Effects of prior aging at 288°C in argon environment on time‐dependent deformation behavior of a thermoset polymer at elevated temperature,Part 2: Modeling with viscoplasticity theory based on overstress

The viscoplasticity based on overstress (VBO) is augmented to model the effects of prior isothermal aging in an argon environment on the inelastic deformation behavior of PMR‐15 neat resin, a high‐temperature thermoset polymer. VBO is a unified state variable theory with growth laws for three state variables: the equilibrium stress, the kinematic stress and the isotropic stress. A systematic model characterization procedure based on a limited number of well defined experiments is employed to determine the VBO parameters. Experimental findings presented in Part I reveal the equilibrium stress and the kinematic stress to be affected by prior aging. Based on the experimental results, the isotropic stress is developed as a function of prior aging time. In addition, several VBO model parameters are made dependent on prior aging time. Comparison with experimental data demonstrates that the modified VBO successfully predicts the inelastic deformation behavior of the PMR‐15 polymer subjected to prior isothermal aging for up to 2000 h. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of prior aging at 288°C in air and in argon environments on creep response of PMR‐15 neat resin

The creep behavior of PMR‐15 neat resin, a polyimide thermoset polymer, aged in air and in argon environments at 288°C for up to 1000 h was evaluated. Creep tests were performed at 288°C at creep stress levels of 10 and 20 MPa. Creep periods of at least 25‐h in duration were followed by 50‐h periods of recovery at zero stress. Prior isothermal aging increased the elastic modulus and significantly decreased the polymer's capacity to accumulate creep strain. The aging environment had little influence on creep and recovery behaviors. However, aging in air dramatically degraded the tensile strength of the material. Dynamic mechanical analysis revealed an increase in the glass transition temperature from ∼330°C to ∼336°C after 1000 h in argon or in air at 288°C. The rise in the glass transition temperature with aging time is attributed to an increase in the crosslink density of the PMR‐15 polyimide. Increase in the crosslink density due to aging in both air and argon environments is likely behind the changes in the elastic modulus and the decreased capacity for inelastic straining. A visibly damaged surface layer of ∼0.16 mm thickness was observed in specimens aged in air for 1000 h. Results indicate that the unoxidized core material governs the overall mechanical response, whereas the oxidized surface layer causes a decrease in tensile strength by acting as a crack initiation site and promoting early failures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Linear viscoelastic properties of HFPE‐II‐52 polyimide

The polyimide HFPE‐II‐52 was developed at NASA Glenn Research Center for use as a matrix in high temperature composite materials. The unique properties of such composites stem largely from the performance of the matrix at high temperature. Thus, as part of a larger effort to study high temperature composite materials, the linear viscoelastic properties of HFPE are measured and a mathematical model of the properties is developed. In particular, storage, loss, and stress relaxation moduli were obtained from cyclic and transient loading experiments. A Prony series was fit to the relaxation modulus data. As a cross check, the fit to the relaxation modulus was converted to storage and loss moduli and compared with those measured directly. Effects of postcuring and of moisture on the properties are investigated as well. These results provide researchers with a constitutive model for HFPE‐II‐52 and provide some insight into the performance of HFPE matrix composites at high temperatures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3255–3263, 2006     

Some aspects of the mechanical response of BMI 5250‐4 neat resin at 191°C: Experiment and modeling

The inelastic deformation behavior of BMI‐5250‐4 neat resin, a high‐temperature polymer, was investigated at 191°C. The effects of loading rate on monotonic stress–strain behavior as well as the effect of prior stress rate on creep behavior were explored. Positive nonlinear rate sensitivity was observed in monotonic loading. Creep response was found to be significantly influenced by prior stress rate. Effect of loading history on creep was studied in stepwise creep tests, where specimens were subjected to a constant stress rate loading followed by unloading to zero stress with intermittent creep periods during both loading and unloading. The strain‐time behavior was strongly influenced by prior deformation history. Negative creep was observed on the unloading path. In addition, the behavior of the material was characterized in terms of a nonlinear viscoelastic model by means of creep and recovery tests at 191°C. The model was employed to predict the response of the material under monotonic loading/unloading and multi‐step load histories. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Application of time‐temperature superposition to energy limit of linear viscoelastic behavior

