An intrinsic time to fracture criterion for amorphous polymers

An energy probability theory of global fracture is formulated using the notion of intrinsic time starting with first principles. Comparisons are made between the theory and experiments on Styrene-Butadiene Rubber, thus explaining various aspects of failure.It is proposed that fracture occurs as a result of accumulation of broken carbon-carbon bonds. When a critical concentration of broken bonds is reached, catastrophic failure begins and the specimen fractures. It is assumed that the probability of fracture of a single carbon-carbon bond is determined by the energy content of the bond. Non-uniform distribution of the free energy of the specimen among bonds is taken into account by means of an exponential distribution function. The intrinsic time measure pertinent to the constitutive equation of the material is used as the time measure of fracture. This allows use of the time-temperature shift principle, applicable to fracture of polymers, and enables the prediction of lifetimes in high strain rate conditions.Finally the theory predicts correctly that, at constant amplitudes, the number of cycles to failure at low frequencies is directly proportional to the frequency and is independent of the latter at high frequencies.     

Preparation and characterization of low density polyethylene/ethylene methyl acrylate glycidyl methacrylate/organoclay nanocomposites

The effects of organoclay type, compatibilizer, and the addition order of components during melt‐blending process on the morphology and thermal, mechanical, and flow properties of ternary nanocomposites based on low‐density polyethylene (LDPE) were investigated. As a compatibilizer, ethylene/methyl acrylate/glycidyl methacrylate (E‐MA‐GMA), as organoclays Cloisites® 15A, 25A, and 30B were used. All samples were prepared by a corotating twin screw extruder, followed by injection molding. The highest increase of the basal spacing for ternary nanocomposites was obtained in LDPE/E‐MA‐GMA/Cloisite® 30B nanocomposites with interlayer spacing of 59.2 Å. Organoclay and compatibilizer addition did not influence the melting/crystallization behavior of the compositions, and both compatibilizer and organoclays had no significant nucleation activity in LDPE. Among the ternary nanocomposites, the maximum increase in tensile strength and tensile modulus values was observed for nanocomposites containing organoclay Cloisite® 15A. The improvement with respect to neat LDPE was 43% for tensile strength and 44% for tensile modulus. According to the mechanical analysis, the best sequence of component addition was the one in which LDPE, organoclay, and compatibilizer were simultaneously fed to the extruder in the first run, and the product of the first run was extruded once more. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dynamic risk analysis using alarm databases to improve process safety and product quality: Part I—Data compaction

In most industrial processes, vast amounts of data are recorded through their distributed control systems (DCSs) and emergency shutdown (ESD) systems. This two‐part article presents a dynamic risk analysis methodology that uses alarm databases to improve process safety and product quality. The methodology consists of three steps: (i) tracking of abnormal events over an extended period of time, (ii) event‐tree and set‐theoretic formulations to compact the abnormal‐event data, and (iii) Bayesian analysis to calculate the likelihood of the occurrence of incidents. Steps (i) and (ii) are presented in Part I and step (iii) in Part II. The event‐trees and set‐theoretic formulations allow compaction of massive numbers (millions) of abnormal events. For each abnormal event, associated with a process or quality variable, its path through the safety or quality systems designed to return its variable to the normal operation range is recorded. Event trees are prepared to record the successes and failures of each safety or quality system as it acts on each abnormal event. Over several months of operation, on the order of 10⁶ paths through event trees are stored. The new set‐theoretic structure condenses the paths to a single compact data record, leading to significant improvement in the efficiency of the probabilistic calculations and permitting Bayesian analysis of large alarm databases in real time. As a case study, steps (i) and (ii) are applied to an industrial, fluidized‐catalytic‐cracker. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Application of Bismuth(III)-Entrapped XO Biosensing System for Xanthine Determination in Beverages

A xanthine biosensor was prepared by electrochemical immobilization of xanthine oxidize enzyme onto carbon paste electrode via entrapment of Bi³⁺. After the optimization of experimental parameters, analytical characteristics were investigated. Two linear ranges between 0.02 and 0.06 and 1–7.5 μM with the equation y?=?93.00x?+?0.12 and y?=?1.07x?+?18.03 with the correlation coefficients of R ²?=?0.9951 and R ²?=?0.9931, respectively, were obtained for this biosensing system. RSD value was calculated for 0.04 μM xanthine (n?=?5) and found as 3.84%. LOD and LOQ values were also calculated and revealed as 1.30?×?10^?8 and 4.3?×?10^?8 M, respectively. Then, this biosensor was applied for xanthine detection in real samples. As a sample treatment, only necessary dilutions were made. Four types of beverages including wine, energy drink, peach, and sour cherry juice were used for this purpose. Obtained recovery values demonstrate that this system is applicable for xanthine detection in real samples without needing any laborious sample pretreatment procedures.     

