Water states and thermal processability of boric acid modified poly(vinyl alcohol)

To further improve the processability of water plasticized poly(vinyl alcohol) (PVA), boric acid (BA), which can rapidly form reversible crosslinked structure with the hydroxyl groups of PVA, was adopted as a modifier, and the water states, thermal performance, and rheological properties of modified PVA were investigated. The results showed that ascribing to the formation of the crosslinked structure between PVA and BA, the content of nonfreezing water in system increased, indicating that the bondage of PVA matrix on water enhanced, thus retarding the tempestuous evaporation of water in system during melt process and making more water remained in system to play the role of plasticizer. Meanwhile, this crosslinked structure shielded part hydroxyl groups in PVA chains, leading to the further weakening of the self‐hydrogen bonding of PVA, and guaranteeing a lower melting point and higher decomposition temperature, thus obtaining a quite wide thermal processing window, i.e., ≥179°C. The melt viscosity of BA modified PVA slightly increased, but still satisfied the requirements for thermal processing, thus reinforcing the flow stability of the melt at high shearing rate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43246.     

Effects of dianhydrides on the thermal behavior of linear and crosslinked polyimides

To determine the thermal characteristics of linear and crosslinked polyimides (PIs), BTDA, ODPA, and 6FDA were used to synthesize polyimides. Thermal degradation temperature and glass transition temperature of the resulting PIs were measured using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). To measure the change in modulus and coefficient of thermal expansion (CTE) depending on dianhydride structure, a dynamic mechanical analyzer (DMA) and thermo‐mechanical analyzer (TMA) were used. The thermal degradation and glass transition temperature properties of linear PIs varied according to whether the linear chain adopted a bulky or flexible structure. Dynamic modulus and thermal expansion values of linear polyimides also showed good agreement with the TGA and DSC results. As we expected, linear polyimide with bulky 6FDA groups showed better thermal behavior than the flexible polyimides. Crosslinked polyimide nadic end‐capped (norbornene) with a bulky dianhydride group had a lower thermal degradation temperature and higher CTE than flexible BTDA and ODPA polyimides. Our results indicate that the mobility of the dianhydride group affects the thermal behaviors of linear and crosslinked polyimides in different ways. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41412.     

Preparation and characterization of soluble bismaleimide‐triazine resins based on asymmetric bismaleimide

A series of bismaleimide‐triazine resins (EBT) were prepared from 2‐(4′‐maleimido)phenyl‐2‐(4′‐maleimidophenoxyl)phenylbutane (EBA‐BMI) and 2,2‐bis(4‐cyanatophenyl)propane (BADCy). The resins show attractive processability with good solubility in low boiling point solvents and wide processing temperature windows. Introduction of diallylbisphenol A (DBA) can decrease the curing temperature of EBT resins that the curing exothermic peak temperature shifted from 291 to 237 °C as the content of DBA increased from 0 to 20%. The curing condition influenced the thermal properties of the cured EBT resins. The glass transition temperature increased as the curing temperature and curing time increased. The cured EBT resins show high glass transition temperature up to 352 °C, high thermal stability with 5% weight loss temperature over 405 °C, low coefficient of thermal expansion about 45 to 52 ppm/°C, and high storage modulus up to 2.6 GPa at 250 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44519.     

Thermal stability of modified end‐capped poly(lactic acid)

The influence of functional end groups on the thermal stability of poly(lactic acid) (PLA) in nitrogen‐ and oxygen‐enriched atmospheres has been investigated in this article using differential scanning calorimetry, thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). Functional end groups of PLA were modified by succinic anhydride and l ‐cysteine by the addition–elimination reaction. PLA was synthesized by azeotropic condensation of l ‐lactic acid in xylene and characterized by nuclear magnetic resonance. The values of the activation energies determined by TGA in nitrogen and oxygen atmospheres revealed that the character of functional end groups has remarkable influence on the thermal stability of PLA. Moreover, DMA confirmed the strong influence of functional end groups of PLA on polymer chains motion. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41105.     

