Refining cottonseed oil at high rates of shear

Summary Ten crude cottonseed oils obtained from different areas in the South and Southwest were refined with and without the use of high-shear agitation in the step involving the initial mixing of the crude oil and caustic soda solution. In each instance the use of high shear produced a lower color in the refined oil. The improvement with some oils was not marked because they either refined very well by the ordinary method or failed for some unexplained reason to respond readily to high-shear mixing. However a good proportion of the oils which were quite dark after refining by the ordinary method refined to a much lighter oil when high shear was used. It was established that in high shear refining the color of the refined oil decreased as the temperature at which high shear was used decreased, the time at high shear increased, and the rate at which shear was applied increased. However an increase in the latter above a certain value had no effect. Also it was found that the color of the refined oil decreased as the amount and strength of the caustic soda solution increased. Absorption spectra of some of the processed oils indicated that high shear was more effective than ordinary mixing in removing from an oil the gossypol-like and carotenoid color bodies. Presented at the 28th fall meeting of The American Oil Chemists’ Society, Minneapolis, Minn., Oct. 11–13, 1954. One of the laboratories of the Southern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Constitutive response of calcium‐silicate‐hydrate layers under combined loading

Calcium‐silicate‐hydrate (C‐S‐H) is the main hydration product for ordinary Portland cement (OPC) materials that exhibits a layered structure containing interfaces that controls the system response to shear deformation at the nanometer scale. In this work, we used molecular statics simulations to study the mechanical behavior of an atomistic model of C‐S‐H under combined loading conditions that are typical of structural applications of these materials. Combined loading is implemented by first compressing or stretching the atomistic structure to impose an external hydrostatic pressure, and then loading the system through both heterogeneous and homogeneous shear deformation. By utilizing two different shear methodologies, we were able to isolate the interface behavior from the bulk response. Our results show several qualitative similarities with that of macroscale cementitious materials including pressure sensitivity of the maximum shear strength and strength asymmetry in compression and tension. This indicates that the well‐known cohesive‐frictional behavior of cementitious materials is fundamental to interfaces between C‐S‐H grains at the nanoscale. Comparing differences in our results with nanoindentation experiments motivate future investigations of the effect of C‐S‐H particle size and morphology on strength scaling properties at the mesoscale. These mesoscale model interactions should include the normal‐stress or pressure dependency that we observe.     

Deformation and fracture of PMMA at high rates of loading

The scope of this article is to study the influence of loading rates on the deformation and the fracture of PMMA. The dynamic loading was achieved by means of an impact three point bend device for intermediate strain rates and by using a split Hopkinson's tensile bar apparatus for higher rates of loading. Tensile properties (Young modulus, yield stress) and fracture toughness are determined in a wide range of loading rates and compared to the literature results. Scanning electron micrographs of the tensile fracture surfaces are presented to illustrate the dynamic effect on the crack propagation. © 1994 John Wiley & Sons, Inc.     

Intrinsic viscosity of polymer solutions at high shear rates

Although low-shear intrinsic viscosity is a well-accepted tool for polymer characterization, it often happens (particularly with increasing molecular weights) that it is easier to detect the high-shear (second) Newtonian viscosity η₂ rather than its low shear counterpart. It has also been predicted that because of a higher degree of order, due to disentanglement and orientation, high-shear viscosity data should simplify the prevailing correlations. The possibility of using high-shear viscometric data for polymer characterization was examined by determining intrinsic viscosities for several polyisobutylene samples through extrapolation of the high-shear ultimate viscosity numbers, UVN, to zero concentration: [η]₂ = lim UVN_{C → 0} = lim_{C → 0} (η₂–η_s)/η_sC where η_s is the viscosity of the pure solvent. Five samples of unfractionated polyisobutylene (molecular weights of 1.1 × 10⁶–6.6 × 10⁶) in toluene, kerosene, decalin, and gas oil at concentrations of 0.05–2.4 g./dl. were studied. Higher dilution was avoided because of the problem of onset of turbulence. The absence of shear degradation was ascertained by measuring low-shear intrinsic viscosity data before and after the polymer was exposed to high-shear conditions. The data show two types of behavior: for the lower molecular weight samples in the low-viscosity solvents the UVN decreases linearly with dilution, and for the higher molecular weights and higher solvent viscosities the UVN increases with high dilution, i.e., shows an upturn effect. The first type of data can be successfully correlated with appropriate molecular weights by using a typical Mark-Houwink equation. The exponents in these relationships are in the range of 0.28–0.64, increasing systematically with decrease of solvent viscosity and independent of the “goodness” of the latter. The data that show an upturn effect are not currently amenable to reliable extrapolation techniques. The upturn, however, predicts the conformation of very flexible, isolated polymer chains in viscous solvents under conditions of high shear.     

