Development of a multi-objective coagulation system for long-term fouling control in dead-end ultrafiltration

In this paper, a multi-objective control system has been developed and experimentally tested. The multi-objective control system can be effectively used to control short-term fouling as well as long-term fouling. In an earlier study it was found that coagulant dosing in ultrafiltration can be used effectively to control the short-term fouling resistance during several sequential filtration cycles. To control long-term resistance increase during sequential chemical cleaning cycles, usually, in open-loop setting of the cleaning frequency or variables which influence the cleaning efficiency, such as, the cleaning time and the chemical composition are adjusted. Additional introductory experiments showed that changes in the coagulant dosing have a more pronounced effect on long-term fouling than changes in the usual applied variables. For this reason, it was decided to develop a closed-loop multi-objective controller where the coagulant dosing is used as the manipulated variable to accomplish both control objectives namely the fouling resistance over multiple filtration cycles (the short-term objective), as well as the irreversible fouling resistance over multiple chemical cleaning cycles (long-term objective). However, the controller is too slow to deal with temperature changes influencing the effectiveness of the coagulant dosing. To handle these influences a kind of gain scheduler should be included in the control algorithm.     

Laboratory investigation of biodegradability of a polyurethane foam under anaerobic conditions

Polyurethane (PU) foams can be used in many remediation applications as an isolation material to prevent the release of hazardous materials into the environment. The integrity of a PU foam was investigated in this study using short-term accelerated laboratory experiments including bioavailability assays, soil burial experiments, and accelerated bioreactors to determine the fate of PU foam in the soil where anaerobic processes are dominant. The experimental results have shown that the studied PU foam is likely not biodegradable under anaerobic conditions. Neither weight loss nor a change in the tensile strength of the PU material after biological exposure was observed. The FT-IR chemical signature of the PU foams was also nearly identical before and after biological exposure. The composition of the PU material (aromatic polyester and polyether PU) used in this study could have played a significant role in its resistance to microbial attack during the short-term accelerated experiments.     

Long-term in vitro operation of enzyme electrode-based glucose sensors

A model has been developed that simulates the effects of enzyme inactivation in long-term, continuously operated enzyme electrode-type glucose sensors. Predictions of the model have been verified in short-term experiments. The model suggests sensor designs to achieve long-term stability.     

The regression of isothermal thermogravimetric data to evaluate degradation Ea values of polymers: A comparison with literature methods and an evaluation of lifetime predictions reliability. Part II

The kinetics of the isothermal degradation in static air atmosphere of four well known polymers, polyethylene (PE), polystyrene (PS), polycarbonate (PC) and poly(methyl methacrylate) (PMMA) was studied by both a long-term (more than three years) experiment at relatively low temperature (423 K) and a set of short-term experiments at higher temperatures. The activation energy (E_a) values of degradation were determined by both the MacCallum and Wilkinson literature methods, and were compared with those obtained through a new very simple method we set up, based on the direct regression of TG mass loss data. About two years ago we published the results concerning PE and PS because their mass losses during long-term experiments were sufficiently high. The long-term degradation experiments were continued until now and in this second part we report the results concerning PC and PMMA. The degradation E_a values calculated from short-term experimental data through the three different methods were in good agreement with each other for both PC and PMMA, thus confirming the general applicability of our simple method for the determination of E_a. The experimental data at lower temperature of PC were not in agreement with those at higher temperatures, thus confirming the low reliability of the kinetic parameters (and then of lifetime predictions) at low temperature determined by experiments at higher temperatures. Partially disagreeing results were obtained for PMMA, which were discussed and interpreted.     

A Universal Reduced Rupture Creep Approach for Prediction of Long Term Failure Behavior of Aged Glass Polymers from the Short Term Test of Rupture Creep Compliance by the Unified Master Curved Extrapolation

The prediction of long term failure behaviors and lifetime of aged glass polymers from the short term tests of reduced rupture creep compliance (or strain) is one of difficult problems in polymer science and engineering. A new “universal reduced rupture creep approach” with exact theoretical analysis and computations is proposed in this work. Failure by creep for polymeric material is an important problem to be addressed in the engineering. A universal equation on reduced extensional failure creep compliance for PMMA has been derived. It is successful in relating the reduced extensional failure creep compliance with aging time, temperature, levels of stress, the average growth dimensional number and the parameter in K-W-W function. Based on the universal equation, a method for the prediction of failure behavior, failure strain criterion, failure time of PMMA has been developed which is named as a universal “reduced rupture creep approach”. The results show that the predicted failure strain and failure time of PMMA at di?erent aging times for different levels of stress are all in agreement with those obtained directly from experiments, and the proposed method is reliable and practical. The dependences of reduced extensional failure creep compliance on the conditions of aging time, failure creep stress, the structure of fluidized-domain constituent chains are discussed. The shifting factor, exponent for time-stress superposition at differentlevels of stress and the shifting factor, exponent for time-time aging superposition at different aging time are theoretically defined respectively.     

