Phase relationships of rigid rod polymer/flexible coil polymer/solvent ternary systems

Phase diagrams of two types of rigid rod polymer/flexible coil polymer/methanesulfonic acid (MSA) ternary systems were determined by polarized optical microscopy at ambient conditions. The rigid rod polymer is a wholly aromatic high temperature resistant (no measurable T_g) poly (p-phenylenebenzobisthiazole) (PPBT). One of the flexible coil polymers is a wholly aromatic high temperature resistant poly (2,5′(6′) benzimidazole) (ABPBI), the other is a thermoplastic poly[2,2′ -(1–4-phenylene)-6,6′ -bis (3-phenyl-quinoxaline)] (PPQ) with T_g of 359°C. The solvent is methane-sulfonic acid (MSA). The experimentally determined critical concentration points, C_cr, are in excellent agreement with Flory's recent theory. Total phase segregation between the polymer pair in ternary solution was predicted and observed at C > C_cr. Different decomposition mechanisms of phase separation were observed as a function of concentration.     

A high temperature polymer of phthalonitrile‐substituted phosphazene with low melting point and good thermal stability

A phthalonitrile‐substituted phosphonitrilic monomer has been synthesized from phosphonitrilic chloride trimer and then polymerized with addition of 4‐(hydroxylphenoxy)phthalonitrile (HPPN). The chemical structures of the phosphonitrilic monomer and polymer were characterized by Fourier Transform Infrared spectroscopy (FT‐IR) and proton Nuclear Magnetic Resonance spectroscopy (¹H NMR). Curing behaviors and thermal stabilities of the polymer were investigated through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Analysis showed that the monomer has large processing temperature window and good thermal stability. Apparent activation energy, initial curing temperature (T_i), curing temperature (T_p), and termination curing temperature (T_f) of the phosphonitrilic polymer were explored. Dynamic mechanical analysis (DMA), glass transition temperature (T_g) were studied, and limiting oxygen index (LOI) were estimated from the van Krevelen equation, which indicates the polymer process high modulus and good flame retardance. Micro‐scale combustion calorimetry (MCC) was also used for evaluating the flammability of the polymers. Postcuring effects were explored, showing excellent thermal and mechanical properties with postcuring. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42606.     

Laser Ignition of Various Pyrotechnic Mixtures – an Experimental Study

Ignition of several pyrotechnic mixtures by diode‐laser was studied experimentally using a novel combustion chamber. The ignition delay times dependence on laser intensity could be fit by the expression t_ign=aI⁻ⁿ for all compositions, with I being the laser intensity at target and n=1.4–2.1. This is roughly in accordance with thermal ignition theories assuming a semi‐inert solid. Differences in ignition delay times did not depend on fuel alone or oxidizer alone. The temperature of oxidizer decomposition does not correlate with ignition delay time. Furthermore, the steady state combustion temperature, deduced from emission spectra of the composition products are not correlated with ignition delay time. It is proposed that chemical reactions, taking place in the gas‐phase or in the solid‐phase, play a significant role, but are not solely responsible for ignition delay time. The seemingly uncorrelated ignition delay results between pyrotechnics containing either the same fuel or oxidizer hamper the construction of a “unified theory” for laser ignition of pyrotechnic mixtures.     

Metal‐coordinated epoxy polymers with suppressed combustibility. Preparation technology,thermal degradation,and combustibility test of new epoxy‐amine polymers containing the curing agent with chelated copper(II) carbonate

