A kinetic investigation of thermal degradation of poly(vinyl formals)

Several samples of poly(vinyl formal) having the same vinyl alcohol content (8–9%) but varying contents of vinyl acetate (6–22%) and vinyl formol (70–85%) were prepared and subjected to thermogravimetric analysis, in air and nitrogen atmospheres, employing both isothermal and dynamic methods. Kinetic parameters determined from both the isothermal and dynamic TGA data are compared. The activation energy is seen to be largely dependent on the degree of conversion, implying a complex degradation reaction. The activation energy is also much less for degradation in air than in nitrogen, which can be explained by a reaction with oxygen-producing structures favoring degradation. The activation energy is less sensitive to variation in polymer composition for degradation in air than in nitrogen. Thus, in the dynamic process, the activation energy value decreases (from 36 to 23 kcal/mole) with increasing acetate content (from 6 to 22%) in nitrogen atmosphere, while in air the activation energy value increases only moderately (from 21 to 27 kcal/mole) with increasing acetate content (from 6 to 22%). The order of reaction is nearly unity, irrespective of the composition of the polymer, both in air and nitrogen.

A kinetic investigation of thermal degradation of poly(vinyl formals)

Several samples of poly(vinyl formal) having the same vinyl alcohol content (8–9%) but varying contents of vinyl acetate (6–22%) and vinyl formol (70–85%) were prepared and subjected to thermogravimetric analysis, in air and nitrogen atmospheres, employing both isothermal and dynamic methods. Kinetic parameters determined from both the isothermal and dynamic TGA data are compared. The activation energy is seen to be largely dependent on the degree of conversion, implying a complex degradation reaction. The activation energy is also much less for degradation in air than in nitrogen, which can be explained by a reaction with oxygen-producing structures favoring degradation. The activation energy is less sensitive to variation in polymer composition for degradation in air than in nitrogen. Thus, in the dynamic process, the activation energy value decreases (from 36 to 23 kcal/mole) with increasing acetate content (from 6 to 22%) in nitrogen atmosphere, while in air the activation energy value increases only moderately (from 21 to 27 kcal/mole) with increasing acetate content (from 6 to 22%). The order of reaction is nearly unity, irrespective of the composition of the polymer, both in air and nitrogen.

Chemical toughening of epoxies. I. Structural modification of epoxy resins by reaction with hydroxy-terminated poly (butadiene-co-acrylonitrile)

In an attempt to toughen the epoxy resin matrix for fiber-reinforced composite applications, a chemical modification procedure of a commercially available bisphenol-A-based epoxy resin using reactive liquid rubber HTBN [hydroxy-terminated poly(butadiene-co-acrylonitrile)] and TDI (tolylene diisocyanate) is described. The progress of the reaction and the structural changes during modification process are studied using IR spectroscopy, viscosity data, and chemical analysis (epoxy value determination). The studies support the proposition that TDI acts as a coupling agent between the epoxy and HTBN, forming a urethane linkage with the former and an oxazolidone ring with the latter. The chemical reactions that possibly take place during the modification are discussed.

Chemical toughening of epoxies. II. Mechanical, thermal, and microscopic studies of epoxies toughened with hydroxyl-terminated poly(butadiene-co-acrylonitrile)

Diglycidyl ether–bisphenol-A-based epoxies toughened with various levels (0–12%) of chemically reacted liquid rubber, hydroxyl-terminated poly(butadiene-co-acrylonitrile) (HTBN) were studied for some of the mechanical and thermal properties. Although the ultimate tensile strength showed a continuous decrease with increasing rubber content, the toughness as measured by the area under the stress-vs.-strain curve and flexural strength reach a maximum around an optimum rubber concentration of 3% before decreasing. Tensile modulus was found to increase for concentrations below 6%. The glass transition temperature Tg as measured by DTA showed no variation for the toughened formulations. The TGA showed no variations in the pattern of decomposition. The weight losses for the toughened epoxies at elevated temperatures compare well with that of the neat epoxy. Scanning electron microscopy revealed the presence of a dual phase morphology with the spherical rubber particles precipitating out in the cured resin with diameter varying between 0.33 and 6.3 μm. In contrast, a physically blended rubber–epoxy showed much less effect towards toughening with the precipitated rubber particles of much bigger diameter (0.6–21.3 μm).