Membrane based strategies for the pre-treatment of acid dye bath wastewaters

This paper, as part of a study carried out for the recovery of the acid dye bath wastewaters of a carpet manufacturing industry by membrane processes, describes the evaluation of alternative strategies for the pre-treatment of acid dye bath wastewaters. Dead-end microfiltration (MF) simulating sand filtration with MF media having pore sizes of 2.5, 1.0, 0.45 and 0.2 microm and ultrafiltration (UF) with an UF membrane having a molecular weight cut off (MWCO) of 50,000 Da were tested in single and sequential stages in order to achieve the best treatment efficiency. Four alternative process trains were tested; single MF, sequential MF, single UF, and MF followed by UF. For both MF and UF, application of sequential filtration did not provide any significant benefit over single processes. In addition, chemical oxygen demand (COD) removal performance of all the alternative processes was similar where the highest removal was only 5%. On the other hand, color removals were much better; ranging from 15 to 100%, even with single MF. Comparison of all the process alternatives revealed that, single MF (0.45 microm), as the simplest process, is the most suitable pre-treatment method for the acid dye bath wastewaters.     

Reactive extrusion of poly(ethylene terephthalate)–(ethylene/methyl acrylate/glycidyl methacrylate)–organoclay nanocomposites

This study was conducted to investigate the effects of component concentrations and addition order of the components on the final properties of ternary nanocomposites composed of poly(ethylene terephthalate), organoclay, and an ethylene–methyl acrylate–glycidyl methacrylate (E‐MA‐GMA) terpolymer acting as an impact modifier for PET. In this context, first, the optimum amount of the impact modifier was determined by melt compounding binary PET‐terpolymer blends in a corotating twin‐screw extruder. The amount of the impact modifier (5 wt%) resulting in the highest Young's modulus and moderate elongation at break was selected owing to its balanced mechanical properties. Thereafter, by using 5 wt% terpolymer content, the effects of organically modified clay concentration and addition order of the components on the properties of ternary nanocomposites were systematically investigated. Mechanical testing revealed that different addition orders of the materials significantly affected the mechanical properties. Among the investigated addition orders, the best sequence of component addition (PI‐C) was the one in which poly(ethylene terephthalate) was first compounded with E‐MA‐GMA. Later, this mixture was compounded with the organoclay in the subsequent run. In X‐ray diffraction analysis, extensive layer separation associated with delamination of the original clay structure occurred in PI‐C and CI‐P (Clay + Impact Modifier followed by PET) sequences with both 1 and 3 wt% clay contents. X‐ray diffraction patterns showed that at these conditions exfoliated structures resulted as indicated by the disappearance of any peaks due to the diffraction within the consecutive clay layers. POLYM. COMPOS., 28:251–258, 2007. © Society of Plastic Engineers     

Viscoelastic characteristics of chain extended/branched and linear polyethylene terephthalate resins

Two chemically modified chain extended/branched polyethylene terephthalate (PET) resins and one unmodified resin, considered to be linear, were characterized in terms of their melt flow, die swell, and viscoelastic properties. The three resins had reportedly similar nominal intrinsic viscosities but exhibited different viscoelastic behavior. The modified resins had lower melt flow index, higher die swell, higher complex viscosity and higher storage modulus than the unmodified one. The Cole–Cole plots of the resins were independent of temperature, and the data for modified resins formed a group that lay below the data group for the unmodified PET. The distribution of relaxation times was determined. The modified resins had higher relaxation strength, G_i, especially at high relaxation times, λ_i. The mean relaxation times of the chain extended/branched resins were approximately an order of magnitude higher than that of the unmodified resin, implying pronounced elastic character. The modified resins had better foaming characteristics in extrusion foam processing than the unmodified one owing to their elastic nature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1371–1377, 2000     

Mechanical behavior and dilatation of particulate-filled thermosets in the glassy state

