Effects of Stearic Acid on the Injection Molding of Alumina

This research investigated the influence of stearic acid on the injection molding of alumina, by varying the concentration of stearic acid. The interaction between stearic acid and alumina was identified using transmission infrared spectroscopy, indicating stearic acid preferentially adsorbed onto the alumina powder surface. In addition to slightly modifying the intrinsic binder viscosity, stearic acid adsorbed onto the powder surface changed the flow behavior of the mixtures from dilatant flow to pseudoplastic flow at low temperatures. As a result, inhomogeneous distribution of binder in the injection-molded parts was minimized with increased stearic acid concentration. However, the possibility of forming bubbles in the mixtures arising from vaporization of stearic acid was enhanced. Additionally, the binder burnout temperature range was broadened with the increase of stearic acid concentration.     

Fatty acid selectivity of lipases: Erucic acid from rapeseed oil

The fatty acid selectivity of several commercial lipases was evaluated in the hydrolysis of high-erucic acid rapeseed oil (HEARO). The lipase ofPseudomonas cepacia catalyzed virtually complete hydrolysis of the oil (94–97%), while that ofGeotrichum candidum discriminated strongly against erucic acid, especially in esterification. A two-step process is suggested for obtaining a highly enriched erucic acid in which theG. candidum lipase is employed to selectively esterify the fatty acid residues of unsaturated C-18, and shorter chain acids, from a mixture of HEARO fatty acids obtained from total hydrolysis of the oil withP. cepacia lipase.     

Bulk and suspension polymerization of styrene in the presence of n-pentane. An evaluation of monofunctional and bifunctional initiation

The plasticizing effect of n-pentane on the rate of bulk free radical polymerization of styrene and molecular weight distribution development has been modeled on the basis of the free volume theory for both monofunctional and bifunctional initiation. A strong decrease in the reaction rate in the late stages of the polymerization, due to the displacement of the onset of the gel effect, has been observed for both types of initiation. This decrease in the polymerization rate limited the terminal conversion to values well below 100% for mono-functional initiation. However, in bifunctionally initiated polymerization, terminal conversions close to 100% were obtained in spite of the decrease in reaction rate. Contrary to what was expected, the molecular weight distribution obtained at terminal conversion was almost completely insensitive to these changes in polymerization rate. This phenomenon is explained in terms of limited transfer to monomer reactions when n-pentane is present in the system. In suspension polymerization, the limiting conversion and plasticizing effects of n-pentane in monofunctionally initiated systems, caused enhanced coalescence leading to suspension set-up. In bifunctionally initiated systems this enhanced coalescence was completely overcome by the short duration of the particle growth stage, owing to high polymerization rates, and stable suspensions were achieved. For these systems the particle size distributions obtained were similar to that of suspension polystyrene without n-pentane. © 1993 John Wiley & Sons, Inc.     

Catalysis of gasification of coal-derived cokes and chars

Calcium is the most important in-situ catalyst for gasification of US coal chars in O₂, CO₂ and H₂O. It is a poor catalyst for gasification of chars by H₂. Potassium and sodium added to low-rank coals by ion exchange and high-rank coals by impregnation are excellent catalysts for char gasification in O₂, CO₂ and H₂O. Carbon monoxide inhibits catalysis of the CH₂O reaction by calcium, potassium and sodium; H₂ inhibits catalysis by calcium. Thus injection of synthesis gas into the gasifier will inhibit the CH₂O reaction. Iron is not an important catalyst for the gasification of chars in O₂, CO₂ and H₂O, because it is invariably in the oxidized state. Carbon monoxide disproportionates to deposit carbon from a dry synthesis gas mixture (3 vol H₂ + 1 vol CO) over potassium-, sodium- and iron-loaded lignite char and a raw bituminous coal char, high in pyrite, at 1123 K and 0.1 MPa pressure. The carbon is highly reactive, with the injection of 2.7 kPa H₂O to the synthesis gas resulting in net carbon gasification. The effect of traces of sulphur in the gas stream on catalysis of gasification or carbon-forming reactions by calcium, potassium, or sodium is not well understood at present. Traces of sulphur do, however, inhibit catalysis by iron.     

Slow stable crack growth in high density polyethylenes

The phenomenon of slow stable crack growth in polyethylene is investigated using notched specimens subject to constant load and the concepts of fracture mechanics. The effect of specimen geometry and dimension, the loading and the mode of loading on the applied stress intensity factor versus crack speed ($\text{K}{}_{\mathrm{c}}\text{-}\text{a}\text{?}$) curves has been studied to demonstrate that K_c is the controlling stress parameter for crack growth under suitable conditions. $\text{K}{}_{\mathrm{c}}\text{-}\text{a}\text{?}$ curves are obtained for a high density polyethylene homopolymer in distilled water and in a diluted detergent solution at four different temperatures. Results are also obtained for a much tougher medium density polyethylene copolymer whenever possible. Several mechanisms can be identified from the form of the $\text{K}{}_{\mathrm{c}}\text{-}\text{a}\text{?}$ curves. Two, in particular, have been observed but not explained before: (i) crack growth with a time dependence of 0.25, and (ii) the high $\text{K}{}_{\mathrm{c}}\text{-}\text{a}\text{?}$ slopes for crack growth in a tough copolymer. With the help of scanning electron microscopic studies of the fracture surfaces, (i) is postulated to be due to diffusion controlled void growth process and (ii) is considered to be the result of crack tip blunting effects. From the temperature dependence of crack growth, the activation energy of the diffusion controlled crack growth process is found to coincide with that of the x-relaxation process in polyethylene implying that diffusion controlled crack growth may be related to the motion of main chains in the polymer.     

