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61.
Solid-state 13C NMR was utilized in analysis of the crosslink structure in silica-filled polyisoprene. Samples containing either a pre-coated coupling agent, a coupling agent added in the mixing process, or polyethylene glycol (PEG) were vulcanized and the type and density of crosslinking determined. The precoated coupling agent sample gave lower %swelling, lower extraction amounts, and a lower T 2 relaxation than the mixed coupling agent, indicating increased crosslinking or increased filler –rubber interaction. The precoated also showed less cis –trans isomerization than the mixed, which may be due to its more uniform coating effect on the silica. The PEG sample yielded a 13C spectrum similar to an unfilled sample indicating decreased silica adsorption of vulcanization agents. Neither coupling agent significantly decreased the total sulfurization nor the percent monosulfidic crosslinks from that of a silica-filled sample without coupling agent. 相似文献
62.
Sarah Forrest John Bridgwater Paul R. Mort James Litster David J. Parker 《Powder Technology》2003,130(1-3):91-96
Particle flow patterns were investigated for wet granulation and dry powder mixing in ploughshare mixers using Positron Emission Particle Tracking (PEPT). In a 4-l mixer, calcium carbonate with mean size 45 μm was granulated using a 50 wt.% solution of glycerol and water as binding fluid, and particle movement was followed using a 600-μm calcium hydroxy-phosphate tracer particle. In a 20-l mixer, dry powder flow was studied using a 600-μm resin bead tracer particle to simulate the bulk polypropylene powder with mean size 600 μm. Important differences were seen between particle flow patterns for wet and dry systems. Particle speed relative to blade speed was lower in the wet system than in the dry system, with the ratios of average particle speed to blade tip speed for all experiments in the range 0.01–0.25. In the axial plane, the same particle motion was observed around each blade; this provides a significant advance for modelling flow in ploughshare mixers. For the future, a detailed understanding of the local velocity, acceleration and density variations around a plough blade will reveal the effects of flow patterns in granulating systems on the resultant distribution of granular product attributes such as size, density and strength. 相似文献
63.
H.P. Kuo P.C. KnightD.J. Parker A.S. BurbidgeM.J. Adams J.P.K. Seville 《Powder Technology》2003,132(1):1-9
The motion of sand particles close to a single moving blade was investigated using Positron Emission Particle Tracking (PEPT) during the period in which the free bed surface profile was evolving to an equilibrium shape. The area affected by the blade was divided into active and inactive regions and these were analysed separately. The characteristic heart-shape of the active region in the plan view was determined. An approximately 10-particle-diameter wide velocity transition zone is found between the two regions. While the tracer particle is in the inactive region moving away from the blade, the time dependence of the axial displacement is well described by a logarithmic relationship. The probability of particle movement towards the centre of the blade was quantified using a “central tendency” index. The calculated central tendency shows maxima at each side of the blade. The separation of the two maxima, which indicates the width of the active region, increases with fill level but is independent of rotational speed. 相似文献
64.
Multiple fractal dimensions are used to characterize morphological changes that occur when an aerosol composed of irregularly shaped agglomerates is subject to condensation followed by evaporation. The agglomerates change from a branched, chainlike structure to a more regular, near-spherical or clumplike structure reflected in a decrease in the structural fractal dimension. The textural fractal dimension remains constant because the primary particles, of which the agglomerates are composed, do not change in shape. The degree of supersaturation and the number of condensation-evaporation cycles that the aerosol undergoes are major factors that influence morphological change. Even at low supersaturations, increasing the number of condensation-evaporation cycles makes the agglomerates more regular and thus decreases the structural fractal dimension. The transition point in the Richardson plot is a good indicator of the size of the primary particles in the agglomerate. 相似文献
65.
Gizem Ozbuyukkaya Robert S. Parker Goetz Veser 《American Institute of Chemical Engineers》2022,68(3):e17538
Accurate chemical kinetics are essential for reactor design and operation. However, despite recent advances in “big data” approaches, availability of kinetic data is often limited in industrial practice. Herein, we present a comparative proof-of-concept study for kinetic parameter estimation from limited data. Cross-validation (CV) is implemented to nonlinear least-squares (LS) fitting and evaluated against Markov chain Monte Carlo (MCMC) and genetic algorithm (GA) routines using synthetic data generated from a simple model reaction. As expected, conventional LS is fastest but least accurate in predicting true kinetics. MCMC and GA are effective for larger data sets but tend to overfit to noise for limited data. LS-CV strongly outperforms these methods at much reduced computational cost, especially for significant noise. Our findings suggest that implementation of CV with conventional regression provides an efficient approach to kinetic parameter estimation with high accuracy, robustness against noise, and only minimal increase in complexity. 相似文献
66.