The energy approach for evaluation of the limits of linear viscoelastic (LVE) behavior is considered. The approach of Foux and Bruller based on the Reiner‐Weissenberg dynamic theory of strength is developed for the temperature effect. Value of the stored energy at the limit of LVE is considered as the material characteristic independent on loading conditions and temperature. Time–temperature superposition principle is extended for the energy calculations. Curves of the stored energy calculated for different temperatures are shifted to each other in the logarithmic time axes similarly as creep compliance and relaxation modulus curves in creep and tension tests, respectively. Temperature is considered as a factor that accelerates transition form linear to non‐LVE at the same stored energy threshold. This is proved by example of polyvinylchloride by comparing temperature dependences of the stress limits of LVE determined in two independent test series: tensile creep and constant strain rate tests. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,cure and pyrolysis behavior of heat‐resistant boron‐silicon hybrid polymer containing acetylene

The synthesis and characterization of a novel heat‐resistant boron‐silicon hybrid polymer containing acetylene (PBSA) and its conversion to a highly crosslinked thermoset were discussed. The polymer was synthesized from phenylboron dichloride using Grignard reagent method. The structure of PBSA was characterized by using Fourier transform infrared spectra, ¹H‐NMR, ¹³C‐NMR, and gel permeation chromatography. PBSA was thermosetting, highly heat‐resistant, high‐viscous, orange liquid at room temperature and good solubility in common organic solvents. Differential scanning calorimetry and thermogravimetric analysis analyses showed that the PBSA had excellent thermal and oxidative stability and the temperature of 5% weight loss (Td₅) were 650 and 638°C under nitrogen and air, respectively, and the residue at 1000°C were 93.3 and 91.3%, respectively, which indicated that the incorporation of boron and silicon into polymeric backbone was found to improve thermal and oxidative properties. X‐ray diffraction and scanning electron microscope were also used to analyze the formation of pyrolytic products. The results showed that the pyrolysis of PBSA resin was made up of β‐SiC and graphite. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fatigue of three advanced SiC/SiC ceramic matrix composites at 1200°C in air and in steam

High‐temperature mechanical properties and tension‐tension fatigue behavior of three advanced SiC/SiC composites are discussed. The effects of steam on high‐temperature fatigue performance of the ceramic‐matrix composites are evaluated. The three composites consist of a SiC matrix reinforced with laminated, woven SiC (Hi‐Nicalon?) fibers. Composite 1 was processed by chemical vapor infiltration (CVI) of SiC into the Hi‐Nicalon? fiber preforms coated with boron nitride (BN) fiber coating. Composite 2 had an oxidation inhibited matrix consisting of alternating layers of silicon carbide and boron carbide and was also processed by CVI. Fiber preforms had pyrolytic carbon fiber coating with boron carbon overlay applied. Composite 3 had a melt‐infiltrated (MI) matrix consolidated by combining CVI‐SiC with SiC particulate slurry and molten silicon infiltration. Fiber preforms had a CVI BN fiber coating applied. Tensile stress‐strain behavior of the three composites was investigated and the tensile properties measured at 1200°C. Tension‐tension fatigue behavior was studied for fatigue stresses ranging from 80 to 160 MPa in air and from 60 to 140 MPa in steam. Fatigue run‐out was defined as 2 × 10⁵ cycles. Presence of steam significantly degraded the fatigue performance of the CVI SiC/SiC composite 1 and of the MI SiC/SiC composite 3, but had little influence on the fatigue performance of the SiC/SiC composite 2 with the oxidation inhibited matrix. The retained tensile properties of all specimens that achieved fatigue run‐out were characterized. Composite microstructure, as well as damage and failure mechanisms were investigated.     

