the observed discrepancy and identify the more likely origins relating to both measurement and errors in predictions based on the rule-of-mixtures. The explored content in this discussion facilitates the design of a future investigation to (1) identify the sensitivity of the discrepancy between measured and predicted fibre properties to the various potential origins, (2) form a unified hypothesis on the observed phenomenon, and (3) determine whether the rule-of-mixtures model (in specific cases) can be improved and may be able to predict properties precisely.     

Influence of plasma treatment on the adhesion between a polymeric matrix and natural fibres

The aim of this work is to study the influence of low-pressure plasma treatment on cellulose fibres to improve the adhesion between a polymeric matrix and natural fibres used as reinforcement. To evaluate fibre wettability, contact angle measurements were carried out on flax fibres after treatment with plasma under several conditions. Similarly, contact angle measurements were performed without plasma treatment. A comparison between all the samples led to the definition of the optimal plasma treatment conditions. Once the latter were determined, composite materials were prepared with treated and untreated flax fibres and a low-density polyethylene matrix. Composites, with different fibre contents (5 and 40%) and different fibre lengths (1 and 10 mm), were manufactured using a mixer and a hot plate press. The tensile strengths of the composites were assessed to determine optimal fibre content and length, and the plasma treatment effect was also quantified. It was found that the higher the fibre content, the higher the tensile strength, and the higher the Young’s modulus; however, fibre length did not affect tensile strength. Regarding plasma treatment, composites with treated fibres exhibited a considerably improved tensile strength and Young’s modulus. Plasma treatment effects were also studied by X-ray photoelectron spectroscopy and by differential scanning calorimetric. Finally, an analysis of the fibre surface and an interaction study between the matrix and the fibres was conducted with scanning electron microscopy.     

Recycled injection-molded and fibre-reinforced polyethylene/polypropylene

In this presentation, we are concerned with the fabrication and characterization of samples of compression-molded and injection-molded recycled polyethylene, with, in some cases, addition of cellulose fibre. We wish to know what is the performance of such plastics, as compared to the virgin materials and what is the effect of added fibre in both molding modes.     

Particle capture processes and evaporation on a microscopic scale in wet filters

This paper details results of an experimental study of the capture of solid and liquid aerosols on fibrous filters wetted with water. A microscopic cell containing a single fibre (made from a variety of materials) was observed via a microscope, with a high speed CCD camera used to dynamically image the interactions between liquid droplets, zeolite and PSL particles and fibres. Variable quantities of liquid irrigation were used, and the possibility for subsequent fibre regeneration after clogging or drying was also studied. It was found that drainage of the wetting liquid (water) from the fibres occurred, even at very low irrigation rates when the droplet consisted almost completely of captured particles. It was also found that the fibre was rapidly loaded with captured particles when the irrigation was not supplied. However, almost complete regeneration (removal of the collected cake) by the liquid droplets occurred shortly after recommencement of the water supply. The study also examined the capture of oily liquid aerosols on fibres wetted with water. A predominance of the barrel shaped droplet on the fibre was observed, with oil droplets displacing water droplets (if the oil and fibre combination created a barrel shaped droplet), creating various compound droplets of oil and water not previously reported in literature. This preferential droplet shape implies that whatever the initial substance wetting a filter, a substance with a greater preferential adherence to the fibre will displace the former one.     

Multilayered Nanocomposites Prepared through Quadruple-Layering Approach towards Enhanced Mechanical Performance

Multilayered materials are widely studied due to their special structures and great properties, such as their mechanical ones. In this paper a novel and effective technique, a quadruple-layering approach, was used to fabricate multilayered materials. This approach increases the number of layers rapidly via simple operations. Materials with 4, 16, and 64 layers with alternating layers of polypropylene and nanocomposites were fabricated using this approach, and their film morphology and mechanical properties were studied. The influence of the number of layers on the mechanical properties of the materials and the relationship between the mechanical properties of each material were investigated. The results illustrated that the tensile modulus and strength were enhanced and elongation at the break increased when the layer numbers of the multilayered materials increased. However, this approach has a defect in that as the layer number increases, the layer thickness was not uniform, thus restricting the improvement of properties. This may need to be further studied in future work.