The diethylenetriamine chelate complex of copper(II) carbonate—DETA‐CuCO₃ (a fire retardant hardener of epoxy resins)—and the CuCO₃‐containing epoxy‐amine polymers—DGEBA/DETA‐CuCO₃(6), DGEBA/DETA‐CuCO₃(12), DGEBA/DETA‐CuCO₃(40), and DGEBA/DETA‐CuCO₃(80) with suppressed combustibility—have been obtained in the DETA‐DGEBA‐CuCO₃ system (DETA and DGEBA are diethylenetriamine and bisphenol A diglycidyl ether, respectively). The DETA‐CuCO₃ chelate complex was characterized by X‐ray powder diffraction, infrared spectra, and thermal analysis. The thermal gravimetric analysis results have revealed that thermal destruction of DETA‐CuCO₃ was finished at 400°С, and the maximal temperature of the combustion gases amounted to 520°С. The thermal behavior and combustibility of the CuCO₃‐containing epoxy‐amine polymers were studied using thermal analysis and “Ceramic tube” (CT) method. Thermal gravimetric analysis confirms that incorporation of the DETA‐CuCO₃ into DGEBA appreciably heightens the thermal stability and antiflammability of the CuCO₃‐containing epoxy‐amine polymers. Results of CT measurement reveal that maximal temperature of the combustion gases under burning of the DGEBA/DETA‐CuCO₃(12) sample in comparison with unmodified epoxy‐amine polymer (DGEBA/DETA) is lowered on 219°С and the loss of weight is decreased on 20.5 wt%. According to ASTM 635‐14, ASTM D2863‐13, and ASTM D1929‐16, the flame propagation rate, limiting oxygen index, and temperatures of ignition and self‐ignition have been measured for the elaborated polymer samples.     

Thermal and chemical analysis of flammability and combustibility of fir wood in cone calorimeter coupled to FTIR apparatus

This paper deals with the thermal degradation of fir wood in a cone calorimeter under well‐ventilated atmosphere used with a piloted ignition. The thermal and chemical sample decompositions were studied with heat fluxes varying from 15 to 60 kW m^?2. With the cone calorimeter results and equations found in literature, the significant parameters of fir wood sample flammability and combustibility were deduced from ignition time (t_ig), mass loss and gas analysis. These parameters are thermal response parameter, critical heat flux, ignition surface temperature, thermal thickness, mass loss rate, thermal inertia, effective heat of combustion, heat release rate, heat of gasification and others. Moreover, during each experiment, the main gaseous species emissions were continuously and simultaneously monitored. Furthermore, the solid degradation and combustion process for fir wood were described in details. Experimental results from cone calorimeter were compared with data found in literature, and generally, a quite good accordance was found between the both sets of results. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermoanalytical Investigation of Some Binary Pyrotechnic Mixtures of Ammonium Azide as Chemical Gas Generating Systems

The conventional NaN₃/oxidants gas generator pyrotechnic mixtures suffer from leaving undesirable solid residues. The presented investigation aimed to overcome this problem through mixing of NH₄N₃ particles with some metallic components, and to introduce some new gas generator pyrotechnic mixtures. In this work, volatile ammonium azide particles were initially stabilized via microencapsulation technique, and blended with Zr, Ti, ZrH₂, and TiH₂ powders to produce different gas generation mixtures. Thermal properties and kinetic parameters of these pyrotechnic mixtures were investigated by using thermal analysis (TG/DTA and DSC) techniques. The apparent activation energy (E), ΔG^#, ΔH^#, ΔS^#, and critical ignition temperature (T_b) of the ignition processes of the mixtures were obtained from the DSC experiments. Among the investigated mixtures, NH₄N₃/ZrH₂ composition was found to show desirable efficiency, and also it can be considered as a safe pyrotechnic composition for gas generation property, due to its moderate ignition temperature.     

Development of a numerical approach based on coupled CFD/FEM analysis for virtual fire resistance tests—Part A: Thermal analysis of the gas phase combustion and different test specimens

In the present two‐parted study, a numerical approach is shown to consider fire resistance tests in virtual space, including the combustion, thermal analysis of the test specimen, and the deformation process. This part is dealing with the combustion process and thermal analysis of different building materials tested in a fire resistance furnace. Instead of using coupled computational fluid dynamics (CFD)/finite element method simulation for the combustion and thermal heat conduction in the solid, which is commonly used in literature, the present approach considers these transport phenomena in one CFD simulation. This method enables a two‐way coupling between the gas phase and the solid material, where chemical reactions and the release of volatile components into the gas phase can occur (eg, release of water vapour from gypsum). To validate the numerical model, a fire resistance test of a steel door, which is a multilayer construction, and a wall made of gypsum blocks were experimentally and numerically investigated. Due to the chemical reactions inside the gypsum, water vapour is released to the gas phase reducing the flue gas temperature about 80 K. This effect was taken into account using a two‐way coupling in the CFD model, which predicted temperatures in close accordance to the measurement.     