Curing reaction of molybdenum–phenolic resins

The curing behavior and curing reaction kinetics of novel molybdenum–phenolic resins were studied with differential scanning calorimetry and thermogravimetry methods, the thermal degradation properties of the cured products were studied with thermogravimetry, and the mechanism of the curing reaction was investigated with Fourier transform infrared. When the mixing ratio of the molybdenum–phenolic resin (with 12% molybdenum) to the curing agent was 100/10 (w/w), the curing temperature and activation energy were at a minimum, the thermal degradation stability of the cured product was optimal, and the temperature corresponding to the maximum extent of curing was 200°C. The curing mechanism was similar to that of conventional phenolic systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1410–1415, 2003     

Structure–property relationship of poly(cyclohexane 1,4-dimethylene terephthalate) modified with high trans-1,4-cyclohexanedimethanol and 2,6-naphthalene dicarboxylicacid

A series of novel poly(1,4-cyclohexanedimthylene terephthalate-co-1,4-cyclohxylenedimethylene 2,6-naphthalenedicarboxylate) (PCTN) copolyesters were successfully melt polymerized using different content of trans- or cis-isomers. Before evaluations, the performance properties, their actual chemical composition, chemical structure, and molecular weight were determined using proton nuclear magnetic resonance (¹H-NMR), Fourier transform infrared spectroscopy (FTIR), and intrinsic viscosity (IV) measurements. Thermal studies of obtained copolyesters were carried out using differential scanning calorimetry (DSC). Thermal degradation behaviors were analyzed by thermogravimetric analysis (TGA). Randomly oriented film specimens were developed using a hot-press and their thermal, barrier, dimensional stability, and optical properties were analyzed and compared with conventional poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN). The results revealed that glass transition temperature (T_g), melting temperature (T_m), and crystallinity (X_c) of the synthesized copolyesters are increased in a linear trend by increasing the trans-1,4-cyclohexanedimethanol (trans-CHDM) isomers. It was also found that synthesized films had better thermal, barrier, optical, and dimensional stability properties than conventional PET and PEN films. Results clearly indicated that high trans-CHDM isomers significantly improve the performance properties of the fabricated films. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48950.     

The effect of formaldehyde/phenol (F/P) molar ratios on function and curing kinetics of high‐solid resol phenolic resins

A series of high‐solid resol phenolic resins (HSRPRs) were synthesized with different molar ratios (1.6, 1.8, 2.0, 2.2, and 2.4) of formaldehyde to phenol using calcium oxide and sodium hydroxide as catalyst. The effects of F/P molar ratios on physical properties, free formaldehyde and phenol, activity, structure, and thermally resistant properties of HSRPRs were fully investigated by chemical assays, liquid and solid ¹³C‐NMR, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The curing kinetics of different F/P molar ratios were explored with differential scanning calorimeter at four different heating rates (5, 10, 15, 20°C/min) from 35 to 200°C. Overall, HSRPRs with F/P = 2.0 had excellent comprehensive properties. The study was significant in solving the wastewater problem during the process of industry‐scale preparation of HSRPRs. We believed that the experimental findings would provide a new avenue for further study and application of HSRPRs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of low molecular weight silk fibroin by high‐temperature and high‐pressure method

A low molecular weight silk fibroin powder (LMSF) was prepared through high temperature (200°C) and high pressure (20 kgf/cm²), without any addition of chemicals. The carbonized adducts produced during this process were then removed by treatment with activated charcoal. The yield of LMSF by this preparation method was over 60% after the removal of carbonized adducts by using activated charcoal. Amino acid analysis showed an observable decrease in contents of serine and tyrosine in LMSF prepared by this method, as compared to those prepared by neutral salt. The molecular weight of this LMSF was also observably decreased with an increase in the reaction time. From the measurements of differential scanning calorimeter (DSC) and thermal gravimetric analyzer (TGA), thermal properties of LMSF through high temperature and high pressure were also decreased as compared to those produced by neutral salts. In addition, wide‐angle X‐ray diffraction (WAXD) patterns showed that the crystallinity of LMSF differed from that of the original silk fibroin. It can be said that the preparation method of LMSF in this study is a simple, economical, and environmentally compatible process with many advantages. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2890–2895, 2002     

