Ideality of pressure‐sensitive paint. I. Platinum tetra(pentafluorophenyl)porphine in fluoroacrylic polymer

The pressure sensitive paint (PSP) properties of a fluoroacrylic polymer, FIB, with the luminophor platinum tetra(pentafluorophenyl)porphine (PtTFPP) are presented. This paint forms a hard coating that displays Stern–Volmer plots with a high dynamic range (∼ 0.9) [defined as (I_vac − I_atm)/I_vac], good photostability, a response time of less than 1 s and a relatively low temperature dependence (∼ 0.6% per degree). The temperature dependence is low because FIB has a unusually low activation energy for the diffusion of oxygen. Pressure and temperature affect intensity independently making this PSP “ideal.” The basecoat affects the functionality of the PSP it underlies, and the optimal basecoat used to date also includes the FIB polymer. The synthesis of the FIB polymer is a copolymerization that occurs in one step with a peroxide initiator. Annealing the painted model above T_g = 70°C procures adhesion and ideality. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2795–2804, 2000     

Effect of polymer matrix on the performance of pressure‐sensitive paint comprising 5,10,15,20‐tetrakis(pentafluorophenyl)porphinato platinum(II) and poly(1,1,1,3,3,3‐hexafluoroisopropyl‐co‐tert‐butyl methacrylates)

Copolymers of 1,1,1,3,3,3‐hexafluoroisopropyl methacrylate (HFIPM) and tert‐butyl methacrylate (TBM) were prepared by conventional radical copolymerization as a novel binders for pressure‐sensitive paints (PSP). The monomer reactivity ratios r_HFIPM and r_TBM were determined as 0.45 and 0.67, respectively. The glass transition temperature of the copolymers increased from 77 to 126°C with increasing mole fraction of TBM units in the copolymer. The PSP were formed by combining the resulting copolymers and 5,10,15,20‐tetrakis(pentafluorophenyl)porphinato platinum(II). The pressure and temperature sensitivities of the PSPs were measured at air pressures ranging from 5 to 120 kPa and at temperatures ranging from 0 to 60°C. Modified Stern–Volmer plots indicated slight increases in the pressure sensitivity, but significant decrease in the temperature sensitivity as the mole fraction of HFIPM units increased in the copolymer. Applying a theoretical model to our calibration data, we inferred that luminescence quenching is primarily responsible for increasing the temperature sensitivity in the resulting copolymers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43316.     

Effects of diffusion on the kinetic study of an epoxy system diglycidyl ether of bisphenol A/1,2‐diamine cyclohexane/calcium carbonate filler

The curing reactions of an epoxy system consisting of a diglycidyl ether of bisphenol A (BADGE n = 0), 1,2‐diamine cyclohexane (DCH) with calcium carbonate filler, were studied to determine different kinetic parameters. Two models—one based solely on chemical kinetics and the other accounting for diffusion—were used and compared to experimental data both for systems with and without filler. It was found that 100°C is the optimum service temperature, and also that the presence of the filler has no influence on the optimal service temperature range (60–100°C) of the epoxy system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2285–2295, 2000     

Investigation of rare earth ions adsorption properties of PP‐g‐AA

Acrylic acid (AA) was grafted onto the powdered isotactic polypropylene (i‐PP) with the electron‐beam‐induced preirradiation method (Chen, D.‐T.; Shi, N.; Xu, D.‐F. J Appl Polym Sci 1999, 73, 1357–1362). Some rare earth ions, including Sm³⁺, Nd³⁺, Eu³⁺, Gd³⁺, and Er³⁺, were adsorbed onto the grafting product PP‐g‐AA. The properties of Sm³⁺ adsorbed were investigated in detail. These properties include the influences of the adsorption time, acidity, ion concentration of the solution, grafting yield of AA onto i‐PP, and temperature on the quantity and efficiency of the ion adsorption. Some kinetic and thermodynamic equilibrium constants of the adsorption were obtained in the experiments. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1549–1553, 2000     

Influence of irradiation conditions on the electrical behavior of polyethylene–carbon black conductive composites