Dilatation of specimens is measured during tensile tests to investigate the mechanical response of particulate-filled amorphous networks in the glassy state. The effects of particle size, volume fraction of filler, coupling agents, and crosslink density of the matrix on the mechanical-dilatational behavior are studied on model composites of glass-bead-filled polyurethanes. It is found that the stress-strain response of composites with untreated glass beads shows nonlinearity and subsequent yielding due to dewetting of particles from the matrix. In contrast, composites containing particles coated with a comupling agent fracture in a brittle manner, showing no significant nonlinearity and dewetting. Coated particles provide a higher tensile strength, but a lower strain at fracture, than uncoated particles. The volume fraction of the filler has an effect on Young's modulus, which is independent of the degree of coupling between the matrix and the filler. Tensile strength and strain at break decrease with increasing filler content for coated and uncoated particles. No strong effect of particle size is observed on either the tensile modulus or the dilatational behavior in the 25 μm to 160 μm diameter range. However, strain at break increases with decreasing particle size. When the accompanying yield phenomena shift to smaller strains, and a transition to brittle fracture takes place at high crosslink densities.     

Compatibilization and characterization of blends of styrene–maleic anhydride copolymer with modified polyethylenes

Potentially reactive blends of styrene–maleic anhydride (SMAH) with ethylene/methyl acrylate/glycidyl methacrylate (E‐MA‐GMA) and nonreactive blends of SMAH with ethylene/methyl acrylate (E‐MA) were produced in a Brabender batch mixer and in a corotating twin‐screw extruder. The products were characterized in terms of rheology, morphology, and mechanical properties to understand the reaction characteristics between anhydride/epoxy functional groups. Storage modulus, G′, loss modulus, G″ and complex viscosity, η* of the reactive blends were higher than those of nonreactive ones. At 25% E‐MA‐GMA content, maximum in η* was obtained for the reactive blends. The reactive blends showed finer morphology than the nonreactive ones at all concentrations studied. Mechanical characterization showed that reactive SMAH/E‐MA‐GMA blends had higher tensile strength, % strain at break, and tensile modulus than the nonreactive blends for all corresponding modified polyethylene contents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 790–797, 2001     

Mechanical and burning properties of highly loaded composite propellants

An improvement in the performance of solid rocket motors was achieved by increasing the oxidizer content of HTPB-based solid propellants. To minimize the adverse changes in the mechanical and rheological properties due to the increased amount of hard solid particles in the soft polymeric binder matrix, the optimum combination of the particle sizes and volume fractions of the bimodal ammonium perchlorate and the aluminum powder in the solid load was obtained from the results of testing a series of propellant samples prepared by using ammonium perchlorate in four different average particle sizes, 9.22, 31.4, 171, and 323 μm. The maximum packing density of solids in the binder matrix was determined by changing the sizes and the volume fractions of fine and coarse ammonium perchlorate at constant solid loading. The average size (10.4 μm) and concentration of aluminum powder used as metallic fuel were maintained constant for ballistic requirements. Optimum sizes and fine-to-coarse ratio of ammonium perchlorate particles were determined to be at mean diameters of 31.4 and 323 μm and fine-to-coarse ratio of 35/65. Solid content of the propellant was then increased from 75 to 85.6% by volume by using the predetermined optimum sizes and fine to coarse ratio of ammonium perchlorate. Mechanical properties of the propellant samples were measured by using an Instron tester with a crosshead speed of 50 mm/min at 25°C. The effect of oxidizer content and fine-to-coarse ratio of oxidizer on the burning rate of the propellant was also investigated by using a strand burner at various pressures. From experiments in which the size and the fine-to-coarse ratio of ammonium perchlorate were changed at constant solid loading, a minimum value of initial modulus was obtained for each fine-to-coarse ratio, indicating that the solids packing fraction is maximum at this ratio. The tensile strength and the burning rate increase, while the elongation at maximum stress decreases with increasing fine-to-coarse ratio of ammonium perchlorate. Experiments in which the total solid loading was increased at constant fine-to-coarse ratio of ammonium perchlorate show that the modulus, the tensile strength and the burning rate increase, while the elongation at maximum stress decreases with increasing solid loading. Propellants having solid loading of up to 82% exhibit acceptable mechanical properties and improved burning properties suitable for rocket applications. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1457–1464, 1998