Creep characterization and modelling of ordinary refractory ceramics under combined compression and shear loading conditions

Creep behaviour of ordinary refractory ceramics is evidently asymmetric under uniaxial tension and compression. In service, they are often exposed to multiaxial stress states. In the present paper, the modified shear test specimens were applied for a creep study in the shear-compression zone of the p-q diagram, and the pure shear creep parameters following the Norton-Bailey strain hardening equation were inversely identified in combination with a weighting function between pure shear and uniaxial compressive conditions. The weighting function was implemented in an in-house asymmetric creep constitutive model. The experimental curves can be well predicted with identified parameters of the asymmetric creep constitutive model. It shows that the shear creep of ordinary refractory ceramics is evidently different to uniaxial compressive/tensile creep. Consideration of shear creep in the thermomechanical modelling of industrial vessels increases the accuracy of simulation results and supports the lining concept optimization investigation.     

DC conductivity and dielectric response in amorphous polycarbonate of Bisphenol-A

We report the dielectric response measurements of amorphous polycarbonate of Bisphenol-A at room temperature in the frequency range from 12 to 10⁵ Hz. The data is analyzed within the graphical representation of Wei and Sridhar. Such an approach has allowed us to estimate the DC conductivity value of the order of 5 × 10^?11 S/m in good agreement with the direct DC measurements.     

Structure and properties of ultra‐high molecular weight bisphenol a polycarbonate synthesized by solid‐state polymerization in amorphous microlayers

The structure and properties of ultrahigh molecular weight polycarbonate synthesized by solid‐state polymerization in micro‐layers (SSP_m) are reported. A low molecular weight prepolymer derived from the melt transesterification of bisphenol A and diphenyl carbonate as a starting material was polymerized to highly amorphous and transparent polycarbonate of molecular weight larger than 300,000 g mol^?1 in the micro‐layers of thickness from 50 nm to 20 µm. It was observed that when the polymerization time in micro‐layers was extended beyond conventional reaction time, insoluble polymer fraction increased up to 95%. Through the analysis of both soluble and insoluble polymer fractions of the high molecular weight polycarbonate by ¹H NMR spectroscopy and pyrolysis‐gas chromatography mass spectrometry (Py‐GC/MS), branches and partially crosslinked structures have been identified. The thermal, mechanical and rheological properties of the ultra‐high molecular weight nonlinear polycarbonates synthesized in this study have been measured by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and rheometry. The nonlinear chain structures of the polymer have been found to affect the polymer's thermal stability, mechanical strength, shear thinning effect, and elastic properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41609.     

The large strain compression,tension, and simple shear of polycarbonate

Polymeric materials subjected to large strains undergo an evolution in molecular orientation. The developing orientation and corresponding strengthening are highly dependent on the state of strain. In this paper, we examine and compare the very different stress-strain results of polycarbonate produced from four types of mechanical testing: uniaxial compression, plane strain compression, uniaxial tension, and simple shear. These tests produce different states of orientation within the material and, in the case of simple shear, the principle axes of orientation rotate during the deformation. The ability of the recent constitutive model of Arruda and Boyce (1992) to predict the to predict the observed behavior is evaluated. The model has been incoporated into a finite element code in order to properly simulate the material behavior during the inhomogenous deformations of tension (cold drawing) and simple shear. The material properties of the model are obtained from the uniaxial compression test and the model is then found to be truly predictive of the other states of deformation demonstrating its fully three dimensional capability. The disadvantages of the tensile and simple shear tests for obtaining the data needed to accurately quantify the large strain material behavior of polymers are shown and discussed.     

