Thermal properties of Nafion–TiO<Subscript>2</Subscript> composite electrolytes for PEM fuel cell

Thermal analysis has been used to evaluate the stability, glass transition, and water retention of Nafion based polymer–ceramic electrolytes. These electrolytes are envisioned as promising replacement of Nafion in fuel cells operating above 100 °C. The polymeric matrix prepared by casting exhibits lower crystallinity than the extruded Nafion, a feature that affects the water absorption properties. The addition of titania-based nanotubes and nanoparticles to the polymer has enhanced the water retention at high temperatures (~130 °C) and the glass transition temperature, respectively. Such results are important for the design of composite electrolytes for the operation of fuel cells at high temperatures.     

Coefficient of thermal expansion evolution for cryogenic preconditioned hybrid carbon fiber/glass fiber-reinforced polymeric composite materials

Polymeric matrix composites are susceptible to degradation and material properties changes if subjected to low-temperature environmental conditions. This paper attempts to present a study on effective coefficient of thermal expansion for various hybrid carbon fibers/glass fibers polymeric composite structures previously subjected to low-temperature environmental conditioning. The hybrid composite architectures were made from various layers of glass mat and/or glass woven embedded along with layers of unidirectional carbon fibers into a polymeric matrix. The samples were preconditioned to a low-temperature environment at a constant temperature of ?35 °C for 1-week long, 24 h/day. The instantaneous CTE and thermal strain fields were recorded with a DIL 402 PC/1 dilatometer from Netzsch GmbH (Germany) by setting a monotonically linear rise of temperature from 20 to 250 °C, at a rate of 1 °C min^?1. The experimentally retrieved data were compared with the values obtained by running a micromechanical-based approach simulation on a representative volume element.     

Development and characterization of fully bio‐based polybenzoxazine‐silica hybrid composites for low‐k and flame‐retardant applications

In the present work, new classes of bio‐based polybenzoxazines were synthesized using eugenol as phenol source and furfurylamine and stearylamine as amine sources separately through solventless green synthetic process routes and were further reinforced with varying percentages (1, 3, 5, and 10 wt%) of silica (from rice husk) to attain hybrid composites. The molecular structure, cure behaviour, thermal stability, dielectric properties, and flame‐retardant behaviour of both benzoxazine monomers and benzoxazine composites were characterized using appropriate modern analytical techniques. The eugenol‐based benzoxazines synthesized using furfurylamine (FBz) and stearylamine (SBz) were cured at 223°C and 233°C, respectively. The differential scanning calorimetry (DSC) data reveal the glass transition temperatures (T_g) of FBz and SBz were 157°C and 132°C, respectively, and the maximum decomposition temperature (T_max) as obtained from thermogravimetric analysis (TGA), were found to be 464°C and 398°C for FBz and SBz, respectively. The dielectric constants for FBz and SBz obtained at 1 MHz were 3.28 and 3.62, respectively. Furthermore, varying weight percentages (1, 3, 5, and 10 wt%) of 3‐mercaptopropyltrimethoxysilane (3‐MPTMS) functionalized bio‐silica reinforced the composite materials as evidenced by their improved thermal stability and lower dielectric constant. Data obtained from thermal and dielectric studies suggested that these polybenzoxazines could be used in the form of adhesives, sealants, and composites for high performance inter‐layer low‐k dielectric applications in microelectronics.     

Synthesis and characterization of core–shell‐type polymeric micelles from diblock copolymers via reversible addition–fragmentation chain transfer

