Environmentally friendly polymer hybrids Part I Mechanical, thermal, and barrier properties of thermoplastic starch/clay nanocomposites

As an attempt to develop environmentally friendly polymer hybrids, biodegradable thermoplastic starch (TPS)/clay nanocomposites were prepared through melt intercalation method. Natural montrorillonite (Na⁺ MMT; Cloisite Na⁺) and one organically modified MMT with methyl tallow bis-2-hydroxyethyl ammonium cations located in the silicate gallery (Cloisite 30B) were chosen in the nanocomposite preparation. TPS was prepared from natural potato starch by gelatinizing and plasticizing it with water and glycerol. The dispersion of the silicate layers in the TPS hybrids was characterized by using wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). It was observed that the TPS/Cloisite Na⁺ nanocomposites showed higher tensile strength and thermal stability, better barrier properties to water vapor than the TPS/Cloisite 30B nanocomposites as well as the pristine TPS, due to the formation of the intercalated nanostructure. The effect of clay contents on the tensile, dynamic mechanical, and thermal properties as well as the barrier properties of the nanocomposites were investigated.     

Cover Picture: Assembly of Wiseana Iridovirus: Viruses for Colloidal Photonic Crystals (Adv. Funct. Mater. 8/2006)

Assembly of colloids is a versatile tool for micro‐ and nanofabrication. Natural and artificially engineered viruses offer the opportunity to expand the functionality and versatility of such assemblies. The cover shows optically iridescent, thin polycrystalline arrays (background) as well as bulk pellets (inset right) that exhibit reversible hydration‐dependent reflection spectra, as reported by Vaia and co‐workers on p. 1086. The films and pellets were created in vitro with classical colloid‐assembly techniques from Wiseana iridescent virus (inset, center) harvested from infected Wiseana spp larvae (inset, left). In vitro assembly of Wiseana iridescent virus (WIV) yields iridescent pellets and films with structural color more vivid than in the native insect. WIV is icosahedral in shape, 140 nm in diameter, with 30 nm long fibrils attached to the outer surface, and exhibits a surface charge ca. 1/6th that of a comparable polymer colloid. The low surface charge and tethered chains on the virus surface allow the facile modification of the interparticle distance. Directed sedimentation yields predominantly an amorphous liquid‐like packing of the virus. Such samples exhibit a broad reflection band that is angle independent and for which the broad maximum can be reversibly shifted from blue towards red with increased hydration. Slow sedimentation and flow‐assisted assembly methods produce thin films with a polycrystalline morphology that exhibit narrower, more intense reflectivity peaks, which are hydration and angle dependent. This study points toward the potential of viral particles for photonic crystals where their unique structural features (icosahedral symmetry, extreme monodispersity, precise surface functionalization, and tethered surface chains of low surface‐charge density) may lead to superior control of optical properties of their assembled arrays.     

A research on hydrogen cracking in α-Fe

The mechanism of hydrogen cracking in α-Fe has been studied by positron annihilation technique and transmission electron microscopy (TEM). It was revealed that microvoids were promoted by hydrogen-vacancy complex, and microcracks were initiated by coalescence and growth of such microvoids along grain boundaries of α-Fe during cathodic charging. The thermostability of such microcracks was also studied.     

Effect of protein on nutrient digestion and milk production by Holstein cows

Four multiparious Holstein cows fitted with ruminal and duodenal cannulae were in a 4 X 4 Latin square experiment to assess effects of increasing dietary protein on ruminal blood and duodenal traits, milk production, and nutrient digestion. Protein percents of 13, 15, 17, and 19 dry matter were achieved by rolled barley replaced with 0, 12, 24, and 36% rapeseed (canola) meal in pelleted concentrate mixtures. Increasing dietary protein concentration increased ruminal ammonia nitrogen, urea nitrogen in blood serum, and concentration of duodenal total, nonammonia, and feed nitrogen. Highest microbial nitrogen concentration was in cows fed the 15% protein diet; ruminal ammonia nitrogen was 6 mg/100 ml at this percent of protein. Cows fed 13% protein lost body weight (.43 kg/day), whereas those at 15, 17, and 19% protein gained .59, .38, and .59 kg/day. Efficiency of conversion of feed protein to milk protein declined, but digestibility of dry matter, organic matter, and nitrogen was improved with increasing dietary protein. From the traits measured, 15% crude protein appeared to be optimum for cows producing an average of 28 kg milk per day.     

Plasticization of chitosan membrane for pervaporation of aqueous ethanol solution

The process of pervaporation in which two components diffuse through a nonporous polymer membrane was modelled when one of the penetrants can exert a plasticization action to the membrane material. Thereat a phenomenological model was employed for describing the plasticization effect on the diffusivities for penetrants in the membrane. The sorption equilibria and permeation fluxes for aqueous ethanol solutions in a chitosan membrane were measured, and the permeation fluxes for water were compared with those predicted by the proposed model. The concentration of sorbed water was linear with its weight fraction (x₄) in the feed solution, whereas the permeation flux of water was. affected by the plasticization action of sorbed water to the polymer. This plasticization effect on the diffusion process can be simulated in terms of the proposed phenomenological model.     

