Phase behavior,density, and crystallization of polyethylene in n‐pentane and in n‐pentane/CO2 at high pressures

The phase behavior and volumetric properties of polyethylene (PE) in solutions of n‐pentane and n‐pentane/CO₂ were studied in a temperature (T) range of 370–440 K at pressures up to 60 MPa. Measurements were conducted with a variable‐volume view‐cell system equipped with optical sensors to monitor the changes in the transmitted light intensity as the P or the T of the system was changed. Lower‐critical‐solution‐temperature‐type behavior was observed for all of the liquid–liquid (L–L) phase boundaries, which shifted to higher pressures in solutions containing CO₂. The solid–fluid (S–F) phase boundaries were investigated over a P range of 8–54 MPa and took place in a narrow T range, from 374 to 378 K in this P interval. The S–F phase boundary showed a unique feature in that the demixing temperatures showed both increasing and decreasing trends with P depending on the P range. This was observed in both the PE/n‐pentane and PE/n‐pentane/CO₂ mixtures. The density of these solutions were measured as a function of P at selected temperatures or as a function of T at selected pressures that corresponded to the paths followed in approaching the phase boundaries (S–F or L–L) starting from a homogeneous one‐phase condition. The data showed a smooth variation of the overall mixture density along these paths. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2201–2209, 2003     

KINETICS FOR LOW TEMPERATURE PYROLYSIS OF BLACK LIQUOR

A kinetic study of pyrolysis of dried black liquor was performed using a Netzsch 429 Thermogravimetric Analyzer. It was found that as conversion increases from 10 to 45% the apparent pyrolysis activation energy for black liquor increases from 77.20 to 112.74 KJ/mol. For black liquor the order of reaction was found to be first-order. The reaction rate constant was found to be 2.12×10⁹ min. These results are in agreement with the data reported by other investigators on biomass pyrolysis.     

Morphological changes in poly(?-caprolactone) in dense carbon dioxide

Morphological changes that take place in poly(?-caprolactone) upon exposure to carbon dioxide at high pressures have been explored as a function of pressure and temperature. SEM and DSC results point to a competition between CO₂-modulated crystallization and pressure-induced phase separation which leads to unique morphologies. At 293 K, exposure to CO₂ at pressures up to 45 MPa leads to recrystallization resulting in higher level of crystallinity and higher melting temperatures. Highest crystallinity levels along with distinct crystal morphology were observed after exposure to CO₂ at 308 K and 21 MPa. At a higher pressure at this temperature (308 K/34 MPa) polymer undergoes melting, and foaming is achieved during depressurization prior to solidification. At 323 K, the polymer is found to display unique crystal morphology with concave crystal geometry as well as porous domains. The results are discussed in terms of the crystallization and phase separation paths that are followed during exposure to CO₂ and the depressurization stages.     

Solubility of polyethylene in n-pentane at high pressures

The high pressure solubility of polyethylene standards (M_w = 2100, 16400, 108000 and 420000 and M_w/M_n = 1.14, 1.16, 1.32 and 2.66, respectively) in n-pentane has been studied. Concentrations of up to 15 wt% polymer have been investigated. For each polymer sample and concentration, pressures that are required to achieve single-phase solutions have been determined over a range of temperatures. The solutions are found to all show lower critical solution temperatures. Demixing pressures are observed to depend strongly on the molecular weight of the polymer.     

Phase behavior and density of polysulfone in binary fluid mixtures of tetrahydrofuran and carbon dioxide under high pressure: Miscibility windows

Mixtures of tetrahydrofuran (THF) and carbon dioxide (CO₂) were identified as new solvent systems for polysulfone. The miscibility and density of polysulfone in binary fluid mixtures of THF and CO₂ were investigated from 300 to 425 K at pressures up to 70 MPa. The influence of the CO₂ and polysulfone concentrations was studied, with the concentrations of the other two components kept constant. At a 4.5 wt % polymer concentration, the demixing pressures in a 10 wt % CO₂ and 90 wt % THF mixture increased with temperature (310–425 K) from 15 to 40 MPa. With increasing CO₂ concentration (from ca. 10 to 14 wt %), a significant increase (from 15 to 70 MPa at 310 K) was observed in the demixing pressures. Furthermore, with an increasing amount of CO₂, the nature of the phase boundary shifted from lower critical solution temperature behavior to upper critical solution temperature behavior. The influence of the polymer concentration was studied in the 0–5 wt % range at two CO₂ levels, with solvent compositions of 10 wt % CO₂ and 90 wt % THF and 13 wt % CO₂ and 87 wt % THF. The system with a higher level of CO₂ (13 wt %) showed highly unusual phase behavior: on pressure–composition and temperature–composition diagrams, the system displayed two distinct regions of miscibility. In the system with 10 wt % CO₂, the distinct regions of miscibility that were observed in the system with 13 wt % CO₂ partially overlapped and led to a W‐shape phase boundary. The densities of the polymer solutions were measured from the one‐phase region through the demixing point into the two‐phase region at a constant temperature. No significant change in density was found around the phase boundary; this indicated that the coexisting phases had similar densities, as is often the case with liquid–liquid phase separation in polymer solutions under high pressure. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2357–2362, 2002     