Thermal degradation of high‐temperature fluorinated polyimide and its carbon fiber composite

High‐temperature polymers are being used for a broad range of applications, such as composite matrices for structural applications (e.g., high speed aircraft). Polyimides are a special class of polymers that meet the thermal and oxidative stability requirements for high temperature composite aerospace applications. A weight loss study was performed on a fluorinated polyimide resin and its carbon fiber composite in an effort to determine its thermal stability and degradation mechanisms. Experiments were conducted using a preheated oven and thermogravimetric analysis to obtain the weight loss. Regardless of the method used, the resin and composite exhibited excellent thermal stability (less than 1% weight loss) below 430°C, regardless of 2–20 min of exposure. After 20 min of exposure at 510°C, the composite remained relatively stable with only 5.3% weight loss using the oven technique, whereas the neat polyimide sustained 12.6%. When degradation occurred, it was found to be the result of thermolysis and oxidation (to a lesser extent). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication of nearly stoichiometric polycrystalline SiC fibers with excellent high‐temperature stability up to 1900°C

Due to the extensive applications of SiC fiber‐reinforced composite materials in the fields of aviation, aerospace, and nuclear power, there are increasing demands for SiC fibers with both excellent mechanical performance and high‐temperature stability. In this work, nearly stoichiometric polycrystalline SiC fibers were fabricated using amorphous Si–C–Al–O fibers with excess carbon and oxygen (C/Si = 1.34, O content: 7.74 wt%). The nearly stoichiometric composition (C/Si = 1.05) of the product fibers was achieved by thermal decomposition of the starting fibers. The fibers were well‐crystallized with grain sizes of ~200 nm due to sintering at a high temperature of 1900°C. The fibers exhibited a high tensile strength and a high elastic modulus and were composed of SiC grains with twins and stacking‐faults, exhibiting intragranular fracture behavior. Furthermore, the fibers maintained their original tensile strength after being maintained at 1800°C for 5 hour or at 1900°C for 1 hour under an inert atmosphere, and they exhibited a high strength retention (97%) after exposure at 1300°C for 1 hour under air. The high‐temperature stability and creep resistance of the fibers were comparable to that of commercial Hi‐Nicalon S and Tyranno SA fibers.     

High‐temperature strength and plastic deformation behavior of niobium diboride consolidated by spark plasma sintering

Bulk niobium diboride ceramics were consolidated by spark plasma sintering (SPS) at 1900°C. SPS resulted in dense specimens with a density of 98% of the theoretical density and a mean grain size of 6 μm. During the SPS consolidation, the hexagonal boron nitride (h‐BN) was formed from B₂O₃ on the powder particle surface and residual adsorbed nitrogen in the raw diboride powder. The room‐temperature strength of these NbB₂ bulks was 420 MPa. The flexural strength of the NbB₂ ceramics remained unchanged up to 1600°C. At 1700°C an increase in strength to 450 MPa was observed, which was accompanied by the disappearance of the secondary h‐BN phase. Finally, at 1800°C signs of plastic deformation were observed. Fractographic analysis revealed a number of etching pits and steplike surfaces suggestive of high‐temperature deformation. The temperature dependence of the flexural strength of NbB₂ bulks prepared by SPS was compared with data for monolithic TiB₂, HfB₂ and ZrB₂. Our analysis suggested that the thermal stresses accumulated during SPS consolidation may lead to additional strengthening at elevated temperatures.     

The start‐up of anaerobic sequencing batch reactors at 20 °C and 25 °C for the treatment of slaughterhouse wastewater