Micromechanics of semicrystalline polymers: Yield kinetics and long-term failure

The process of plastic deformation in semicrystalline polymers is complicated due to the operation of a variety of mechanisms at different levels and is strongly dependent on their underlying microstructure. The objective of this work is to establish a quantitative relation between the microstructure and the mechanical performance of semicrystalline polymers, as characterized by elasto-viscoplastic deformation. To do that, a micromechanically based constitutive model is used. The model describes the material as an aggregate of two-phase layered composite inclusions, consisting of crystalline lamellae and amorphous layers. The starting point for adding quantitative abilities to the model, in particular for the yield kinetics, is formed by experimental observations on both the yield kinetics and the time-to-failure of polyethylene at different temperatures, which reveal the contribution of two relaxation processes. To predict the thermo-rheologically complex short-term and long-term failure behavior, the crystallographic slip kinetics and the amorphous yield kinetics are re-evaluated, and the Eyring flow rule is modified by adding a temperature shift function. To enable the prediction of both tension and compression, a non-Schmid effect is added to the constitutive relation of each slip system. The creep behavior of polyethylene is then simulated directly using the multiscale, micromechanical model, predicting the time-to-failure, controlled by plastic deformation. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

The radiation resistance of thermoset plastics—VI. Unsaturated polyester plastics

Samples of two unsaturated polyester plastics, both with inorganic fillers, were irradiated under two very different conditions. One set of samples was irradiated with electrons, under exclusion of oxygen, using a high dose rate. The second set was irradiated with γ-rays, in air, using a very low dose rate of only 13.8 Gy/h. In the case of the short-term experiment the flexural strength, the impact strength and the deflection temperature passed through maxima as a function of dose. A significant deterioration of the strength did not occur up to a dose of 10 MGy. However, in contrast to this result, in the long-term experiment the strength was remarkably reduced at doses above 0.5 MGy. The electrical properties of four samples of different formulations were investigated. Irradiation with high dose rate had little influence on the electrical properties, but an abrupt drop of the surface resistance was found at 0.1 MGy in the long-term experiment. The tracking resistance showed a similar behaviour. Only the dielectric constants remained unchanged under all conditions of irradiation.     

Mechanical behavior and tensile fractography of compatible vinylchloride–vinylacetate–maleic acid terpolymer and nitrocellulose blends

Vinylchloride–vinylacetate–maleic acid terpolymer (VMCH) and nitrocellulose (NC) were blended at 10% (W/V) concentration is cyclohexanone at different weight fractions. Compatible blends were obtained at all weight fractions. This paper reports the mechanical behavior of solvent cast blend films of VMCH and NC. The films were prepared by solution blending and subsequent casting on a mercury surface. Depending on the composition, the tensile behavior ranged from brittle to ductile. The effect of the blend ratio on the properties shows that within the Hookeian region the modulus and strength have a positive deviation from linearity, whereas the elongation has a negative deviation. The effect of the blend ratio on the ultimate properties of the materials shows a positive deviation in strength up to 63 wt% VMCH composition and a negative deviation in elongation and toughness. The tensile fractography of the pure VMCH and VMCH/NC blends shows the presence of peaks, foldings of fibrils along with cavities or voids, which indicate a ductile mode of failure with craze-initiated fracture. Fractography of the pure NC Indicates a brittle mode of failure wit h craze-initiated fracturing.     

Mechanical Properties and Failure Mechanisms of Graphene under a Central Load

By employing molecular dynamics simulations, the evolution of deformation of a monolayer graphene sheet under a central transverse loading are investigated. Dependence of mechanical responses on the symmetry (shape) of the loading domain, on the size of the graphene sheet, and on temperature, is determined. It is found that the symmetry of the loading domain plays a central role in fracture strength and strain. By increasing the size of the graphene sheet or increasing temperature, the tensile strength and fracture strain decrease. The results have demonstrated that the breaking force and breaking displacement are sensitive to both temperature and the symmetry of the loading domain. In addition, we find that the intrinsic strength of graphene under a central load is much smaller than that of graphene under a uniaxial load. By examining the deformation processes, two failure mechanisms are identified namely, brittle bond breaking and plastic relaxation. In the second mechanism, the Stone–Wales transformation occurs.     

Creep behavior and lifetime prediction of PMMA immersed in liquid scintillator

The creep behavior of PMMA immersed in liquid scintillator at room temperature was experimentally studied with a new type of creep test machine. Both short-term and creep-rupture tensile tests at eight stress levels were performed. A master curve of creep compliance at a reference stress was obtained according to the Time-Stress Superposition Principle. The master curve was compared with the actual long-term creep curve. It demonstrates that the two curves coincide well at short times. However, the actual creep data shows a higher creep rate as time goes on. The actual lifetime is much shorter than that predicted by the master curve. Furthermore, the relationship between long-term creep limited strength and service life was determined. The results can be used to guide the safety design of PMMA vessels for application in a neutrino observatory.     