Critical evaluation of coupling particle size distribution with the shrinking core model

The shrinking core model (SCM) is widely used to model fluid-solid reactions such as the leaching of metals from minerals. In most cases, however, the particle size distribution (PSD) of the solid material was disregarded. In this paper the erroneous shift in the control regime when neglecting PSD was quantified and the dependence of the shift on the coefficients of variation (CV) and the type of PSD was analysed. By coupling the SCM with a Gamma PSD, it was found that neglecting the PSD would shift the control regime from chemical reaction to inert/ash layer diffusion, when the CV was between 0.7 and 1.2. For a system controlled by liquid film diffusion, neglect of the PSD, would shift the control regime to chemical reaction when CV is between 0.3 and 0.7 or to inert/ash layer diffusion when CV is greater (0.9-1.5). It was therefore postulated that some researchers had unknowingly made invalid conclusions about the control regime due to the neglect of PSD. However, an inert/ash layer diffusion-controlled process was insensitive to the neglect of PSD. When CV<0.3, neglect of the PSD would not cause any erroneous shifts, irrespective of the control regime. Experimental data confirmed the observation. For a given CV, the deviation in the fraction reacted from the mono-PSD increases with CV and decreases with time. The maximum deviation, which occurs at the beginning, is about 10% with a gamma PSD of CV=0.3. The percent deviation is dependent of the type of PSDs. Gamma PSD gives the lowest deviation while Gaudin-Schuhmann results in the largest deviation (maxi. ∼19%, with CV=0.3) in the first half of dissolution process. Log-normal distribution gives a larger deviation than gamma but quickly approaches the latter with time. The deviation for Rosin-Rammler is between log-normal and Gaudin-Schuhmann. For systems with CV less than 0.3, the SCM can be fairly used without considering PSD. When CV is greater than 0.3, particularly in the early stage of a dissolution process with a PSD other than gamma, PSD should be included to avoid substantial errors.     

The onset of Taylor-Görtler vortices in impulsively decelerating swirl flow

The onset of hydrodynamical instability induced by impulsive spin-down to rest in a cylinder containing a Newtonian fluid is analyzed by using propagation theory. It is well-known that the primary transient swirl flow is laminar, but with initial high velocities secondary motion sets in at a certain time. The dimensionless critical time Τ_c to mark the onset of instability is presented here as a function of the Reynolds number Re. Available experimental data indicate that for large Re deviation of the velocity profiles from their momentum diffusion occurs starting from a certain time Τ≈4Τ_c. This means that secondary motion is detected at this characteristic time. It seems evident that during Τ_c⪯Τ⪯4Τ_c, secondary motion is relatively very weak and the primary diffusive momentum transfer is dominant.     

Spectroscopic and electrical properties of 3-alkyl pyrrole-pyrrole copolymers

Three types of copolymers composed of pyrrole and 3-alkyl pyrroles (with alkyl being pentyl, nonyl and undecyl) have been synthesized. A strong linear dependency of the alkyl chain length on the as-prepared copolymer physical properties is demonstrated via (a) DSC (for phase transition temperatures and enthalpy changes) and (b) UV-vis (for wavelengths of the polaronic and bipolaronic electronic transitions, and ratio of the corresponding absorbances). A trend in the copolymers' doping level vs alkyl chain length is also estimated, via IR, by taking the ratio of band intensities of the stretching modes of the polaronic and bipolaronic species. The copolymers are found to be soluble in organic solvents and their solutions can be cast onto glass substrates or metals resulting in thin films, which can be used as the electroactive component of Schottky diodes. The electrical properties of these diodes are also found to be dependent on increasing 3-alkyl chain length.     

Isosteric heat of sorption of CO2 in poly(ethylene terephthalate)

Sorption isotherms for carbon dioxide in poly(ethylene terephthalate) have been measured at 35–55°C. The isotherms were measured gravimetrically on a Mettler Thermoanalyzer-1 from vacuum to 1 atmosphere. The sorption data were used to generate sorption isotherms from which the isosteric heat of sorption of CO₂ in PET was determined. At 45°C the isosteric heat of sorption increases from −10 kcal/mole at a concentration of 0.5 cm³ (STP)/cm³ (polymer) to −8 kcal mole⁻¹ at a concentration of 1.5 cm³ (STP)/cm³ (polymer). It has been reported in the literature that the isosteric heat of sorption for this system decreased through a minimum before increasing with increasing concentration. Our measurement of the low-pressure sorption isotherms shows that this is not the case.