The objective of this research was to evaluate the feasibility, the stability and the efficiency of a start‐up at 20 °C and 25 °C of anaerobic sequencing batch reactors (ASBRs) treating slaughterhouse wastewater. Influent chemical oxygen demand (COD) and suspended solids concentrations averaged 7500 and 1700 mg dm^?3, respectively. Reactor start‐up was completed in 168 and 136 days at 20 °C, and 25 °C, respectively. The start‐up process was stable at both temperatures, except for a short period at 20 °C, when effluent volatile fatty acid (VFA) concentrations increased from an average of 40 to 400 mg dm^?3. Effluent quality varied throughout start‐up, but in the last 25 days of the experiment, as the ASBRs were operated under organic loading rates of 2.25 ± 0.21 and 2.86 ± 0.24 kg m^?3 d^?1 at 20 °C and 25 °C, respectively, total COD was reduced by 90.3% ± 1.3%. Methanogenesis was not a limiting factor during start‐up. At 20 °C, the limiting factor was the acidification of the soluble organics and, to a smaller extent, the reduction of propionic, isobutyric and isovaleric acids into lower VFAs. At 25 °C, the limiting factor was the hydrolysis of particulate organics. To minimize biomass loss during the start‐up period, the organic loading rate should be increased only when 75 –80% of the COD fed has been transformed into methane within the design hydraulic retention time. © 2001 Society of Chemical Industry     

Working mechanism of a high temperature (200°C) synthetic cement retarder and its interaction with an AMPS®‐based fluid loss polymer in oil well cement

A copolymer comprising of 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS®) and itaconic acid (molar ratio 1 : 0.32) was synthesized by aqueous free radical polymerization and probed as high temperature retarder for oil well cement. Characteristic properties of the copolymer including molar masses (M_w and M_n), polydispersity index and anionic charge amount were determined. The copolymer possesses a M_w of ～ 2 × 10⁵ g/mol and is highly anionic. HT/HP consistometer tests confirmed effectiveness of the retarder at temperatures up to 200°C. The working mechanism of NaAMPS®‐co‐itaconic acid was found to rely exclusively on its huge calcium binding capacity (5 g calcium/g copolymer). It reduces the amount of freely dissolved, nonbound calcium ions present in cement pore solution and thus hinders the growth of cement hydrates because of lack of calcium. The value for the calcium binding capability is 46 times higher than the stoichiometric amount per ? COO^? functionality. Consequently, calcium also coordinates to other donor atoms present in the retarder. NaAMPS®‐co‐itaconic acid also adsorbs onto cement, as was evidenced by TOC analysis of cement filtrates, zeta potential measurement and decreased rheology of cement pastes. However, adsorption plays no role in the retarding mechanism of this copolymer. Combination of NaAMPS®‐co‐itaconic acid retarder with a common CaAMPS®‐co‐NNDMA fluid loss additive (FLA) revealed that competitive adsorption on cement between these two admixtures occurs. The retarder fills interstitial adsorption sites on cement located between those occupied by the larger FLA molecules. In consequence, fewer amounts of CaAMPS®‐co‐NNDMA can adsorb and its effectiveness is reduced. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Development of a lead‐free copper co‐fired BNT‐based piezoceramic sintered at low temperature

Compatibility of Bi‐based piezoelectric ceramic and copper electrodes is demonstrated by co‐firing 0.88Bi_1/2Na_1/2TiO₃–0.08Bi_1/2K_1/2TiO₃–0.04BaTiO₃ (BNKBT88) with copper. A combination of Bi₂O₃, CuO, ZnO, Li₂CO₃, and B₂O₃ are used as additives to reduce firing temperature to 900°C with minimal effect on the electromechanical properties compared to sintering at 1150°C without additives. Co‐firing with copper electrodes requires controlled oxygen sintering at low temperature. The atmosphere is controlled using carbon dioxide and hydrogen gas to maintain an oxygen partial pressure of 6.1 × 10^?8 atm, which is necessary for the coexistence of Cu metal and Bi₂O₃. The thermodynamic activity of bismuth oxide in BNKBT88 is calculated to be 0.38. BNKBT88 ceramics were successfully co‐fired with internal as well as surface Cu metal electrodes. The copper co‐fired ceramics were successfully polarized and the dielectric and piezoelectric properties are evaluated.     