DSC experiments on gel-spun polyethylene fibers

The tensile strength of gel-spun polyethylene fibers obtained after hot-drawing depends on spinning conditions such as spinning speed, spinning temperature, spinline stretching, polymer concentration, and molecular weight/molecular weight distribution. High deformation rates in the spinline result in shish-kebab structures which after hot-drawing lead to fibers with poor properties. This is in contrast to hot-drawn fibers obtained from gel-spun fibers with a lamellar structure. Lamellar or shish-kebab structures in the gel-spun fibers can be distinguished by means of DSC experiments on strained fibers. On the basis of these experiments a qualitative prediction of the final tensile properties can be made. DSC experiments on (un)strained hot-drawn fibers show that in the case of shish-kebab structures an incomplete transformation into a fibrillar structure takes place which partly explains the low tensile strength. Chain slippage which becomes possible after the orthorhombic-hexagonal phase transition is involved in the fracture mechanism. The shift of the orthorhombic-hexagonal phase transition to higher temperatures with increasing tensile strength indicates that the increase in strength corresponds to an increase in length of the crystal blocks. Consequently, creep failure also occurs at higher stresses. The melting behavior of cold-drawn and hot-drawn fibers is qualitatively similar, but the transformation into a fibrillar structure is more complete in the latter case.     

Measurement of thermo-oxidative stability of isotactic polypropylene by isothermal long-term differential thermal analysis

The thermo-oxidative stability of isotactic polypropylene with different antioxidant concentrations between 0% and 0·1% has been studied using isothermal long-term differential thermal analysis (ILDTA). In the temperature range from 90°C to 210°C the oxidation maximum times were measured up to 2000 h. The Arrhenius plot of the reaction maxima showed straight lines over the whole temperature range, which were not affected by the crystallite melting range. Thus, extrapolations from short-term experiments at elevated temperatures to long-term behaviour at lower temperatures are possible.Ageing tests in a circulating-air oven at 140°C showed that the loss of thermo-oxidative stability with increasing ageing time was nearly linear. So the state of thermo-oxidative deterioration of isotactic polypropylene can be estimated by measurement of residual life time in an ILDTA experiment.The end of the oven life of polypropylene coincided with the loss of mechanical properties which was confirmed by a long-term tensile test at 100°C and 120°C.     

心脏胶原蛋白中交联氨基酸的质谱分析

心脏衰竭可能与心脏胶原蛋白交联异常有关,因为交联过程对心脏胶原蛋白的机械强度起决定作用.研究表明,某些交联氨基酸的含量可以用作对应胶原蛋白交联异常的分子标记,但心脏胶原蛋白交联异常的分子标记尚不清楚.本研究建立了串联质谱的分析方法可以高选择性的检测水解胶原蛋白质中两种重要的交联氨基酸-吡啶诺林(PYD)和去氧吡啶诺林(DPD).在小鼠心室胶原蛋白酸性水解产物中检测到DPD,未检测到PYD,说明PYD与心脏胶原蛋白的交联过程无关,而DPD在心脏胶原蛋白交联中起更重要的作用,有可能成为与心脏衰竭相关的分子标记.本研究提供了一种基于质谱的研究心脏胶原蛋白交联产物的方法,也可用于其它胶原蛋白的分析.     

Influence of the molding angle on tensile properties of FDM parts with orthogonal layering

Fused deposition molding (FDM) is one of the most widely used three‐dimensional (3D) printing technologies. This paper explores the influence of the forming angle on the tensile properties of FDM specimens. Orthogonal layering details were studied through experiments, theory, and finite element simulations. The stiffness and strength of the specimens were analyzed using the classical laminated plate theory and the Tsai–Wu failure criterion. The experimental process was simulated using finite element simulations. Results show that it is feasible to predict the stiffness and strength of FDM specimens using classical laminated plate theory and the Tsai–Wu failure criterion. A molding angle of 45° leads to specimens with maximized tensile properties. Numerical simulations show that changing the molding angle changes the internal stress and deformation fields inside samples, leading to FDM samples with different mechanical properties due to the orthogonal layers at different molding angles.     