A method was developed to enable the formation of nanoparticles by reversible addition–fragmentation chain transfer polymerization. The thermoresponsive behavior of polymeric micelles was modified by means of micellar inner cores and an outer shell. Polymeric micelles comprising AB block copolymers of poly(N‐isopropylacrylamide) (PIPAAm) and poly(2‐hydroxyethylacrylate) (PHEA) or polystyrene (PSt) were prepared. PIPAAm‐b‐PHEA and PIPAAm‐b‐PSt block copolymers formed a core–shell micellar structure after the dialysis of the block copolymer solutions in organic solvents against water at 20 °C. Upon heating above the lower critical solution temperature (LCST), PIPAAm‐b‐PHEA micelles exhibited an abrupt increase in polarity and an abrupt decrease in rigidity sensed by pyrene. In contrast, PIPAAm‐b‐PSt micelles maintained constant values with lower polarity and higher rigidity than those of PIPAAm‐b‐PHEA micelles over the temperature range of 20–40 °C. Structural deformations produced by the change in the outer polymer shell with temperature cycles through the LCST were proposed for the PHEA core, which possessed a lower glass‐transition temperature (ca. 20 °C) than the LCST of the PIPAAm outer shell (ca. 32.5 °C), whereas the PSt core with a much higher glass‐transition temperature (ca. 100 °C) retained its structure. The nature of the hydrophobic segments composing the micelle inner core offered an important control point for thermoresponsive drug release and the drug activity of the thermoresponsive polymeric micelles. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3312–3320, 2006     

Uniaxial tensile tests and dynamic mechanical analysis of satin weave reinforced epoxy shape memory polymer composite

The utilization of epoxy shape memory polymer composite (SMPCs) as engineering materials for deployable structures has attracted considerable attention in recent decades due to high strength and satisfactory stiffness in comparison with shape memory polymers (SMPs). Knowledge of static and dynamic mechanical properties is essential for analyzing structural behavior and recovery properties, especially for new epoxy SMPCs. In this paper, a new weave reinforced epoxy shape memory polymer composite was prepared with satin weave technique and resin transfer molding technique. Uniaxial tensile tests and dynamic mechanical analysis were carried out to obtain basic mechanical properties and glass transition temperatures, respectively.The tensile strength and breaking elongation of warp specimens were comparable with those of weft specimens. The increment of elastic modulus and hysteresis loop areas became smaller with loading cycles, meaning that cyclic tests could obtain approximate stable mechanical properties. For dynamic mechanical properties, glass transition temperature (T_g) obtained from storage modulus curves was lower than that determined from tan delta curves and T_gs in the warp and weft directions were similar (29.4 °C vs 29.7 °C). Moreover, the storage modulus in response to T_g was two orders of magnitude less than that with respect to low temperature, which demonstrated the easy processibility of epoxy SMPCs near glass transition temperature. In general, this study could provide useful observations and basic mechanical properties of new epoxy SMPCs.     

Low velocity impact and pseudo-ductile behaviour of carbon/glass/epoxy and carbon/glass/PMMA hybrid composite laminates for aircraft application at service temperature

Carbon/glass hybrid composite (CGHC) laminates are some of the most promising composites for lightweight applications. Sometimes these laminates are used in warm environment, such as aircraft frame structures, and this may affect their performance. In order to investigate this issue, the present research aims to study the effect of temperatures on the impact behavior and pseudo-ductile behaviour of CGHC in presence of different types of thermosets “epoxy” and thermoplastic “acrylic poly-methyl methacrylate-PMMA”. The experiments were started with making of CGHC laminates from different stacking sequences of unidirectional carbon and woven glass fibre layers, using a vacuum-assisted resin transfer method followed by curing treatment. In addition to CGHC laminates, four other neat batches (Carbon/epoxy, Carbon/PMMA, Glass/epoxy, Glass/PMMA) were prepared for comparison. The low velocity impact behaviour of the fabricated panels was evaluated at high temperatures (60 °C and 80 °C) according to ISO 6603-2 standard, using drop tower, while pseudo-ductile behaviour and ductility index (DI) of the specimens were estimated based on the measured total energy and elastic energy. Also, the low-velocity impact response was modeled mathematically based on a modified energy-balance model to predict the absorbed energies. Finally, the failure mechanisms were examined using optical microscope to determine the influence of these damage growth on DI of the composites under different temperatures. The results showed that the impact energy response of both hybrid composites i.e. epoxy and PMMA was stable even as the temperature rose, however, carbon/glass/PMMA exhibited better performance compared with carbon/glass/epoxy with an increase in impact energy response estimated at 50% (25 °C) and 53% (80 °C). Also, the pseudo-ductile phenomenon was strongly evident, which facilitates the predictablility of failure.     