Synthesis,characterization, and working mechanism of a synthetic high temperature (200°C) fluid loss polymer for oil well cementing containing allyloxy‐2‐hydroxy propane sulfonic (AHPS) acid monomer

A polymer comprising of 2‐acrylamido‐2‐methyl propane sulfonic acid, N, N‐dimethyl acrylamide, allyloxy‐2‐hydroxy propane sulfonic acid (AHPS), acrylic acid, and N, N‐methylene bisacrylamide was synthesized by aqueous free radical copolymerization and tested as high temperature performing fluid loss additive (FLA) in oil well cement. Successful incorporation of AHPS was confirmed and characteristic properties of the copolymer were determined using size exclusion chromatography. The FLA showed excellent water retention in cement at 200°C/70 bar. At this temperature, polymer structure changed from branched to linear and hydrodynamic size decreased by ～50%, thus indicating potential fragmentation, while performance remained unaffected by these alterations. The FLA copolymer does not viscosify cement slurries which is advantageous in high temperature well cementing. The working mechanism of the AHPS‐based copolymer was found to rely on reduction of filtercake permeability which is caused by a voluminous coprecipitate of the FLA with tartaric acid retarder, mediated by Ca²⁺ ions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

High‐temperature tensile behavior at different crosshead speeds during loading of glass fiber‐reinforced polymer composites

The present study evaluates on the static tensile behavior of glass fiber reinforced polymer (GFRP) composites at 50% and 70% volume fractions of reinforcement tested at room (25 °C), 70 °C, 90 °C, and 110 °C temperatures with 1, 10, 100, 500, and 1000 mm/min crosshead speeds to investigate the impact of high temperature on the mechanical properties and different dominating failures modes. The experimental results reveal that with increase in crosshead speeds the tensile strength of the composite is increasing. The effect of crosshead speeds and temperature with changing fiber volume fractions affects the GFRP composite. Although both the composite systems are found to be crosshead speed sensitive. Crosshead speed sensitivity seems to be more unpredictable at high temperature and at high crosshead speed. Furthermore, it appears to be more unprecedented nature of fluctuation with high fiber volume fraction. The crucial parameters required during the materials designing in various structural components were evaluated and modelled with the help of Weibull constitutive model. The fractography analyses were done to identify the various dominating failure modes in the GFRP composite. There was no significant change found in the glass transition temperatures (T_g) of both the composite system when exposed to different temperature environments. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44715.     

Synthesis,characterization and evaluation of a quadripolymer with low molecular weight as a water based drilling fluid viscosity reducer at high temperature (245 °C)

To construct an ultra‐high temperature stable drilling mud with a relatively low viscosity, a new viscosity‐reducing additive was synthesized and evaluated. This additive is a quadripolymer of acrylic acid (AA), 2‐acryl‐amido‐2‐methyl‐1‐propane sulfonic acid (AMPS), methyl acrylate (MA) and dimethyl diallyl ammonium chloride (DDAC) with low molecular weight synthesized by free radical polymerization, and its general molecular composition was confirmed by Fourier transform infrared spectroscopy. Thermal gravimetric analysis showed that the polymer has a very high temperature tolerance, i.e. it is stable up to 340 °C. Turbidity measurements with a UV?visible spectrophotometer showed that the polymer has a high salt tolerance in solution. It remained in solution at NaCl concentrations of up to 266 958 mg L^?1 and at CaCl₂ concentrations of up to 5000 mg L^?1. The quadripolymer was found to inhibit hydration of the exchangeable ions in the clay particles and this was affirmed by a reduction in interlayer spacing. It also displayed high adsorption on calcium montmorillonite at different pH and even in the presence of NaCl, and caused the breakup of the particle network structure. This additive, when added to drilling mud prepared in both fresh and salt water, was found to reduce the mud viscosity and yield stress before and after aging for 16 h at 245 °C compared to base mud especially below 220 °C and 4.5 MPa. Importantly, this additive in mud was found to perform effectively at a relatively high pH and in a broad pH range of 7–11. © 2015 Society of Chemical Industry     

Polymerization of methyl methacrylate at high temperature with 1‐butanethiol as chain transfer agent

