Simulation of continuous solid‐phase polymerization of nylon 6,6. III. Simplified model

Solid‐phase polymerization (SPP) reactors are used to increase the degree of polymerization (DP) during nylon 6,6 production. In previous articles, a reactor model with partial differential equations (PDEs) in time and two spatial dimensions was developed to describe dynamic changes in polymer property profiles (DP, temperature, and moisture content) over the height of the reactor and within the polymer particles. In the current article, a simplified model is developed by deriving appropriate expressions for heat‐ and mass‐transfer coefficients and performing a lumped heat‐ and mass‐transfer analysis. Using this approach, the radial dimension is removed from the PDEs, so that the effort required to solve the model equations is substantially reduced. Predictions of the complex and simplified models are compared through simulation of two different start‐up processes. Good agreement between simplified and complex models is obtained, indicating that the simplified model can be used in place of the complex model if the polymer properties profiles within individual particles are not of particular concern to the model user. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3701–3712, 2003     

Collaborative test of determination of iodine value in fish oils. 1. Reaction time and carbon tetrachloride or cyclohexane as solvents

Twenty-two laboratories participated in a collaborative test to determine the iodine value (IV) of eight samples of fish oil (four with IV<150, four with IV>150) with either carbon tetrachloride (AOCS Official Method Cd 1–25) or cyclohexane (AOCS Recommended Practice Cd 1b-87) as solvent and either 1 or 2 h of reaction time. Laboratories received coded duplicate samples (hidden duplicates) and carried out duplicate determinations on each oil by each solvent-time combination (open duplicates). Replacing carbon tetrachloride with cyclohexane resulted in a lower IV (P<0.001). The decrease averaged 1.6 IV units for low-IV oils and 3.8 IV units for high-IV oils; this difference in response of 2.2 IV units between low- and high-IV oils was significant (P<0.001). Increasing the reaction time had a relatively small effect (0.34±0.18). There was no interaction of reaction time with solvent or oil type. Cyclohexane caused emulsions, which made it difficult to titrate residual iodine and thus increased the variability of the determination. The repeatability standard deviations (s _r ), based on hidden duplicates, for 1-h reaction time with carbon tetrachloride and cyclohexane were 2.17 and 3.35, respectively. The corresponding reproducibility standard deviations were 2.73 and 4.53.     

High Throughput Screening of Low Temperature SCR and SCD De-NOx Catalysts in Scanning Mass Spectrometer

High-throughput synthesis and screening methods have been developed for the discovery of highly active lead compounds for the selective catalytic reduction as well as direct decomposition of NO in the temperature range 200–300 °C. The discovery libraries for primary screening consisted of 16 × 16 catalyst arrays on 4in. square quartz wafers. Catalysts were prepared by robotic liquid dispensing techniques and screened for catalytic activity in Symyx' scanning mass spectrometer. The scanning mass spectrometer is a fast serial screening tool that uses flat wafer catalyst surfaces, local laser heating, a scanning/sniffing nozzle and a quadrupolar mass spectrometer to compare relative catalytic activities. The feed consisted of NO/NH₃ mixtures with optional O₂ cofeed and Kr as the internal standard in Ar carrier gas. QMS detection allowed for tracking of H₂O, N₂, NO, O₂, N₂O and Kr. Screening protocols for catalytic materials encompassed metal precursors and carriers for supported vanadia systems, extensive doping of V₂O₅/TiO₂, and broad screening of mixed redox metal oxides and supported base and noble metal systems. More than 500 samples could be screened in a single day. Active hits (high NO consumption accompanied by corresponding N₂ production) identified in discovery libraries were re-synthesized as focus libraries for lead confirmation and further optimization. These libraries used shallower compositional gradients, for example 56 points (compositions) per ternary, with four 56-point ternaries per 4in. wafer. Broad screening ternaries were generally 8 or 15 points. The focus libraries more clearly reveal the trends and provide guidelines for secondary screening and scale-up. High conversions were achieved in scanning mass spectrometer so the scalability risk is small for the short contact time reactions.     

Uptake of blood triglyceride by various tissues

Triglycerides are transported in the blood in chylomicrons and very low density lipoproteins. Electron microscopic studies indicate that these particles, which range in diameter from 0.03–0.6 μ, cannot cross the capillary endothelium in most tissues. There is now considerable evidence that the triglycerides are hydrolyzed to free fatty acids (FFA) during uptake and that this process is catalyzed by lipoprotein lipase. The enzyme is found in nearly all tissues that utilize circulating triglyceride, and the level of activity, in individual tissues, varies with nutritional and physiological states that affect triglyceride uptake, such as fasting, diabetes and pregnancy. Studies in perfused adipose tissue with doubly labeled chylomicrons showed that hydrolysis occurs outside of the blood stream. Two-thirds of the fatty acids are incorporated into tissue triglyceride and the rest are release as FFA, with glycerol, to the blood. Infusion of heparin causes immediate release of lipoprotein lipase activity to the blood and decreases the amount of chylomicron-triglyceride hydrolyzed by the tissue. Electron microscopic cytochemical studies showed that hydrolysis of blood glycerides by lipoprotein lipase in adipose tissue occurs within the capillary endothelial cells and in the subendothelial space near the pericytes, but not in the capillary lumen or near the fat cells. The results indicate that the fatty acids of chylomicrons cross the capillary endothelium as glycerides and FFA, within a membrane-bounded system, and cross the extravascular space to the fat cells as FFA. Presented at the AOCS Meeting, Atlantic City, October 1971.     