Effect of fiber orientation on viscoelastic properties of polymer matrix composites subjected to thermal cycles

Fibers in polymer composites can be designed in various orientations for their usage in service life. Various fiber orientated polymer composites, which are used in aeroplane and aerospace applications, are frequently subjected to thermal cycles because of the changes in body temperatures at a range of −60 to 150°C during flights. It is an important subject to investigate the visco‐elastic properties of the thermal cycled polymer composite materials which have various fiber orientations during service life. Continuous fiber reinforced composites with a various fiber orientations are subjected to 1,000 thermal cycles between the temperatures of 0 and 100°C. Dynamic mechanic thermal analysis (DMTA) experiments are carried out by TA Q800 type equipment. The changes in glass transition temperature (T_g), storage modulus (E′), loss modulus (E′′) and loss factor (tan δ) are inspected as a function of thermal cycles for different fiber orientations. It was observed that thermal and dynamic mechanical properties of the polymer composites were remarkably changed by thermal cycles. It was also determined that the composites with [45°/−45°]_s fiber orientation presented the lowest dynamic mechanical properties. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

A modified quasi‐creep model for assessment of deformation of topas COC substrates in the thermal bonding of microfluidic devices: Experiments and modeling

The effects of thermomechanical properties of dissimilar polymer plates on thermal bonding were investigated and the resultant deformation of cover Topas COC plate was modeled using a simplified quasi‐creep model. The appropriate conditions for thermal bonding for minimal deformation of both the Topas cover and substrate plates could be established through simulation using the quasi‐creep model. Both the cover plate and the substrate containing microchannels were fabricated by injection molding. The elastic modulus of the COC plate at different temperatures was measured using three‐point bending test. The thermal bonding was conducted at different temperatures, pressures, and holding times. The deformation of the cover plate (consisting of Topas with a lower glass transition temperature, T_g) into the microchannel of the substrate plate (consisting of Topas with a higher T_g) was found to be significant even at lower bonding pressures when the bonding temperature was higher than a critical temperature. Such deformation was dependent on the viscoelastic creep behavior of the material and the thermal bonding temperature and load. This deformation behavior was predicted by the numerical model, and the predicted results agree well with the experimental data. The bonding strength of the sealed microchannels was evaluated using the burst test. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure modification of isotactic polypropylene by bi‐component nucleating systems

The efficiency of heterogeneous nucleation of isotactic polypropylenes (iPP) with various isotacticity and MWD is estimated by an increase of the crystallization temperature (T_cr). A bi‐component nucleating system, composed of a pimelic acid and a calcium stearate, was added to the polymeric matrix in the molten state. The relative increase of T_cr is found to be independent on the structure stereo‐regularity of iPP. On the contrary, dependent on the polymer structure, the investigated nucleating system influences in a different way the creation of the β‐phase. The form of the DSC melting curves, for the β‐phase rich iPP samples, is discussed in terms of various preliminary cooling conditions. The transformation from a multi‐modal form of the DSC melting peak to a simple one is related to the lowering of the cooling rate and to the increase of the heating rate.     

Prediction of the gas permeability of heterogeneous polymer blends

A recently introduced predictive scheme is used to calculate the permeability of various types of heterogeneous polymer blends, which are characterized by the ratio of the permeability of constituents in the range 10–10,000. The scheme combines a two‐parameter equivalent box model and the data on the continuity of constituting phases acquired by modifying equations proposed by the percolation theory; it takes into account the permeability of components and the interval of phase duality (co‐continuity) delimited by the critical volume fractions of components v_1cr and v_2cr. The scheme can be used in two ways: (i) permeability of blends predicted by using the “theoretical” value of parameters v_1cr = v_2cr = 0.16 should be regarded as a first approximation which may not well approximate experimental data due to the fact that real v_1cr and v_2cr are affected by relative viscosities of the components, interfacial energy, conditions of blend mixing, phase structure coarsening, etc.; (ii) conversely, by fitting experimental data, it is possible to determine v_1cr and v_2cr for the studied system; thus the scheme can be alternatively viewed as an efficient tool for phase structure analysis of polymer blends.     