Confined compression of elastic adhesives at high rates of strain

Elastic adhesives are used in composite armours to bond the ceramic front face and the metallic backing plate. The mechanical behaviour of different elastic adhesives under impact loads have been studied by means of dynamic compression tests performed in a split Hopkinson pressure bar. In this experiments, the stress-strain curve of confined materials at high strain rates and the capability of transmitting and reflecting the impact energy have been determined. The influence of thickness and ageing on the response of the adhesive layer have been also considered.     

Stress-strain behaviour of concrete and mortar at high rates of tensile loading

The Split-Hopkinson-Bar technique was used in the investigation on tensile stress-strain behaviour of concrete and mortar at high stress rates (5–30 N/mm²ms).The single loading tests showed that the impact tensile strength was higher than the static one, and that impact strains at the maximum stress were larger than static strains.The impact fatique tensile tests indicated an increase of strains in the course of fatigue loading and increasing fatique life with decreasing maximum stress level.These phenomena are discussed with the aid of fracture mechanics concepts and explanations for differences in the behaviour of concrete and mortar are suggested.     

Model for tensile fracture of concrete at high rates of loading

Mechanisms of tensile fracture of concrete are described. A model is developed for an idealized material. The amount of simultaneous cracking and the path of each crack depend on the rate of stressing. The fracture energy and the tensile strength have been determined as functions of the rate of loading. The results of earlier experiments on concrete under impact tensile loading can be explained by this model.     

Uniaxial time‐dependent ratcheting behavior of bronze powder filled polytetrafluoroethylene at room and high temperature

A series of tensile and ratcheting experiments for cold compaction polytetrafluoroethylene (PTFE) and bronze filled PTFE (PTFE/bronze) were conducted with Dynamic Mechanical Analyzer (DMA‐Q800) at room and high temperature (473 K). The effects of peak stress‐holding time, creep, recovery, mean stress history, stress‐rate history, and pretension on the ratcheting behavior of PTFE/bronze were investigated. It is found that longer peak stress‐holding time leads to larger ratcheting strain accumulation. In the meantime, the ratcheting strain accumulates more rapidly at high temperature and the influence of temperature is more obvious than that of the additive fraction of bronze. Creep strain produced during the uploading and the stress‐holding time only partially recovers in the unloading process. Moreover, prior lower stress rate enhances the deformation resistance and restrains the ratcheting of subsequent cycling at higher stress rate. The ratcheting strain in the subsequent cyclic loading at lower mean stress is also restrained by previous cyclic loading at higher mean stress. Finally, the elastic modulus increases and the ratcheting strain is restrained apparently after the pretension. In addition, the elastic modulus and ratcheting strain of the PTFE/bronze with both pretension and recovery are smaller than those with pretension but without recovery. POLYM. ENG. SCI., 54:1571–1578, 2014. © 2013 Society of Plastics Engineers     

Mechanical response and rheological properties of polycarbonate layered‐silicate nanocomposites

The effect of clay loading on the mechanical behavior and melt state linear viscoelastic properties of intercalated polycarbonate (PC) nanocomposites was investigated. At low frequencies, the linear dynamic oscillatory moduli data revealed diminished frequency dependence with increasing nanoclay loading. The 3.5 and 5 wt% clay nanocomposites exhibited dramatically altered relaxation behavior, from liquid‐like to pseudo‐solid–like, compared to the pure PC and the 1.5 wt% clay nanocomposite. Thermal degradation of PC resulted from the melt compounding of organo‐modified nanoclays was evident from the reduction in the glass transition temperature and molecular weight of the PC nanocomposites. These nanocomposites also exhibited a significant decrease in the extent of tensile elongation and ductility with respect to the nanoclay incorporation. A concomitant decrease in the rheological properties at high frequencies was also observed, and was consistent with the lowering of the molecular weight of PC, particularly near or above the percolation threshold of nanoclay. These nanocomposites, nevertheless, exhibited elastic‐plastic deformation in compression, regardless of nanoclay content. Polym. Eng. Sci. 44:825–837, 2004. © 2004 Society of Plastics Engineers.     