Chemical toughening of epoxies. I. Structural modification of epoxy resins by reaction with hydroxy-terminated poly(butadiene-co-acrylonitrile)

In an attempt to toughen the epoxy resin matrix for fiber-reinforced composite applications, a chemical modification procedure of a commercially available bisphenol-A-based epoxy resin using reactive liquid rubber HTBN [hydroxy-terminated poly(butadiene-co-acrylonitrile)] and TDI (tolylene diisocyanate) is described. The progress of the reaction and the structural changes during modification process are studied using IR spectroscopy, viscosity data, and chemical analysis (epoxy value determination). The studies support the proposition that TDI acts as a coupling agent between the epoxy and HTBN, forming a urethane linkage with the former and an oxazolidone ring with the latter. The chemical reactions that possibly take place during the modification are discussed.

Out-of-equilibrium microrheology using optical tweezers to probe directional viscoelastic properties under shear

Many wormlike micellar systems exhibit appreciable shear thinning due to shear-induced alignment. As the micelles get aligned introducing directionality in the system, the viscoelastic properties are no longer expected to be isotropic. An optical-tweezers-based active microrheology technique enables us to probe the out-of-equilibrium rheological properties of a wormlike micellar system simultaneously along two orthogonal directions-parallel to the applied shear, as well as perpendicular to it. While the displacements of a trapped bead in response to active drag force carry signature of conventional shear thinning, its spontaneous position fluctuations along the perpendicular direction manifest an orthogonal shear thickening, an effect hitherto unobserved. Copyright (C) EPLA, 2010

Monte Carlo simulation of network formation based on structural fragments in epoxy-anhydride systems

A method combining the Monte Carlo technique and the simple fragment approach has been developed for simulating network formation in amine-catalysed epoxy-anhydride systems. The method affords a detailed insight into the nature and composition of the network, showing the distribution of various fragments. It has been used to characterize the network formation in the reaction of the diglycidyl ester of isophthalic acid with hexahydrophthalic anhydride, catalysed by benzyldimethylamine. Pre-gel properties like number and weight distributions and average molecular weights have been calculated as a function of epoxy conversion, leading to a prediction of the gel-point conversion. Analysis of the simulated network further yields other characteristic properties such as concentration of crosslink points, distribution and concentration of elastically active chains, average molecular weight between crosslinks, sol content and mass fraction of pendent chains. A comparison has been made of the properties obtained through simulation with those predicted by the fragment approach alone, which, however, gives only average properties. The Monte Carlo simulation results clearly show that loops and other cyclic structures occur in the gel. This may account for the differences observed between the results of the simulation and the fragment model in the post-gel phase. Copyright (C) 1996 Elsevier Science Ltd.

Tunable Brownian vortex at the interface

A general kind of Brownian vortices is demonstrated by applying an external nonconservative force field to a colloidal particle bound by a conservative optical trapping force at a liquid-air interface. As the liquid medium is translated at a constant velocity with the bead trapped at the interface, the drag force near the surface provides enough rotational component to bias the particle's thermal fluctuations in a circulatory motion. The interplay between the thermal fluctuations and the advection of the bead in constituting the vortex motions is studied, and we infer that the angular velocity of the circulatory motion offers a comparative measure of the interface fluctuations.

Treatment of electroplating effluent through emulsion-free liquid embrane

Separation of dissolved heavy metals such-as Cr(VI) and Cu(II) from electroplating effluents using a new technique of emulsion-free liquid membrane (EFLM) has been studied. Experimental results show that nearly 95% extraction is obtained resulting in stripping phase enrichment up to 50 times relative to feed. It is also found that emulsion-free liquid membranes are highly efficient and superior to other types of liquid membranes.