Electric strength of epoxide resins and its relation to the structure

Epoxide resins having various ratios of ether and ester bonds were investigated as to the relation between electric strength and polymer characteristics. The electric strength over a wide range of temperature is presented here. A marked reduction of strength characteristics of the epoxide resins occurs at a critical temperature indistinguishable from the glass transition temperature T_g, which is related to the free volume and molecular relaxation process. At temperatures exceeding T_g, the electric strength has a strong dependence on polymer structure, film thickness, and applied pulse width. This behavior is considered to obey the thermal breakdown mechanism, and it is assumed that the ion is important in the precursory region of electric breakdown.     

Plasticizer diffusion as the rate-determining step in dry blending of poly(vinyl chloride)

Differential thermal analysis has been used to examine the process of dry blending of plasticizer and PVC. The rate of transformation of the glass transition from that of the polymer initially in the cold mix to the glass transition of the blend (blend T_g) has been examined at various temperatures from room temperature to above the polymer T_g. The dependence on temperature of this rate of transformation of the observed T_g is similar to the temperature dependence of the diffusion of plasticizer into PVC. It is concluded that diffusion of plasticizer into polymer particles is the rate-determining step in the dry blending of PVC. It also appears that a single mechanism of diffusion is involved both below and above the glass transition of the polymer.     

Molding of syndiotactic polystyrene under its melting temperature

Syndiotactic polystyrene (SPS), a thermoplastic polymer that exhibits a high T_m in some crystalline forms, can be conveniently processed by a cold‐compaction technique. Processing temperatures in the range of 150–210°C, well below the T_m, gives rise to physicomechanical properties comparable and even better than those obtained by thermal compression or injection molding. The optimum treatment temperature seems to fall around 175°C. X‐ray diffraction analysis, thermal analysis, and density measurements suggest that such behavior is connected to phase transitions of SPS and favored by the presence of styrene included in the crystalline fraction. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 377–383, 2001     

Effect of heating on the structure and existence limits of the combustion front in two-layer specimens

The thermal and concentration structures of the combustion front in two-layer specimens are studied using the methods of mathematical modeling. The combustion limits are determined for various thermal effects and thermophysical characteristics of the layers on the basis of heat losses. Increasing the temperature of the medium in which a specimen is placed is shown to be an effective method of controlling the combustion process. It is established that, for the values of the determining parameters used in the calculations, increasing the temperature by one characteristic intervalT _amb,1=T _in+RT _b,1 ² /E (T _in is the initial temperature of the specimen andT _b,1 is the combustion temperature of the undiluted layer) increases the critical value of the heat-loss coefficient by more than twentyfold. Translated fromFizika Goreniya i Vzryva, Vol. 35, No. 4, pp. 67–74, July–August 1999.     

The microwave processability of semicrystalline polymers

The overall objective of these studies was to investigate the relationship between polymer structure and microwave absorptivity. In this paper, the microwave processing of semicrystalline polymers such as poly(ether ether ketone) (PEEK), nylons, and poly(ethylene terephthalate) (PET), via a cylindrical resonance wave cavity and a rectangular standing wave applicator is described. These polymeric materials were irradiated in low power (< 50W) electric fields at 2.45 GHz. Silicone flexible molds were necessary for improved processing of nylons and PEEK at temperatures below their T_c Rapid heating rates were observed between the glass transition temperature, T_g, and the melting temperature, T_m, for all these polymers provided that T_c was exceeded. Both dynamic mechanical thermal analysis (DMTA) and dielectric thermal analysis (DETA) spectra were utilized to predict the heating phenomena between amorphous and semicrystalline materials and to explain the rapid crystallizing rate of PEEK. above its glass transition temperature. Correlations were drawn between (a) the apparent activation energy and the critical temperature (T_c) and (b) the shape of the dielectric spectra at 2.45 GHz and its shape in kHz region.     