Dynamic mechanical analysis of ethylene tetrafluoroethylene (ETFE) foils in use for transparent membrane buildings

Glass transition temperature and tan delta (the ratio of loss modulus to storage modulus) are indispensable parameters for determining appropriate application range of ETFE foils. In this study, ETFE foils in terms of specimen number, material direction and thickness were investigated with dynamic mechanical analysis (DMA) over a temperature range of -70-100 °C at frequencies of 0.1, 1, and 10 Hz. Glass transition temperatures were obtained with storage modulus, loss modulus and tan delta curves. It is found that frequency effect on glass transition temperature was proportional and that frequency effect was more significant than material direction effect. Moreover, a comparison study showed that elastic modulus determined with quasi-static experiments was greater than storage modulus calculated with dynamic mechanical experiments. To propose suitable glass transition temperature ranges for engineering application, an approach to determine confidence interval based on statistical analysis was employed. The resulting intervals with confidence coefficient of 95% were 31.2–32.7 °C, 60.5–66.4 °C and 79.6–83.3 °C for storage modulus, loss modulus and tan delta, respectively. In general, this study could provide useful observations and values for evaluating dynamic mechanical properties of ETFE foils.     

Shape memory effect and recovery stress property of carbon nanotube/waterborne epoxy nanocomposites investigated via TMA

Shape memory polymers (SMPs) have received great attention and scientific interest in widespread technological development during last few decades. Besides the development of novel SMPs, various techniques have been practiced for characterization of shape memory effect (SME) of SMPs. In this study, the shape memory effect and recovery stress property of the carbon nanotube (CNT)/waterborne epoxy (WEP) nanocomposites below and above the glass transition temperature (T_g) of the nanocomposites and under isostrain and isostress were systematically investigated via thermal mechanical analysis (TMA), respectively. The experimental results showed that the nanocomposites exhibit excellent shape memory effect. The shape memory fixity and recovery ratios were approximately 100% even below glass transition temperature (T_g). A remarkable point is that the strain of the nanocomposites suddenly increased with the temperature decreasing in a certain period of the heating-cooling cycles under isostress condition and the strain increment increased with temperature in general. Especially at low temperature, the recovery stress was very sensitive to temperature under isostrain condition of ±0.25 °C temperature with differential of 25.5 °C developed pressure difference of 0.20 MPa. Moreover, TMA is a practical method for quantifying the SME and recovery stress properties of SMPs and their composites.     

Thermal,mechanical and dielectric behaviour of poly(aryl ether ketone) with low melting temperature

New poly(aryl ether ketone)s (PAEKs) with a low melting temperature (relative to PEEK) are of interest in order to simplify the manufacturing of high-performance polymers or composites. In this study, we propose to investigate the physical properties of a new PAEK from Victrex, namely PAEK LM. Combinations of thermal analyses were used as follows: standard and modulated temperature differential scanning calorimetry, dynamic mechanical analysis, dynamic dielectric analysis and guarded hot plate technique. We found that the global mechanical, dielectric and thermal properties are very similar to the PEEK reference. The glass transition temperature was observed in the same range than PEEK (∼ 150 °C) while the melting temperature T_m was measured at 307 °C for PAEK LM which is about 35 °C below the melting temperature of PEEK. The degree of crystallinity of PAEK LM was found to be 27% while for PEEK it is 38%, depending on the processing conditions. This work explored crystalline structure–property relationships to explain the behaviour of PAEK LM.

     

New polymer electrolyte membrane for medium-temperature fuel cell applications based on cross-linked polyimide Matrimid and hydrophobic protic ionic liquid

New hydrophobic protic ionic liquid, 2-butylaminoimidazolinium bis(trifluoromethylsulfonyl)imide (BAIM-TFSI), has been synthesized. The ionic liquid showed good thermal stability to at least 350 °C. The conductivity of BAIM-TFSI determined by electrochemical impedance method was found to be 5.6 × 10^?2 S/cm at 140 °C. Homogeneous composite films based on commercial polyimide (PI) Matrimid and BAIM-TFSI containing 30–60 wt% of ionic liquid were prepared by casting from methylene chloride solutions. Thermogravimetric analysis data indicated an excellent thermal stability of PI/BAIM-TFSI composites and thermal degradation points in the temperature range 377 °C–397 °C. The addition of ionic liquid up to 50 wt% in PI films does not lead to any significant deterioration of the tensile strength of the polymer. The dynamic mechanical analysis results indicated both an increase of storage modulus E′ of PI/BAIM-TFSI composites at room temperature and a significant E′ decrease with temperature compared with the neat polymer. The cross-linking of the PI with polyetheramine Jeffamine D-400 allowed to prepare PI/Jeffamine/BAIM-TFSI (50%) membrane with E′ value of 300 MPa at 130 °C. The ionic conductivity of this cross-linked composite membrane reached the level of 10^?2 S/cm at 130 °C, suggesting, therefore, its potential use in medium-temperature fuel cells operating in water-free conditions.     