Confined batch foaming of semi-crystalline rubbery elastomers with carbon dioxide using a mold

Confined foaming of poly(ethylene-co-vinyl acetate-co-carbon monoxide) using carbon dioxide as a physical blowing agent in a mold with either permeable or impermeable boundaries has been explored as a strategy to control final foam dimensions and morphology. The results are discussed in terms of comparisons to free-foaming experiments conducted at the same pressure and temperature conditions following the same pressurization and depressurization paths. Foaming experiments were carried out at 30 and 40°C and 100, 200, and 300 bar followed by rapid depressurization of the foaming cell. Confined foaming led to smaller pores with more uniform distributions across the polymer cross-section. However, bulk foam densities of the foams generated under confinement were higher than those generated under the free-foaming mode. Surface characteristics and skin layer formation were altered by expansion against both the permeable and impermeable boundaries. Confined foaming promotes uniform pore distribution and overall dimensional uniformity and may impart surface texture but the trade-off is in the degree to which the bulk foam density can be lowered.     

Adaptive three-dimensional cellular genetic algorithm for balancing exploration and exploitation processes

This paper presents a new adaptive algorithm that aims to control the exploration/exploitation trade-off dynamically. The algorithm is designed based on three-dimensional cellular genetic algorithms (3D-cGAs). In this study, our methodology is based on the change in the global selection pressure induced by dynamic tuning of the local selection rate. The parameter tuning of the local selection method is a way to define the global selection pressure. A diversity speed measure is used to guide the algorithm. Therefore, the integration of existing techniques helps in achieving our aims. A benchmark of well-known continuous test functions and real world problems was selected to investigate the effectiveness of the algorithm proposed. In addition, we provide a comparison between the proposed algorithm and other static and dynamic algorithms in order to study the different effects on the performance of the algorithms. Overall, the results show that the proposed algorithm provides the most desirable performance in terms of efficiency, efficacy, and speed for most problems considered. The results also confirm that problems of various characteristics require different selection pressures, which are difficult to be identified.     

Assessment of the effectiveness of the educational environment supported by computer aided presentations at primary school level

The objective of this study is to assess the effectiveness of the educational environment supported by computer aided presentations at primary school. The effectiveness of the environment has been evaluated in terms of students’ learning and remembering what they have learnt. In the study, we have compared experimental group and control group in terms of learning and recalling what has been learned regarding the effect which computer aided learning environment imposes. Data have been collected through the control grouped pretest–final test model. During the experiment, we have prepared an achievement test, which explains behaviors the students should acquire. According to the findings obtained, a computer aided educational environment has been observed to be more effective than that of conventional education in terms of learning. However, in terms of the permanence of what has been learned, no meaningful difference between the educational environment supported by computer aided presentations and that of conventional education has come out. According to the results of the follow-up tests performed, even though students in the test group have forgotten more of what they have learnt, it has been concluded that students in both groups have forgotten on the same level. Consequently, it has been observed that though the educational environment supported by computer aided presentations has positive contributions to learning activity, it does not have effects on the permanence of what has been learnt.     

Routing table updating by using intelligent agents

In a network, one of the important problems is making an efficient routing decision. Many studies have been carried out on making a decision and several routing algorithms have been developed. In a network environment, every node has a routing table and these routing tables are used for making routing decisions. Nowadays, intelligent agents are used to make routing decisions. Intelligent agents have been inspired by social insects such as ants. One of the intelligent agent types is self a cloning ant. In this study, a self cloning ant colony approach is used. Self cloning ants are a new synthetic ant type. This ant assesses the situation and multiplies through cloning or destroying itself. It is done by making a routing decision and finding the optimal path. This study explains routing table updating by using the self cloning ant colony approach. In a real net, this approach has been used and routing tables have been created and updated for every node.