The temperature‐dependent resistivity behavior of carbon black–loaded polyethylene (PE) composites irradiated both at room temperature and 170°C above the PE melting point was studied. The irradiation doses were varied. At a given loading level, irradiation at room temperature corresponded to an energy treatment on a low‐resistive, solid, three‐phase composite system, while at a high temperature it corresponded to a treatment on high‐resistive, viscous, two‐phase system. The irradiation condition had a complicated influence on the electrical response to temperature. The resulting composite structure was analyzed by using differential scanning calorimetry, gel fraction, and wide‐angle X‐ray diffraction. The results were then discussed by comparing them with those of the unirradiated sample. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 494–499, 2000     

Effect of high‐temperature annealing on the microstructure and mechanical properties of polypropylene with shish kebab or spherulite structure

Various annealing temperatures below, near, or above the melting temperature were used to anneal polypropylene with oriented shish kebab and isolated spherulite structures in this work. The results showed that a high annealing temperature decreases the time needed to achieve the ideal material property. When the annealing temperature is near or above the melting temperature, the impact strength would be 1.6 times improved by partial melting and recrystallization. The crystal structure of the oriented shish kebab or isolated spherulite structures was improved when annealed at 150 °C, whereas annealing at 165 or 170 °C recombined the crystal lamellae of the structure. Moreover, the high crystallinity and thick lamellae improved the impact and yield strength values of the spherulite structure. However, excessively high crystallinity and thick lamellae in the oriented shish kebab structure did not result in good mechanical performance. Therefore, the prediction of mechanical properties for the shish kebab structure based on crystallinity and lamellar thickness is not feasible. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46465.     

Humid aging of polyetherimide. I. Water sorption characteristics

The sorption and desorption kinetics of water into polyetherimide (ULTEM 1000) were studied at various temperatures ranging from 20 to 100°C. The water equilibrium concentration increases slightly with temperature from 1.39% (by weight) at 20°C to 1.50% at 100°C. The solubility coefficient, S, calculated from these data, and the water vapor pressure decrease with temperature. The calculated heat of dissolution H_s is close to −43 kJ mol⁻¹, which explains the low effect of temperature on the equilibrium concentration. The diffusion coefficient, D, varies from about 1.10⁻¹² m² · s⁻¹ at 20°C to about 16.10⁻¹² m² · s⁻¹ at 100°C. The apparent activation energy of diffusion, E_D, and the heat of dissolution, H_s, of water in the polymer have opposite values (respectively, +43 and −42 kJ · mol⁻¹). From this observation and a comparison of these data with water diffusion characteristics in other glassy polar polymers, it is hypothesized that the transport rate of water is kinetically controlled by the dissociation of water–polymer complexes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1439–1444, 2000     

Volatile products of poly(ethylene terephthalate) thermal degradation in nitrogen atmosphere

Thermal degradation of PET was studied in a nitrogen atmosphere at 200–700°C. The experiments were carried out in a tubular furnace under isothermal conditions. The volatile substances evolved from PET were identified and quantified. Weight losses of PET during the thermal degradation in different temperatures were determined. The results are presented on plots as a function of the degradation temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1894–1901, 2000     

Rheology of cellulosic N‐methylmorpholine oxide monohydrate solutions

Shear dynamic and elongational rheology of concentrated solutions of cellulose in N‐methylmorpholine oxide monohydrate (lyocell) were investigated at different temperatures and for two Hencky strains. Shear thinning and strain thinning behavior is characteristic for dynamic viscosity and effective elongational viscosity of lyocell solutions. Body forces, enthalpy, and entropy of orientation are high at low temperature and high deformation rates, showing a strong orientation effect. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1369–1377, 2000     

Epoxy–imide resins from N‐(4‐ and 3‐carboxyphenyl)trimellitimides. I. Adhesive and thermal properties

Epoxy–imide resins were obtained by curing Araldite GY 250 (diglycidyl ether of bisphenol‐A and epichlorohydrin; difunctional) and Araldite EPN 1138 (Novolac–epoxy resin; polyfunctional) with N‐(4‐ and 3‐carboxyphenyl)trimellitimides derived from 4‐ and 3‐aminobenzoic acids and trimellitic anhydride. The adhesive lap shear strength of epoxy–imide systems at room temperature and at 100, 125, and 150°C was determined on stainless‐steel substrates. Araldite GY 250‐based systems give a room‐temperature adhesive lap shear strength of about 23 MPa and 49–56% of the room‐temperature adhesive strength is retained at 150°C. Araldite EPN 1138‐based systems give a room‐temperature adhesive lap shear strength of 16–19 MPa and 100% retention of room‐temperature adhesive strength is observed at 150°C. Glass transition temperatures of the Araldite GY 250‐based systems are in the range of 132–139°C and those of the Araldite EPN 1138‐based systems are in the range of 158–170°C. All these systems are thermally stable up to 360°C. The char residues of Araldite GY 250‐ and Araldite EPN 1138‐based systems are in the range of 22–26% and 41–42% at 900°C, respectively. Araldite EPN 1138‐based systems show a higher retention of adhesive strength at 150°C and have higher thermal stability and T_g when compared to Araldite GY 250‐based systems. This has been attributed to the high crosslinking possible with Araldite EPN 1138‐based systems arising due to the polyfunctional nature of Araldite EPN 1138. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1729–1736, 2000     