Removal of monochlorobenzene from air in a trickling biofilter at high loading rates

BACKGROUND: In this study, the biofiltration of air streams laden with monochlorobenzene (MCB) vapours was investigated using a trickling biofilter operated co‐currently. The device was filled with ceramic material and inoculated with an acclimated microbial culture. A neutralization process was carried out in a separate unit using crushed oyster shells. Long‐term biofilter performance was evaluated over a 10‐month period of continuous experiments under different influent pollutant concentrations from 0.10 to 1.75 g m^?3, sequentially stepped up through three different apparent air residence times of 60, 30, and 15 s. RESULTS: Pollutant removal was shown to be complete at influent concentrations up to 1.25, 0.75 and 0.20 g m^?3, and apparent air residence times of 60, 30, and 15 s, respectively. The maximum elimination capacity was found to be 95.0 g m_PM^?3 h^?1 for an influent concentration of 1.0 g m^?3 and an apparent air residence time of 30 s, corresponding to a loading rate of 120.0 g m_PM^?3 h^?1. Monochlorobenzene and biomass concentration profiles along the biofilter evidenced the dependence of microbial concentration distribution on the pollutant loading rate and the existence of a linear relationship between biomass concentration and specific pollutant removal rate, regardless of the operating conditions applied. A macrokinetic analysis shows that the MCB removal rate is zeroth order for low values of MCB concentration. A critical value of MCB concentration exists at all superficial air velocity at which the biomass growth is inhibited. A simple kinetic model is developed which is able to describe the inhibition behaviour under any operating conditions. CONCLUSION: The experimental results indicated that the system was effective and stable under various working conditions and over a long operating period, provided that the loading conditions corresponding to substrate inhibition of microbial growth are not exceeded. Copyright © 2012 Society of Chemical Industry     

Mechanical and acoustic performance of compression‐molded open‐cell polypropylene foams

Open‐cell materials are lightweight and multifunctional capable of absorbing acoustic energy and supporting mechanical load. The acoustic and mechanical performance of open‐cell materials can be optimized through processing. In this article, the relationships between processing parameters and acoustic and mechanical performance are shown for polypropylene (PP) foams. PP foam samples are fabricated using a combined compression molding and particulate leaching process. The results from a parametric study showed that both salt size and salt to polymer ratio affect the acoustic and mechanical performance of open‐cell PP foams. As salt size increases, cell size increased and cell density decreased. The salt to polymer ratio had opposite affect on cell density, and increasing the salt to polymer mass ratio increased the open‐cell content. The airflow resistivity decreased significantly by increasing the cell size, which means that foam samples with smaller cell size have better sound absorption. When foam samples were thin, smaller cell sizes produced better sound absorption; however, as thickness of the sample increases, medium cell size offered the best acoustic performance. The compressive strength of the foams was increased by increasing the relative density. Acoustic performance results from the parametric study were compared to the Johnson‐Allard model with good agreement. Finally, optimal cellular morphologies for acoustic absorption and mechanical performance were identified. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Compressive response of PMMA microcellular foams at low and high strain rates

Microcellular foams are widely applied in various applications in both civil and military applications for barriers and energy absorption materials. Poly(methyl methacrylate) microcellular foams were fabricated via supercritical foaming method. Field emission scanning electron microscopy, differential scanning calorimetry, and mechanical test machine were used to visualize the foam structure and test the quasi‐static compression properties. Moreover, Split Hopkinson Bar (SHPB) setups were adopted to explore the dynamic compression properties. The experimental results show that the microcellular foams have homogeneous cell size distribution and exhibit superior compressive behavior at both quasi‐static and high strain rates. The mechanical properties depend on both foam density and strain rate. Strain rate effects are clearly observed. At quasi‐static strain rate and 7500 S^?1 regime, cell wall bucking and folding are the main failure mechanism. However, at high strain rate regime, softening phenomenon is observed. By roughly calculating the energy absorbed and the temperature rise, the temperature of the foams will rise up to as high as 130 °C after conducting high strain rate compression, and it is postulated that the generated heat will destroy the cell structure of the foams. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46044.     