Oxidation of aqueous sulphur dioxide catalysed by poly-4-vinylpyridine-Cu(II) complex .2. Combined homogeneous and heterogeneous phase oxidation

Aqueous phase oxidation of sulphur dioxide at low concentrations catalysed by a PVP-Cu complex in the solid phase and dissolved Cu(II) in the liquid phase is studied in a rotating catalyst basket reactor (RCBR). The equilibrium adsorption of Cu(II) and S(VI) on PVP particles is found to be of the Langmuir-type. The diffusional effects of S(IV) species in PVP-Cu resin are found to be insignificant whereas that of product S(VI) are found to be significant. The intraparticle diffusivity of S(VI) is obtained from independent tracer experiments. In the oxidation reaction HSO3- is the reactive species. Both the S(IV) species in the solution, namely SO2(aq) and HSO3- get adsorbed onto the active PVP-Cu sites of the catalyst, but only HSO3- undergoes oxidation. A kinetic mechanism is proposed based on this feature which shows that SO2(aq) has a deactivating effect on the catalyst. A rate model is developed for the three-phase reaction system incorporating these factors along with the effect of concentration of H2SO4 on the solubility of SO2 in the dilute aqueous solutions of Cu(II). Transient oxidation experiments are conducted at different conditions of concentration of SO2 and O-2 in the gas phase and catalyst concentration, and the rate parameters are estimated from the data. The observed and calculated profiles are in very good agreement. This confirms the deactivating effect of nonreactive SO2(aq) on the heterogeneous catalysis.

Irreversibility-to-reversibility crossover in transient response of an optically trapped particle

We study the transient response of a colloidal bead which is released from different heights and allowed to relax in the potential well of an optical trap. Depending on the initial potential energy, the system's time evolution shows dramatically different behaviors. Starting from the short-time reversible to long-time irreversible transition, a stationary reversible state with zero net dissipation can be achieved as the release point energy is decreased. If the system starts with even lower energy, it progressively extracts useful work from thermal noise and exhibits an anomalous irreversibility. In addition, we have verified the Transient Fluctuation Theorem and the Integrated Transient Fluctuation Theorem even for the non-ergodic descriptions of our system. Copyright (C) EPLA, 2011

Use of maleic anhydride-grafted polyethylene as compatibilizer for HDPE-tapioca starch blends: Effects on mechanical properties

Tapioca starch in both glycerol-plasticized and in unplasticized states was blended with high-density polyethylene (HDPE) using HDPE-g-maleic anhydride as the compatibilizer. The impact and tensile properties of the blends were measured according to ASTM methods. The results reveal that blends containing plasticized starch have better mechanical properties than those containing unplasticized starch. High values of elongation at break at par with those of virgin HDPE could be obtained for blends, even with high loading of plasticized starch. Morphological studies by SEM microscopy of impact-fractured specimens of such blends revealed a ductile fracture, unlike blends with unplasticized starch at such high loadings, which showed brittle fracture, even with the addition of compatibilizer. In general, blends of HDPE and plasticized starch with added compatibilizer show better mechanical properties than similar blends containing unplasticized starch. (C) 2001 John Wiley & Sons, Inc.

Analog/RF Built-in-Self-Test Subsystem for a Mobile Broadcast Video Receiver in 65-nm CMOS

A built-in-self-test (BIST) subsystem embedded in a 65-nm mobile broadcast video receiver is described. The subsystem is designed to perform analog and RF measurements at multiple internal nodes of the receiver. It uses a distributed network of CMOS sensors and a low bandwidth, 12-bit A/D converter to perform the measurements with a serial bus interface enabling a digital transfer of measured data to automatic test equipment (ATE). A perturbation/correlation based BIST method is described, which makes pass/fail determination on parts, resulting in significant test time and cost reduction.

Study of Microstructure Evolution during Semi-Solid Processing of an In-Situ Al Alloy Composite

In the present work, effect of pouring temperature (650 degrees C, 655 degrees C, and 660 degrees C) on semi-solid microstructure evolution of in-situ magnesium silicide (Mg2Si) reinforced aluminum (Al) alloy composite has been studied. The shear force exerted by the cooling slope during gravity driven flow of the melt facilitates the formation of near spherical primary Mg2Si and primary Al grains. Shear driven melt flow along the cooling slope and grain fragmentation have been identified as the responsible mechanisms for refinement of primary Mg2Si and Al grains with improved sphericity. Results show that, while flowing down the cooling slope, morphology of primary Mg2Si and primary Al transformed gradually from coarse dendritic to mixture of near spherical particles, rosettes, and degenerated dendrites. In terms of minimum grain size and maximum sphericity, 650 degrees C has been identified as the ideal pouring temperature for the cooling slope semi-solid processing of present Al alloy composite. Formation of spheroidal grains with homogeneous distribution of reinforcing phase (Mg2Si) improves the isotropic property of the said composite, which is desirable in most of the engineering applications.