The heterogeneous nucleation of microcellular foams assisted by the survival of microvoids in polymers containing low glass transition particles. Part I: Mathematical modeling and numerical simulation

The existing models based on classical nucleation theory are not able to explain satisfactorily the nucleation phenomenon of microcellular foams in thermoplastics. Here, we extend the analysis of Kweeder (24), who developed a new model that considers the presence of microvoids, resulting from the thermal processing history of the polymer, as potential nucleation sites. The nucleation model “concentrates” on the stresses and thus void formations in the rubber particles. Since these are pre-existing microvoids, bubble nucleation depends on the survival of these voids to grow rather than the formation of a new phase as modeled by classical nucleation theory. The population of viable microvoids with a sufficiently large radius to survive and overcome surface and elastic forces has been modeled to yield the cell density. A log-normal distribution, which relates to the rubber particle size, has been used to model the distribution of microvoids in the polymer composite material. The model depends on various process parameters such as saturation pressure, foaming temperature, concentration of nucleating agents, solubility of the blowing agent in the polymer, and the modulus. High impact polystyrene (HIPS) was added to polystyrene to obtain polymers with different concentrations of rubber gel particles, the nucleating agent, and used here for this study.     

Effect of partial replacement of di(2‐ethyl hexyl)phthalate,by a polymeric plasticizer,on the permeability and leaching properties of poly(vinyl chloride)

Acrylonitrile butadiene rubber (NBR) was used as a polymeric plasticizer in poly(vinyl chloride) (PVC) for the partial replacement of di(2‐ethyl hexyl)phthalate (DEHP). The effect of this partial replacement on DEHP leaching from the PVC was evaluated at 10, 25, and 40°C. The study shows that the incorporation of NBR reduces the rate of DEHP leaching, the reduction being prominent at lower temperatures. Gas permeability of the NBR‐modified samples was also evaluated at the above temperatures using oxygen and carbon dioxide. A reduction in gas permeability is observed in NBR‐modified samples compared to the PVC plasticized with DEHP alone particularly in the case of carbon dioxide. Water vapor transmission rates of the NBR‐modified samples are higher than that of the control sample. The NBR‐modified PVC sample was found to be noncytotoxic in the in vitro cytotoxic evaluation both by direct contact and test on extract methods. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4720–4727, 2006     

Swelling behavior of hydroxyapatite‐filled chitosan–poly(acrylic acid) polyelectrolyte complexes

A family of hydroxyapatite (HAP)‐filled chitosan (CHI)–poly(acrylic acid) (PAA) polyelectrolyte complexes was prepared for the development of a degradable biocompatible organic matrix with nascent HAP that will degrade in vivo over a period of time. The effects of complexation on the degradation profile of the composites as well as the interaction between the CHI–PAA matrix and HAP in the composite system were evaluated by studying the swelling behavior of these composites in phosphate‐buffered saline (PBS) by varying their CHI–PAA ratio and HAP content. All composite systems showed a general trend of three stages of swelling with the variation in the degree of equilibrium swelling. The percentage weight gain initially decreased in a linear way with increases in the HAP weight percentages, leading to a first equilibrium swelling, represented by the plateau; further increased to a greater extent; and finally stabilized. The CHI/PAA/HAP composites were stable in PBS up to a period of more than 45 days whereas the 50/50 CHI/PAA control sample showed a single equilibrium attained after a period of 288 h. Further exposure of the specimen to the medium led to its disintegration. It was also observed that, even though CHI and PAA were capable of binding HAP, because of the lack of efficient binding, the integrity of the CHI–HAP and PAA–HAP composites were lost within 48 h. The 50/50/80 CHI/PAA/HAP composition showed the minimum amount of swelling in the series. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4716–4722, 2006     

Sodium alginate–poly(hydroxyethylmethacrylate) interpenetrating polymeric network membranes for the pervaporation dehydration of ethanol and tetrahydrofuran

Interpenetrating polymeric network (IPN) membranes of sodium alginate (NaAlg) and various amounts of poly(hydroxyethylmethacrylate) (PHEMA) have been prepared and tested for the pervaporation dehydration of ethanol and tetrahydrofuran (THF). The presence of hydrophilic PHEMA in the IPN matrix was found to be responsible for increase in membrane selectivity to water. NaAlg–PHEMA IPN membrane containing 20 wt % of PHEMA exhibited a selectivity of 571 to water for the water–ethanol mixture and 857 for water–THF mixture. These data are much better than those observed for the pristine NaAlg membrane. However, flux of the IPN membranes was smaller than that of pristine NaAlg membrane. Comparatively higher flux values were observed for water–THF mixture than for water–ethanol mixture. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3324–3329, 2006     

Studies on bitumen production from North Rumaila crude oil

In the present investigation, the effect of three process variables viz., air rate, temperature and time of oxidation has been studied to determine the possibility of making paving bitumens from North Rumaila Crude Oil. In order to have flexibility in the choice of proper feedstock for bitumen production, the effect of these process parameters was studied on three different vacuum residues. Air rate and temperature of oxidation were optimised to produce a bitumen product having less temperature susceptibility. The composition studies of typical feeds and oxidised products indicate that mainly “saturates” components get converted to “asphaltics” on air blowing.     