Measurement of intrinsic rates for homogeneous gas‐phase reactions at high temperatures

A coiled quartz tubular reactor has been designed to measure the intrinsic reaction kinetics for homogeneous reactions at high temperatures up to 1100°C. Actual gas residence times were less than 100 ms. A simple and well‐studied test reaction (i.e., the decomposition of nitrous oxide, N₂O), with published intrinsic kinetics, was used to verify the operation of the experimental reactor. For this system, Peclet numbers (Pe = uL/DL) computed from experimental conversion data were greater than 1000, indicating that the plug flow assumption could be used with this reactor system to determine intrinsic rate expressions with errors of less than 5% for the conditions studied.     

Birefringence in injection‐compression molding of amorphous polymers: Simulation and experiment

The influence of the processing variables on the residual birefringence was analyzed for polystyrene and polycarbonate disks obtained by injection‐compression molding under various processing conditions. The processing variables studied were melt and mold temperatures, compression stroke, and switchover time. The modeling of flow‐induced residual stresses and birefringence of amorphous polymers in injection‐compression molded center‐gated disks was carried out using a numerical scheme based on a hybrid finite element/finite difference/control volume method. A nonlinear viscoelastic constitutive equation and stress‐optical rule were used to model frozen‐in flow stresses in moldings. The filling, compression, packing, and cooling stages were considered. Thermally‐induced residual birefringence was calculated using the linear viscoelastic and photoviscoelastic constitutive equations combined with the first‐order rate equation for volume relaxation and the master curves for the Young's relaxation modulus and strain‐optical coefficient functions. The residual birefringence in injection‐compression moldings was measured. The effects of various processing conditions on the measured and simulated birefringence distribution Δn and average transverse birefringence <n_rr?n_θθ> were elucidated. Comparison of the birefringence in disks manufactured by the injection molding and injection‐compression molding was made. The predicted and measured birefringence is found to be in fair agreement. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Thermal and mechanical properties of compression‐molded pMDI‐reinforced PCL/gluten composites

Many biopolymers and synthetic polymers composites were developed by different researchers for environmental protection and for cost reduction. One of these composites is polycaprolactone (PCL) and vital wheat gluten or wheat flour composites were prepared and compatibilized with polymeric diphenylmethane diisocyanate (pMDI) by blending and compression‐molding. PCL/pMDI blend exhibited glass transition (T_g) at ?67°C (0.20 J/g/°C) and vital gluten at 63°C (0.45 J/g/°C), whereas no T_g was recorded for wheat flour. Although T_g was unmistakable for either PCL or gluten, all composite exhibited one T_g, which is strong indication of interaction between PCL and the fillers. Several samples amongst the blended or compression‐molded composites exhibited no T_g signifying another confirmation of interaction. The ΔH of the endothermic (melting) and the exothermic (crystallization) for PCL was decreased as the percentage of gluten or flour increased, whereas the overall ΔH was higher for all composites compared to the theoretical value. The presence of pMDI appeared to strengthen the mechanical properties of the composites by mostly interacting with the filler (gluten or flour) and not as much with PCL. The FTIR analysis ruled out covalent interaction between PCL, pMDI, or the fillers but suggested the occurrence of physical interactions. Based on the data presented here and the data published earlier, the presence of pMDI did not change the nature of interaction between PCL and gluten, but it improved the mechanical properties of the composite. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Interfacial properties of polycarbonate/liquid‐crystal polymer and polystyrene/high‐impact polystyrene polymer pairs under shear deformation

We developed an energy model derived from the first principle for multilayer configurations to enhance our understanding of the interfacial property between two polymers under shear deformation. We carried out specific experiments satisfying the boundary and loading conditions of the model to obtain the energy dissipation factor (β), which characterized and quantified the interfacial property. Two polymer pairs, the miscible system polystyrene (PS)/high‐impact polystyrene (HIPS) and the immiscible system polycarbonate (PC)/liquid‐crystal polymer (LCP), were investigated. As expected, β was zero for PS/HIPS, reflecting the strong interaction at the PS/HIPS interface. For PC/LCP, the value of β could be significant, and its behavior was complex; it reflected the thermal sensitivity and thermal history effect of the PC/LCP interface. A positive value of β also indicated the possibility of slip at the interface and provided an explanation for the negative deviation from the rule of mixture. This complex behavior of the interface was attributed to the changes in the phases and microstructure of LCPs and, therefore, the LCP/PC interface as thermal cycling was carried out in the melting/nematic range of LCPs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 258–269, 2003