Stress Analysis of Elastic-Plastic Contact Damage in Ceramic Coatings on Metal Substrates

An elastic-plastic analysis of damage in ceramic coatings on metal substrates from contacts with spherical indenters is made using finite element modeling. Computations are carried out specifically for plasma-sprayed alumina:titania on a soft steel. The algorithm assumes an elastic sphere with frictionless contact on a flat elastic-plastic layered specimen, and incrementally evaluates the expanding contact field as a function of applied load. Two key aspects of the contact field are examined: (i) the indentation stress-strain curve; (ii) the damage zone geometry. Composite coating/substrate indentation stress-strain curves are computed for two coating thicknesses, using input material parameters from iterative fits to data from control tests on free-standing coating and substrate materials. Contours of principal shear stresses, most notably those contours corresponding to yield zone boundaries in both the softer substrate and the harder coating, are mapped out in the fully plastic region. Corresponding distributions of tensile stresses are also mapped out, and are shown to correlate with the locations of transverse fractures in the coating. General implications concerning material and geometrical design of ceramic-based layer structures are discussed.     

The ageing Australian firefighter: an argument for age-based recruitment and fitness standards for urban fire services

Currently, there is no enforcement of physical standards within Australian fire services post-recruitment, possibly leading to inappropriate fitness and body composition. This study evaluated the impacts of ageing on physical standards of Australian firefighters. Seventy-three firefighters from three different 10-year age groups [25–34 years (n = 27), 35–44 years (n = 27), 45–54 years (n = 19)] volunteered for physical testing using dual-energy X-ray analysis and existing fitness tests used for recruitment by an Australian fire service. Older (45–54 years) participants demonstrated significantly poorer physical standards compared with younger participants including cardiovascular fitness (p < 0.05), strength (p = 0.001) and simulated operational power testing tasks (p < 0.001). Age-related body composition changes were also observed independent of body mass index. Minimum recruitment standards and fitness programs need to account for age-related declines in physical capabilities to ensure that the minimum standard is maintained regardless of age.

Practitioner Summary: Using dual-energy X-ray analysis and established fitness testing protocols, this study aimed to gain an appreciation of the current standards of body composition and fitness of Australian firefighters and the effects of ageing on their physical abilities post-recruitment. The study demonstrated a significant decline in physical standards due to age.     

Data-based adaptive online prediction model for plant-wide production indices

A data-based adaptive online prediction model is proposed for plant-wide production indices based on support vector regression, a general method which we customized specifically to model very large data sets that are generated dynamically and periodically. The proposed model can update its parameters online according to the statistical properties of the training samples. Further, in order to improve the prediction precision, each sample is weighted with a dynamic penalty factor that considers the effect of each sample on the prediction model accuracy. Moreover, a customized procedure is introduced to handle large training sets. After having been convincingly evaluated on benchmark data, effectiveness and performance of our approach for plant-wide production indices is demonstrated using industrial data from an operating ore dressing plant over a range of scale in training data set size. The higher accuracy and shorter computation times than existing methods suggest that it may prove advantageous in actual application to dynamic production processes.     

Perceiving,learning, and exploiting object affordances for autonomous pile manipulation

Autonomous manipulation in unstructured environments will enable a large variety of exciting and important applications. Despite its promise, autonomous manipulation remains largely unsolved. Even the most rudimentary manipulation task—such as removing objects from a pile—remains challenging for robots. We identify three major challenges that must be addressed to enable autonomous manipulation: object segmentation, action selection, and motion generation. These challenges become more pronounced when unknown man-made or natural objects are cluttered together in a pile. We present a system capable of manipulating unknown objects in such an environment. Our robot is tasked with clearing a table by removing objects from a pile and placing them into a bin. To that end, we address the three aforementioned challenges. Our robot perceives the environment with an RGB-D sensor, segmenting the pile into object hypotheses using non-parametric surface models. Our system then computes the affordances of each object, and selects the best affordance and its associated action to execute. Finally, our robot instantiates the proper compliant motion primitive to safely execute the desired action. For efficient and reliable action selection, we developed a framework for supervised learning of manipulation expertise. To verify the performance of our system, we conducted dozens of trials and report on several hours of experiments involving more than 1,500 interactions. The results show that our learning-based approach for pile manipulation outperforms a common sense heuristic as well as a random strategy, and is on par with human action selection.     

离子取代凝胶——ACA离子取代动力学模型

用动边界模型描述了海藻酸-壳聚糖-海藻酸(ACA)离子取代凝胶对2价离子的取代动力学过程.模型具有较好的可靠性，ACA离子取代凝胶对2价离子的取代属于颗粒扩散控制.ACA离子取代凝胶对Pb²⁺的反应级数是0.76.     

WALL AND PARTICLE-SHAPE EFFECTS ON HEAT TRANSFER IN PACKED BEDS

The effective radial thermal conductivity and apparent heat transfer coefficient for a packed bed were experimentally determined for beds of spheres, full cylinders and hollow cylinders, for flow rates giving particle Reynolds numbers in the range 100-1000, and for tube to particle diameter ratios of 5-12. Over these ranges the radial Peclet number Pe_r showed significant dependence on solid conductivity, gas flow rate and particle shape, while the wall Biot number Bi showed significant dependence on tube to particle diameter ratio, gas flow rate and particle shape. These dependencies were predicted well by equations incorporating the effects of these variables into individual gas and solid phase parameters, which were then combined to give the effective or lumped parameters