Plasma-sprayed hydroxylapatite coating on carbon fibre reinforced thermoplastic composite materials

Plasma-spraying of metallic impiant surfaces is an established method for the application of hydroxylapatite (HA) coatings. Carbon fibre reinforced thermoplastics show different thermal and mechanical properties, compared with titanium substrates. In this paper first results of the influence of the established coating method on carbon fibre reinforced thermoplastics are presented. First investigations of the tensile adhesion strength, tested with a newly developed testing device, showed that the adhesion between the HA coating and the carbon fibre reinforced polyetheretherketone (PEEK) composite is very low. Macromechanical bending tests showed a change to initial tensile instead of compression failure of the coated composite substrate. Micromechanical bending tests in a scanning electron microseope (SEM) hot tensile stage (Raith GmbH) revealed crack propagation within the ceramic coating and in the coating-substrate interface before the total failure of the composite substrate occurred.     

Mechanical Properties of Mica Glass-Ceramics

The mechanical properties of fluorophlogopite mica-based glass-ceramics, such as fracture toughness, flexural strength, and machinability, were investigated. It has been shown that toughening increments in the glass-ceramics occurred by crack deflection and branching by crystals with a high aspect ratio. All the glass-ceramics heat treated at 1000°–1150°C exhibited a higher fracture toughness of 1.2–2.2 MPa-m^1/2 as compared to 0.8 MPa-m^1/2 for the parent glass, and showed average flexural strengths of 140–160 MPa. It has been suggested that ( H/K_Ic )² of the mica glass-ceramic be used to estimate the machinability, because it decreases linearly with machinability.     

Determination of reflector angular position using directionalphase-encoded wavefield

Using a directional phase-encoded wavefield, experiments are performed to determine if reflector angular coordinates can be obtained from the encoded phase. Where the target sizes are small, experiments show that significant phase distortions are introduced in the echoes. A mathematical expression for the reflection-diffraction response of a rectangular plate is derived and confirms major phase distortions can arise due to edge diffractions. A scheme of phase reversal is then devised which eliminates the effects of this phase distortion, enables target direction to be determined, and distinguishes small reflectors from large ones. This scheme also tends to be less sensitive to measurement errors. The new results are yet another important support for the usefulness of the emerging concept on directional phase-encoded wavefield     

Syntheses and properties of polyurethanes containing side‐chain azobenzene groups

Polymers containing azobenzene groups have the characteristic reaction of photo‐induced cis–trans isomerism. The study of new materials for optical information storage has prompted making use of these photo‐isomerizations. In this study, we report the syntheses and properties of four different polyurethanes (DR‐PUns) containing azobenzene groups in the side‐chains. The structurally similar polyurethanes (DR‐PUns) were synthesized by the polycondensation reaction of Disperse Red 19 (DR 19) and four different diisocyanates in dimethylformamide. By introducing of DR 19 into the polymer, we obtained polymers containing a photochromic group in the side‐chain. The weight‐average molecular weights of the DR‐PUns were in the range 5500–12 900. The T_gs of the DR‐PUns range from 119.5 °C to 157.0 °C, depending on the structure of the diisocyanate. Optical properties and solubilities of the polyurethanes were compared. The diffraction efficiencies of films were measured as a function of the reaction time. Typically, the diffraction efficiencies of the DR‐PU1 film prepared from toluene 2,4‐diisocyanate were observed up to a level of 0.25%. For the DR‐PU1 film, the effect of the intensity of the induced laser beam on the diffraction efficiency is also discussed. © 2003 Society of Chemical Industry     

Synthesis and properties of novel poly(meth)‐acrylates containing tricyanocyclopropyl groups for piezoelectric applications

o‐(2,2,3‐Tricyano‐3‐carbomethoxycyclopropyl)phenoxyethyl acrylate ( 5a ) and o‐(2,2,3‐tricyano‐3‐carbomethoxycyclopropyl)phenoxyethyl methacrylate ( 5b ) were prepared by reactions of bromomalononitrile with methyl o‐(2‐acryloyloxyethoxy)benzylidenecyanoacetate and methyl o‐(2‐methacryloyloxyethoxy)benzylidenecyanoacetate respectively. The dipole moments of 5a and 5b , calculated by atom superposition and electron delocalization molecular orbital method, were 2.75–3.47 D. Monomers 5a and 5b were polymerized with free‐radical initiators to obtain the polymers with tricyanocyclopropane ring as a piezoelectric chromophore in the pendant group. The resulting polymers 6a and 6b were soluble in common organic solvents such as acetone and DMF. Polymers 6a and b showed thermal stability up to 280 °C in TGA thermograms. T_g values obtained from DSC thermograms were in the range 125–140 °C. Piezoelectric coefficients (d₃₁) of the poled films were 1.2–1.4 pC N^?1. These polymers showed good temporal and long‐term thermal stabilities which are acceptable for piezoelectric device applications. Copyright © 2003 Society of Chemical Industry