Thermal characterization of dental composites by TG/DTG and DSC

Dental composites can be improved by heat treatment, as a possible way to increase mechanical properties due to additional cure (post-cure). Direct dental composites are essentially similar to the indirect ones, supposing they have the same indication. Therefore, to establish a heat treatment protocol for direct composites, using as indirect (photoactivated by continuous and pulse-delay techniques), a characterization (TG/DTG and DSC) is necessary to determine parameters, such as mass loss by thermal decomposition, heat of reaction and glass transition temperature (T _g). By the results of this study, a heat treatment could be carried out above 160 °C (above T _g, and even higher than the endset exothermic event) and under 180 °C (temperature of significant initial mass loss).     

The dynamic mechanical behavior of random-in-plane short fiber-reinforced epoxy resin composites

In the present paper, the dynamic mechanical properties of random-in-plane short fiber-reinforced epoxy resin composites were studied by using a rheometrics solids analyzer. The three-point bend testing of the four composites (glass fiber/913 epoxy resin, glass fiber/924 epoxy resin, carbon fiber/913 epoxy resin and carbon fiber/924 epoxy resin) was carried out over temperatures from −100°C to 200°C at a frequency of 10 Hz and strain 0.05%. The composites based on 924 epoxy resin, which has been designed specially for high temperature applications, have less energy loss than the 913 epoxy resinbased composites. For the same resin, the carbon fiber-reinforced composites have less energy loss than the glass fiber-reinforced composites. All the composites have less energy loss than their corresponding matrices; the greater the fiber content, the lower the energy loss. The beta transition of 913 epoxy resin has been shifted to a higher temperature after being reinforced. It was shifted from −50°C to −30°C after being reinforced with glass fiber and made a diffuse shoulder-like peak commencing at −30°C after being reinforced with carbon fiber. The 924 epoxy resin has undergone the same change in beta transition as the 913 resin, though to a smaller extent. The phenomenon suggested that interactions between the macromolecules of the epoxy resins and the molecules along the fiber's surface.     

Modified silica-based isoprene rubber composite by a multi-functional silane: Preparation and its mechanical and dynamic mechanical properties

Modified silica-based isoprene rubber (IR) composite has been designed and prepared by using a multi-functional silane, 2-aminoethyl-2-(3-triethoxysilylpropyl)aminoethyl disulfide (ATD), as coupling agent. Such modification significantly improved the dispersity of silica in the corresponding composites, as verified by SEM observation. And the hardness, tensile strength, stress at definite elongation, tear strength and temperature rise as well as the value of dynamic loss coefficient ranging from 0 °C to 80 °C of silica/IR vulcanized composites, are significantly improved, especially with low ATD dosage (2–4 phr). This modification of silica-based IR composite by employing ATD as coupling agent provides a facile and effective method to prepare silica-based rubber composites with improved mechanical properties and low hysteresis.     

Influence of thermal treatment on the glass transition temperature of thermosetting epoxy laminate

The influence of accelerated thermal treatment of thermosetting epoxy laminate on its glass transition temperature was studied. Lamplex^® FR-4 glass fibre-reinforced epoxy laminate (used for printed circuit board manufacturing) was used in these experiments. The composite was exposed to thermal treatments at temperatures ranging from 170 °C to 200 °C for times ranging from 10 to 480 h. The glass transition temperature (T_g) was analysed via dynamic mechanical analysis (DMA). It has been proven that the glass transition temperature rapidly decreases in reaction to thermal stress. The obtained T_g data were used for Arrhenius plots for different critical temperatures (T_g-crit. = 105–120 °C). From their slopes (?E_a/R), the activation energy of the thermal degradation process was calculated as 75.5 kJ/mol. In addition to this main relaxation mechanism, DMA also recorded one smaller relaxation process in the most aged samples. Microscopic analysis of the sample structure showed the presence of pronounced small regions of degradation both on the surface and in the inner structure, which are probably the causes of microscopic delamination and the smaller relaxation process.     