A technique of Positron Emission Particle Tracking (PEPT) was used to obtain information on the flow behavior of coarse particles suspended in pseudoplastic liquids agitated by axial‐hydrofoil Lightnin impellers A320 and A410. PEPT enables the position of a 600 μm radioactive particle tracer inserted inside one of the suspended particles to be detected many times per second and its full trajectory followed inside the vessel. Particle trajectory analysis yielded information on particle circulation, velocity distribution, and spatial occupancy. The minimum speed for complete particle suspension, Njs, was also determined. The well‐known Zwietering correlation failed to predict the measurements by a substantial margin, suggesting that it is inadequate for viscous non‐Newtonian liquids. 相似文献
67.
Correlations between the macroscopic bulk polymer properties storage modulus (E′) and loss modulus (E″) and the microscopic property of cross-polarization as represented by the time constant TCH have been established for a series of polyurethane elastomers. The dependence of E′, E″, and TCH as a function of molecular weight, rigid domain concentration, and temperature are graphically presented as a series of log plots. An experimental relationship is presented that shows that the distribution of motions of the flexible domains appears to be the major factor in the success of these correlations. 相似文献
68.
Samples of plasticized poly(vinyl butyral-co-vinyl alcohol) (PVB) are found to exhibit multiple thermal transitions as observed by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). Arrhenius plots using DSC and DMA data suggest that two of the transitions are glass-type ones. Variable temperature solid-state 13C-NMR experiments show a temperature-dependent line-broadening pattern for all PVB backbone carbons with maximum broadening at 55°C or at about 50°C above the second-order-type transitions α1 and α2 as measured by DSC. Using Arrhenius plots, the NMR transition is found to best correlate with α1, which is consistent with glass transition behavior. The solid-state NMR spectra also show that vinyl alcohol tacticity remains unresolved up to a temperature of about 95°C, beyond which line narrowing begins to occur. High-temperature thermal transitions are also observed by DSC and DMA, which suggest that the onset of motion involving vinyl alcohol sequences may be responsible for these transitions. 相似文献
69.
Chang Ming Fang Gijsbertus de With Stephen C. Parker 《Journal of the American Ceramic Society》2001,84(7):1553-1558
Atomistic simulation techniques have been used to model the dissociative adsorption of water onto the low-index {100}, {110}, and {111} surfaces of spinel MgAl2 O4 . The Born model of solids and the shell model for oxygen polarization have been used. The resulting structures and chemical bonding on the clean and hydrated surfaces are described. The calculations show that the dissociative adsorption of water on the low-index surfaces is generally energetically favorable. For the {110} and {111} orientations, the surfaces cleaved between oxygen layers show high absorption and stability. The calculations also show that, for the {111} orientation, the surfaces may absorb chemically water molecules up to ∼90% coverage and have the highest stability. It is suggested that, during fracture, only partial hydration occurs, leading to cleavage preferentially along the {100} orientation. 相似文献
70.
Xiaobo Dong Halle D. Shannon Caleb Parker Samantha De Jesus Isabel C. Escobar 《American Institute of Chemical Engineers》2020,66(1):e16790
Petroleum-derived solvents commonly used in membrane fabrication are often hazardous and toxic, so the investigation of safer alternatives is important. In this study, two low-hazard solvents, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate (Rhodiasolv® PolarClean) and gamma-valerolactone (GVL), were investigated as sole solvents and as cosolvents to cast polysulfone membranes via nonsolvent induced phase inversion. Normalized viscosity was introduced as an indicator of dope solution homogeneity and was used to compare the required time of mixing to achieve full dissolution of the polymer in the different solvents/solvent mixtures. All dope solutions made with low-hazard solvents were found to be more viscous than those made with traditional solvents, which meant additional mixing time was needed, and that fabricated membranes were morphologically different. With respect to operation, membranes cast from dope solutions containing equal amounts of PolarClean and GVL displayed the most similar flux curves and solute rejection to those made using the traditional solvent tested. 相似文献