Relationship between the crystalline structure and mechanical behavior in isotropic and oriented polyamide 12

This study reports on the relationship between the crystalline structure and mechanical behavior of differently processed and annealed polyamide 12 (PA12) samples. Two sets of samples were obtained: isotropic PA12 films prepared by hot pressing and oriented cables prepared by consecutive extrusion and cold drawing. These samples were isothermally annealed in the range of 80–160°C and then subjected to tensile tests at room temperature. A combination of solid-state ¹³C-NMR and synchrotron wide- and small-angle X-ray scattering was used to obtain reliable structural data from these samples before and after the tensile tests. These structural data were related to the mechanical properties of the respective PA12 samples. Deformation models explaining all the experimental results were suggested for the different PA12 samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of silane‐grafted polypropylene on the mechanical properties and crystallization behavior of talc/polypropylene composites

Talc‐filled polypropylene (PP) composites coupled with silane‐grafted polypropylene (PP‐g‐Si) were prepared. Effect of PP‐g‐Si on the mechanical properties, crystallization, and melting behavior of PP composites was investigated. Compared with the uncoupled composites, the mechanical properties of Talc/PP composites coupled with a small amount of PP‐g‐Si were increased to some extent. Meanwhile, PP‐g‐Si can promote crystallization rate and increase crystallization temperature of PP in the composites. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2974–2977, 2000     

Proton exchange membranes prepared by simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films. II. Properties of sulfonated membranes

Proton exchange membranes were prepared by radiation‐induced grafting of styrene onto commercial poly(tetrafluoroethylene‐co‐hexafluoropropylene) films using a simultaneous irradiation technique followed by a sulfonation reaction. The resulting membranes were characterized by measuring their physicochemical properties such as water uptake, ion exchange capacity, hydration number, and proton conductivity as a function of the degree of grafting. The thermal properties (melting and glass transition temperatures) and thermal stability of the membrane were also investigated using differential scanning calorimetry and thermal gravimetric analysis, respectively. Membranes having degrees of grafting of 16% and above showed proton conductivity of the magnitude of 10⁻² Ω⁻¹ cm⁻¹ at room temperature, as well as thermal stability at up to 290°C under an oxygen atmosphere. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2443–2453, 2000     

Catalytic pyrolysis of polyvinylchloride in the presence of metal chloride

The pyrolysis of polyvinylchloride (PVC) was studied in a quartz reactor with and without the addition of metal chlorides as catalysts. The results indicated that the addition of metal chlorides such us ZnCl₂ or BaCl₂ decreased the temperature of dehydrochlorination of PVC. The introduction of H₂ in pyrolysis enhanced the degradation of PVC at 400°C or higher and decreased the amount of solid residue. Gas chromatography/mass spectroscopy analysis indicated that Zn and Ba chlorides reduced the formation of high molecular weight products. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2464–2471, 2000     

Effect of blending on the multiple melting behavior of polyphenylene sulfide

The effects of melting time (t_melt) and annealing time (t_a) at a temperature closer to the melting point of polyphenylene sulfide (PPS) on the multiple melting behavior of neat PPS, and PPS component in their blends have been investigated by differential scanning calorimetry (DSC). It is found that double endotherm peak of PPS annealed at 275°C for less than three hours is different from that annealed for twelve hours. Double endotherm peak of PPS in PEEK/PPS blends shifts to lower temperature, and the intensity of the upper melting peak decreases significantly by addition of polyether ether ketone (PEEK). An additional third melting peak could be observed. The temperature of third melting peak is above 310°C and increases as the t_a and PEEK content are increased. For PEK-C/PPS blends, the lower and upper melting temperatures of the PPS component are higher than that of neat PPS annealed at 275°C for twenty-three hours. © 1996 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1001–1008, 1997     