Time-parameter Method for Studying Kinetics of Consecutive First-order Reactions in Calorimeter

Thermogravimetric analysis (TG) was used in this work to study the degradation kinetics of industrial PVC plastisols. In order to model the pyrolitic degradation of plastisols in nitrogen, a kinetic model based on phenomenological considerations was developed. Two different processes were observed during the first degradation stage. The model parameters, such as activation energies and pseudo orders of reaction, were calculated using a non-linear regression analysis. The model developed was able to describe the degradation behaviour both in isothermal and in dynamic modes. The results of such analysis were applied to obtain long-term data from short-term experiments as an engineering approach to evaluate the thermal resistance of plastisols. This revised version was published online in July 2006 with corrections to the Cover Date.     

Repeatability and reproducibility of retention data and band profiles on reversed-phase liquid chromatography columns: I. Experimental protocol

A procedure is described for the determination of the short-term and long-term repeatabilities and of the column-to-column and lot-to-lot reproducibilities of the retention and profile characteristics of the peaks obtained with a number of different reversed-phase liquid chromatography (RPLC) C₁₈-bonded silica columns of several commercial brands. Data characterizing the retention, the steric selectivity, the hydrogen bonding capacity, the hydrophobic interaction selectivity, the column efficiency and the peak asymmetry will be acquired for all the probe compounds. These include 30 neutral, acidic and basic compounds distributed into five groups to be eluted under as many different sets of chromatographic conditions. The data will be obtained using an HP 1100 liquid chromatograph. The compounds and experimental conditions selected were similar to those previously used by different authors for comparison purposes. Careful attention will be paid to minimization of external error contributions by adhering to a strict operational procedure. The precision expected will be high because preliminary results gave standard deviations of around 0.04% for the separation factors, below 0.15% for the retention times and around 1% for the column efficiency in short-term repeatability experiments performed with one column.     

Effects of short- and long-term ultraviolet B irradiation on the immune system of the common carp (Cyprinus carpio)

Carp (Cyprinus carpio) were repeatedly exposed to 0, 60, 120 and 240 mJ/cm2 ultraviolet B (UVB) radiation three times in 1 week (short-term exposure) or 12 times in 4 weeks (long-term exposure). The effect of UVB on the functioning of the carp immune system was studied on day 2 after the final irradiation. After short-term UVB exposure, the whole-blood respiratory burst and cytotoxic activity were markedly enhanced, with parallel responses in both the number of circulating granulocytes and in the plasma cortisol concentration of the fish. These changes were not detectable after long-term exposure. The respiratory burst by head kidney granulocytes was suppressed dose dependently after both exposures, but cytotoxic activity was not affected. Exposure to UVB also modulated lymphocyte functions: nonstimulated and PHA-stimulated proliferation of head kidney lymphocytes in vitro was enhanced by both short-term and long-term exposure. LPS-stimulated proliferation was not affected by exposure nor was the number of immunoglobulin-secreting cells in the head kidney. In long-term exposure, the highest dose reduced the level of plasma IgM. This study indicates that UVB irradiation induces immunomodulation in the blood and head kidney of the carp and that the effects of short- and long-term exposure differ from each other. The results emphasize the potentially harmful impact of increased solar UVB radiation on fish immune functions.     

Measurement of oxidation stability of polyolefins by thermal analysis

Isothermal differential thermal analysis has been used to study the thermal stability of polybutene and crosslinked polyethylene in the temperature range from 120°C to 240°C. Oxidation induction times were measured from 2 min up to 7250 h. The Arrhenius-plots of DTA results showed curvature at 150°C, so straight line extrapolations from short-term experiments at elevated temperatures to low temperatures and long times are not possible. Oxidation induction time and mechanical failure in oven ageing experiments coincided over the measured temperature range. Decrease in the molecular weight of polybutene accelerated after the end of the induction period.Thermoanalytically measurable residual thermal stability decreased linearly with ageing time and is a more sensitive indicator of the beginning of thermal degradation than measurement of tensile properties. Finally, the extraction of stabilizer by hot water was measured by isothermal DTA.     

Processing and Properties of Inorganic-Organic Hybrids Containing Various Inorganic Components

Inorganic-organic hybrids containing various inorganic components have been synthesized from silanol-terminated polydimethylsiloxane (PDMS) and three different inorganic components: Al(O-sec-C4H9)3, Ti(OC2H5)4 and Ta(OC2H5)5. The hybrids obtained were transparent and flexible. Dynamic mechanical measurements and stress-strain experiments were carried out in order to study the effect of inorganic component on the properties of the Metal-O-PDMS hybrids. The storage modulus at around room temperature increased in the order Al-O-PDMS, Ti-O-PDMS, Ta-O-PDMS hybrids, indicating that the three-dimensional network structure became denser in this order. The tensile strength increased in the order Al-O-PDMS, Ta-O-PDMS, Ti-O-PDMS hybrids. The difference in tensile strength is considered to be related to the strength of the interaction between the inorganic component and PDMS. The elongation at failure also depended on the inorganic component. Ti-O-PDMS hybrid exhibited the largest elongation of all the samples (more than 200%).