Preparation and characterization of novel semi‐interpenetrating 2‐hydroxyethyl methacrylate‐g‐chitosan copolymeric microspheres for sustained release of indomethacin

A novel semi‐interpenetrating (semi‐IPN) graft copolymer of 2‐hydroxyethyl methacrylate (HEMA) with chitosan (CS) has been prepared in the form of microspheres, using water‐in‐oil (W/O) emulsion technique. Microspheres were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and X‐ray diffractometry (X‐RD) to confirm the crosslinking and polymorphism of indomethacin (IDM). The X‐RD and DSC techniques indicated a molecular‐level dispersion of IDM in the IPN matrix. Scanning electron micrographs (SEM) taken at the cross section of the microspheres have shown rough surfaces around the microspheres. The sustained release characteristics of the matrices for IDM, an anti‐inflammatory drug, were investigated in pH 7.4 media. Particle size and size distribution of the microspheres were studied by laser light diffraction particle size analyzer. The drug was released in a sustained manner for up to 12 h. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

A polyphenolic biomacromolecule prepared from a flavonoid: Catechin as degradable microparticles

Catechin (CAT) was crosslinked with trimethylolpropane triglycidyl ether (TMPTGE) to obtain degradable poly(CAT) particles in a single step. Spherical p(CAT) particles with tens of micrometer size range and an isoelectronic point at pH 1.2 were obtained. The hydrolytic degradation of p(CAT) particles provided sustainable and extended release with 264 mg/g CAT release within 10 days at pH 7.4. The antioxidant capacity of 55.0 ± 0.9 μg/ml gallic acid equivalent in terms of total phenol content, and 0.88 ± 0.3 μmol/g trolox equivalent were estimated for p(CAT) particles displaying strong radical scavenging capability. Blood clotting and hemolysis assays demonstrated dose-dependent blood compatibility revealing higher blood compatibility for p(CAT) particles up to 10 μg/ml concentration. The cytotoxicity results show that p(CAT) particles have almost no toxicity for CCD841 normal colon cells at 250 μg/ml concentration in 24 h incubation time giving ~97% cell viability, whereas CAT molecules only provide ~34% cell viability.     

Effect ofθ-alumina formation on the growth kinetics of alumina-forming superalloys

Alumina-forming ODS superalloys are excellent oxidation-resistant materials. Their resistance relies upon the establishment of a stable, slow-growing, and adherent -alumina. In the present investigation, these alloys exhibited unstable and relatively less adherent -alumina phase, which increased the oxidation rate in the transient stage and converted into -alumina in the later part of the exposure. The oxide-growth process was found to depend upon various parameters such as temperature, time, and presence of an active elecment in the superalloy. Characterization carried out by XRD, SEM/EDAX, and AES on oxidized ODS and non-ODS alloys demonstrated a significant influence of the active element, Y, on the transformation of - to -alumina. SIMS analysis of two-stage oxidation at 900°C for two different durations evidently showed that the change in the transport process is due to -to--alumina transformation. On the basis of these results, a new and consistent mechanism is proposed to explain the influence of -alumina and its transformation on growth kinetics and the effect of yttrium on the transformation leading to good scale adherence and oxidation resistance.     

Thermal error measurement and modelling in machine tools.: Part I. Influence of varying operating conditions

Thermal error in machine tools has been observed to be closely linked to the temperature of critical elements of the machine. It was found, in the experiments conducted herein, that there was a significant increase in the axis positioning error on account of an increase in the temperature of the machine elements due to continuous operation. However, it was also observed that the specific operating parameters of the test cycles carried out also significantly affected the positioning error. Different sets of operating parameters generated significantly different error values even though the temperature of the machine elements generated by those operating conditions was similar. As such, this observation forms a very important consideration in the development of a generic thermal error compensation system. It appears to indicate that such a system needs to be capable of evaluating the compensation depending upon the temperature values of the machine elements as well as account for the effect that different operating parameters induce upon the positioning error under the same thermal condition of the machine. This paper attempts to analyse the thermal behaviour of a three-axis vertical machining centre under the influence of various operating parameters and, through the experimental results obtained, point out and explain the effect of these parameters on the axis positioning error. This behaviour forms the basis of an improved modelling methodology that is presented separately in Part II of this paper.     

Chemically functionalized carbon nanotubes and their characterization using thermogravimetric analysis, fourier transform infrared, and raman spectroscopy

This article reports key findings on the chemical functionalization of carbon nanotubes (CNT). The functionalization of chemical vapor-deposited CNT was carried out by treating tubes with polyvinyl alcohol through ultrasonication in water with the aid of a surfactant. The surfactant is expected to promote the unbundling of aggregated CNT. The characterization of functionalized samples using thermogravimetric analysis, Fourier transform infrared spectroscopy, and Raman spectroscopy revealed that the CNT were functionalized by the interaction of carboxylic acid and hydroxyl groups. From the characterization studies, it is apparent that there is a strong interaction between these functional groups and the covalently bonded carbon in the CNT network. The functionalization process enabled good CNT dispersion in the solution, and the CNT remained in suspension for many days. To support the effective functionalization of the tubes, the interaction of functionalized CNT with Ni ions is also demonstrated. This paper was presented at the fourth International Surface Engineering Congress and Exposition held August 1–3, 2005 in St. Paul, MN.