Analysis of annealed thin polymer films prepared from dichloro(methyl)phenylsilane by plasma polymerization

Thin plasma polymer films were deposited from a mixture of dichloro(methyl)phenylsilane (DCMPS) vapor and gaseous hydrogen in an rf (13.56 MHz) capacitive coupling deposition system on pieces of silicon wafers. Some of samples were annealed in a vacuum to temperatures ranging from 450 to 700°C. The chemical composition, structure, and surface morphology of the annealed samples and those stored in air at room temperature were studied by FTIR, XPS, SEM, and optical microscopy. The thermal stability and decomposition of the plasma polymer with increasing temperature were characterized using thermogravimetry together with mass spectrometry. The plasma polymer was stable to a temperature of 300°C. Above that temperature, the material started to decompose together with additional crosslinking due to the incorporation of extra oxygen atoms forming new siloxane bonds. The plasma polymer was tough at room temperature but much more brittle after annealing. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2106–2112, 2001     

Photon transmission method for studying film formation from polstyrene latexes with different molecular weights

A photon‐transmission method was used to probe the evolution of transparency during film formation from polystyrene (PS) particles with different molecular weights. The latex films were formed at room temperature from the PS particles having two different average molecular weights and annealed at elevated temperatures in various time intervals above the glass transition (T_g). Onset temperatures (T_H) at given times (τ_H) for the optical clarity of films formed from low (LM) and high molecular (HM) weight PS particles were used to calculate the healing activation energies for the minor chains and found to be 22.0 ± 0.5 and 27.0 ± 0.6 kcal/mol, respectively. The increase in the transmitted photon intensity, I_tr, above the T_H was attributed to increase in the number of interfaces that disappeared. The Prager–Tirrell (PT) model was employed to interpret the increase in crossing density at the junction surface. The backbone activation energies (ΔE) were measured and found to be 127.8 ± 2.5 kcal/mol for a diffusing polymer chain across the junction surface for LM and HM latex films. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 866–874, 2000     

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     

On the mechanism of compatibilization of polyolefin/liquid crystalline polymer blends with graft copolymers

The compatibilization mechanism of some compatibilizers for blends of polyolefins with a liquid crystalline polymer (LCP) was studied. Polyethylene (PE) and polypropylene (PP) were blended with a semirigid LCP (SBH) in a batch mixer, either with and without compatibilizers. The latter were two commercially available samples of functionalized polyolefins, that is, a PE‐g‐MA (HDM) and a PP‐g‐AA (Polybond 1001) copolymer and some purposely synthesized PE‐g‐LCP and PP‐g‐LCP copolymers. Microtomed films of the binary and the ternary blends were annealed at 240°C on the hot stage of a polarizing microscope and the changes undergone by their morphology were recorded as a function of time. The results indicate that the compatibilizers lower the interfacial tension, thereby providing an improvement of the minor phase dispersion. In addition to this, the rate of the coalescence caused by the high‐temperature treatment is appreciably reduced in the systems compatibilized with the PE–SBH and PP–SBH graft copolymers. Among the commercial compatibilizers, only Polybond 1001 displayed an effect comparable to that of the above copolymers. HDM improved the morphology of the as‐prepared PE blends, but failed to grant sufficient morphological stabilization against annealing‐induced coarsening. The results are discussed with reference to the chemical structure of the different compatibilizers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3027–3034, 2000     

Viscoelastic properties and structure of the zone‐drawn polyaniline films

The zone‐drawing method was applied to chemically synthesized polyaniline cast films of emeraldine base under various applied tensions and drawing temperatures. The changes in the microstructure and viscoelastic properties of the resulting films were investigated. It was found that the microstructure was strongly affected by the drawing temperature (T_d). The crystallinity, crystallite size, and orientation factor of crystallites, respectively, attained 42%, 23 Å, and 0.975 for the film zone‐drawn at T_d = 170°C, whereas a further increase in the T_d brought about a decrease of these values. The viscoelastic measurements indicated that the dynamic storage modulus attained 12 GPa at room temperature and was 5 GPa at 280°C for the film zone‐drawn at T_d = 210°C, which was comparable to that of the typical engineering plastics. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 566–571, 2000