The free‐radical polymerization of methyl methacrylate (MMA) at high temperature (120 to 180°C) has been studied in the presence of di‐tertiobutyle peroxide as an initiator and 1‐butanethiol as a chain transfer agent. No solvent was used, and the polymerization was run to high monomer conversion. Based on the experimental data collected with a dilatometric reactor, the features of the reaction have been pointed out. Working at high temperature with a chain transfer agent proved efficient to reduce the intensity of the gel effect and control the molecular weight obtained. At a temperature up to 170°C, however, the burn‐out of the initiator limits the final conversion, and the increase of the polymerization rate during the gel effect has been more difficult to detect and quantify. An empirical expression of the termination rate constant has been adopted to describe the autoacceleration and predict the conversion versus time curves and the average molecular weight of the polymer obtained. The mathematical model includes two adjustable parameters that have been determined as a function of the temperature and the initial concentration of the chain transfer agent. The agreement between the predicted and experimental data on conversion and molecular weight was good, while the polydispersity index was often underestimated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1589–1599, 1999     

Thermal analysis of high‐performance mortar containing burnt clay shale as a partial portland cement replacement in the temperature range up to 1000 °C

Clay shale is a specific type of material that contains a large amount of kaolinite. Burnt clay shale belongs to a large group of pozzolans, and its pozzolanic properties are activated after burning at temperatures similar to those when kaolinite is transformed into metakaolin. In this study, fine powder of burnt clay shale was used for the design of a high‐performance mortar as a partial replacement for portland cement up to 60 wt.%. The prepared specimens were subjected to a thermal analysis by using differential scanning calorimetry, thermogravimetry, and thermodilatometry. The investigation was performed in the temperature range 25–1000 °C. The basic physical and mechanical properties were studied as well. It was demonstrated that it is possible to design and produce a high‐performance mortar containing fine burnt clay shale powder and that an appropriate amount of this replacement is up to 20 wt.%. Copyright © 2016 John Wiley & Sons, Ltd.     

Structure and electrical properties of perovskite layer (1−x)Sr2Nb2O7‐x(Na0.5Bi0.5)TiO3 high‐temperature piezoceramics

The structure and electrical properties of perovskite layer structured (PLS) (1?x)Sr₂Nb₂O₇‐x(Na_0.5Bi_0.5)TiO₃ (SNO‐NBT) prepared by solid‐state reaction method are investigated. The addition of NBT is beneficial to speed up mass transfer and particle rearrangement during sintering, leading to better sinterability and higher bulk density up to 96.8%. The solid solution limit x in the SNO‐NBT system is below 0.03, over which Ti⁴⁺ is preferable to aggregate and results in the generation of secondary phase. After the modification by NBT, all SNO‐NBT ceramics have a Curie temperature T_c up to over 1300°C and piezoelectric constant d₃₃ about 1.0 pC/N. The breakthrough of piezoelectricity can mainly be attributed to rotation and distortion of oxygen octahedron as well as higher poling electric field resulting from the improved bulk density. This study not only demonstrates how to improve piezoelectricity by NBT addition, but also opens up a new direction to design PLS piezoceramics by introducing appropriate second phase.     

Toughening of a high‐temperature polymer by the sol–gel,in situ generation of a rubbery silica–siloxane phase

A phenyl ether phenyl phosphate polymer, specifically poly(biphenyl ether triphenyl phosphate), was modified to increase its tractability and to improve its toughness. The first goal was achieved by increasing its solubility by sulfonation of the chain, and the second, by the in situ generation of a rubbery phase. This phase was generated by a modification of the usual sol–gel reaction (which usually generates a hard silicalike material by the hydrolysis of a tetrafunctional organosilicate). In this case, a difunctional silicate was included, thus introducing some softening organic groups into the dispersed phase. A bonding agent, N,N‐diethylaminopropyltrimethoxysilane, was also included to improve the bonding between the two phases in this organic–inorganic composite. As expected, the glass transition temperatures generally increased slightly upon sulfonation, but decreased significantly upon introduction of the rubbery phase. Most important, the toughness of the polymer was successfully increased with, for example, only 8 wt % of the rubbery phase, quadrupling extensibility to 20 % and markedly increasing the toughness. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2326–2330, 2001