Kinetic thermal behavior of nanocellulose filled polylactic acid filament for fused filament fabrication 3D printing

Fused filament fabrication (FFF) with thermoplastic filaments is the most popular 3D printing technology. The continuous polymer filaments undergo a series of thermal processes, including heating, melting, cooling, and solidification. Therefore, it is necessary to investigate the thermal behavior of polymer filaments. The present study aims to provide a fundamental study of the thermal decomposition behavior and the isothermal melting crystallization behavior of nanocellulose filled polylactic acid (PLA) filaments. The influences of nanocellulose contents on the thermal decomposition properties such as onset temperature (137_onset), the temperature at 20-wt % conversion (T_α20), and the temperature at the peak decomposition rate (T_p) were examined by thermogravimetric analysis (TGA). The effects of nanocellulose contents on the glass transition temperature (T_g) and the melting temperature (T_m) were studied by differential scanning calorimetry (DSC). Effects of nanocellulose and polyethylene glycol (PEG) incorporation on the thermal decomposition activation energy, isothermal melting crystallization rate, and semi-crystallization time are also investigated. The addition of nanocellulose improves the thermal stability of PLA filament, whereas the addition of plasticizer PEG decreases the thermal stability. TGA and DSC kinetic analyses indicate that nanocellulose alone or together with PEG could drastically increase the crystallization rate and shorten the semi-crystallization time. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48374.     

Effect of processing conditions on physical properties of 3‐aminophenoxyphthalonitrile/epoxy laminates

To develop high performances of polymer composite laminates, differential scanning calorimetry and dynamic rheological analysis studies were conducted to show curing behaviors of 3‐aminophenoxyphthalonitrile/epoxy resin (3‐APN/EP) matrix and define cure parameters of manufacturing processes. Glass fiber reinforced 3‐APN/EP (GF/3‐APN/EP) composite laminates were successfully prepared through different processing conditions with three parameters such as pressures, temperatures, and time. Based on flexure tests, dynamic mechanical analysis, thermal gravimetric analysis, and scanning electron microscope, the complementary catalytic effect of the three processing parameters is investigated by studying mechanical behavior, thermomechanical behavior, thermal behavior, and fracture morphology of GF/3‐APN/EP laminates. The 50/50 GF/3‐APN/EP laminates showed a significant improvement in flexural strength, glass transition temperature (T_g), and thermal stability with favorable processing parameters. It was also found that the T_g and thermal stability were significantly improved by the postheated treatment method. The effect of manufacturing process provides a new and simple route for the polymer–matrix composites application, which indicates that the composites can be manufactured at low temperatures. But, they can be used in a high temperature environment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39746.     

Structural changes and molecular motion of polyacrylonitrile fibers during pyrolysis

The stabilization process of polyacrylonitrile (PAN) fiber is necessary to develop high-performance carbon fiber. This work is concerned with studies of the activation energy of PAN fibers during the stabilization process. A wide-angle X-ray diffractometer combined with a fiber specimen holder for heating was used to measure the activation energy of crystal transition E_c. E_c is almost the same as the activation energy of the cyclization reaction E which is measured by a differential thermal analysis (DTA). The variation of crystal size in PAN fiber and a model of the ladder polymer in stabilized fiber transformed from acrylontrile (AN) units of PAN fiber are discussed also. The crystal size of PAN fiber increases when the thermal treatment temperature is raised. When exposed to temperatures above the crystal degradation temperature T_d, the molecular rods of PAN fiber are destroyed completely, and ladder polymer is formed in the ordered phase of the original PAN fiber. The transformation of ladder polymer is initiated in the disordered phase, and then at the boundaries of the ordered phase.     

Effect of high‐temperature annealing on the elastoplastic response of isotactic polypropylene in loading–unloading tests

A series of uniaxial tensile loading–unloading tests is performed on isotactic polypropylene at room temperature. Prior to mechanical testing, injection‐molded specimens are annealed for 24 h at temperatures T = 145, 150, 155, 158, 160, 163, and 165°C, which cover the entire region of high‐temperature annealing temperatures. A constitutive model is developed for the elastoplastic behavior of a semicrystalline polymer at small strains. The stress–strain relations are determined by six adjustable parameters that are found by matching observations in cyclic tests. Fair agreement is demonstrated between the experimental data and the results of numerical simulation. It is shown that all material constants are affected by the annealing temperature, which is explained by changes in the crystalline morphology driven by thermal treatment. Some of the adjustable parameters experience finite jumps in the vicinity of the critical temperature T_c = 159°C. These jumps are attributed to the α₂ → α₂′ phase transformation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 186–196, 2003