Evaluation of interfacial region of microphase-separated SEBS using modulated differential scanning calorimetry and dynamic mechanical thermal analysis

The continuous structural changes of Poly(styrene-b-ethylene-butylene-b-styrene) [SEBS] due to the effect of temperature are hard to evaluate using conventional differential scanning calorimetry (DSC). This paper presents an accurate and simple way to evaluate microstructural and glass transitions of SEBS using modulated differential scanning calorimetry (MDSC). The weak crystalline nature of –(CH₂-CH₂)–_n in the ethylene-butylene (EB) block melted around 36 °C. The premature molecular moment and Tg of the styrene block were at 62 °C and 96 °C, respectively. The interfacial region at high temperature was explained with respect to order-order transition (OOT) at 144 °C and a prominent Order-Disorder Transition (ODT) at around 202 °C. Dynamic mechanical thermal analysis (DMTA) and dynamic mechanical rheological testing (DMRT) measurements also revealed that the T_g of the PS transition were consistent at around 96 °C.     

Dielectric study of relaxations and polymorphism in poly(diethyl siloxane)

The dielectric behavior of poly(diethyl siloxane) supports the adiabatic calorimetric findings of Beatty and Karasz. In particular, a sub-T_g transition is observed near ?180°C at 100 Hz, the glass transition near ?135°C at 100 Hz, and a first-order transition near ?70°C (crystal–crystal transformation). This glass-transition temperature is the lowest reported polymeric glass transition for polymers.     

Low percolation conductive graphite flakes-filled poly(urethane-imide) composites with high thermal stability via imidization self-foaming structure

In the study, the conductive graphite flakes filled poly(urethane-imide) composites (PUI/GFs) with high performance were constructed by the thermal imidization self-foaming reaction. It was found that the foaming action could promote the redistribution of GFs during curing process and the formation of stable linear conductive pathways. The percolation threshold of PUI/GFs composites was lowered from 1.26 wt% (2000 mesh GFs) or 0.86 wt% (1000 mesh GFs) to 0.79 wt% (500 mesh GFs), which were relatively low percolation thresholds for polymer/GFs composites so far. When the content of 500 mesh GFs was 4.0 wt%, the electrical conductivity of the composite was as high as 3.96 × 10^?1 S/m. Also, a poly(urethane-imide) (PUI) matrix with excellent thermal stability (T_d10%: 334.97 °C) and mechanical properties (elongation at break: 324.52%, tensile strength: 15.88 MPa) was obtained by introducing the rigid aromatic heterocycle into the polyurethane (PU) hard segments. Moreover, the zero temperature coefficient of resistivity for the composites was observed at the temperature range from 30 °C to 200 °C. Consequently, PUI/GFs composites may provide the novel strategy for considerable conductive materials with high thermal stability in electrical conductivity.     

Cure state detection for pre-cured carbon-fibre epoxy prepreg (CFC) using Temperature-Modulated Differential Scanning Calorimetry (TMDSC)

Carbon-fibre prepregs have found widespread use in lightweight applications. They are based on a carbon-fibre fabric impregnated with reactive epoxy resin. Prepreg materials are generally pre-cured so that they have a higher molecular weight than typical resins in order to reduce resin flow, which facilitates storage and later processing properties.The measurements were carried out using commercially available materials and follow the published DMA investigations of the same material [1]. TMDSC was used to find the correlation between curing conditions, the degree of cure and glass transition temperature. TMDSC has the advantage over standard DSC that it enables better determination of the glass transition temperature, which is often accompanied by an exothermic curing reaction, and thus overshadowed. The influence of the amplitude of temperature modulation was tested in preliminary experiments. For non-cured material a glass transition temperature of approximately 0 °C was determined; whereas for the totally cured material it was approximately 230 °C. The changes in degree of cure, temperature of actual glass transition and post-reaction are given as a function of curing time at 180 °C. The correlation between actual glass transition temperature and degree of cure is derived.