Improvements in the thermal conductivity and mechanical properties of phase‐change microcapsules with oxygen‐plasma‐modified multiwalled carbon nanotubes

The thermal properties and mechanical properties are the key factors of phase‐change microcapsules (microPCMs) in energy‐storage applications. In this study, microPCMs based on an n‐octadecane (C18) core and a melamine–urea–formaldehyde (MUF) shell supplemented with O₂‐plasma‐modified multiwalled carbon nanotubes (CNTs) were synthesized through in situ polymerization. Meanwhile, two different addition methods, the addition of modified CNTs into the emulsion system or into the polymer system, were compared and examined. Scanning electron microscopy micrographs showed that the microPCMs were spherical and had a broadened size distribution. Fourier transform infrared testing demonstrated that the modified CNTs did not affect C18 coated by MUF resin. The results indicate that the thermal conductivity and mechanical properties of the microPCMs were remarkably improved by the addition of a moderate amount of modified CNTs, but the heat enthalpy and encapsulated efficiency decreased slightly. Moreover, the thermal conductivity and mechanical properties of microPCMs modified with CNTs directly added to the polymer system were superior to those with CNTs added to emulsion system. In particular, when 0.2 g of modified CNTs were added to the polymer system, the thermal conductivity of the microPCMs was improved by 225%, and the breakage rates of the microPCMs at 4000 rpm for 5, 10, and 20 min decreased by 74, 72, and 60%, respectively, compared with that of the microPCMs without modified CNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45269.     

Evolution of interactions between water and native corn starch as a function of moisture content

Thermostimulated current spectroscopy, thermogravimetric analysis, and differential scanning calorimetry (DSC) were used to study starch–water systems with moisture contents of 0–50% (on a total weight basis). DSC enabled the calculation of the amounts of bound and free water. The maximum quantity of bound water was detected for a 30% humidity sample. The existence of interactions between water and starch was proved and found to be weakened for samples containing more than 30% water. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2860–2865, 2002     

Thermal properties of acrylonitrile/itaconic acid polymers in oxidative and nonoxidative atmospheres

Thermal stabilization of polyacrylonitrile (PAN) fibers is an indispensable process in the manufacture of carbon fibers. The effects of acidic comonomers on the thermal properties of PAN have attracted much attention because of their importance in the fibers spinning and heat treatment process. In this study, oxidative and nonoxidative atmospheres are adopted in differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) test to disclose the key effects of oxygen on the thermal properties of PAN/itaconic acid (IA) polymers. The DSC results under oxidative atmosphere are consistence to the reports by previous researchers: the exothermic curves of copolymers containing 0.6 wt % and 1.0 wt % IA exhibit lower initiation temperature and more broaden shapes than that of PAN homopolymer, indicating that IA facilitates both cyclization and oxidation reactions. However, copolymers containing the same content of IA shows no apparent improving effect on the thermal properties under inert atmosphere, which has not been mentioned in the published literature. TGA indicates that oxygen remarkably increases the thermal stability of AN/IA copolymers structure, and will bring high carbon yield in the eventual carbon fibers. The influential mechanisms of oxidative and nonoxidative atmospheres on thermal stabilization reactions of PAN were discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of the carbonyl content on the properties of composite films based on oxidized starch and gelatin

To improve the properties of gelatin, oxidized starch (OS) with different carbonyl content was introduced into the gelatin. In this study, we researched the influence of the carbonyl content of OS on the rheological characteristics, swelling behavior, thermal properties, and wettability of the modified gelatin film (MGF). The MGF samples were prepared by the casting of a 10% w/w solution of gelatin and OS with 18.9, 38.7, and 49.3% carbonyl content, respectively. The results of the dynamic viscosity demonstrated that the influence of the temperature on the rheological characteristics of native gelatin film (NGF) was more obvious than that of MGF. Meanwhile, the viscosity of the samples decreased with increasing carbonyl content in OS. Both the differential scanning calorimetry and thermogravimetry curves indicated that the denaturation and pyrogenic decomposition temperatures of the MGF samples were higher than those of NGF; this meant that the crosslinking between NGF and OS improved the physicochemical properties of gelatin. Compared with the NGF sample, MGF was less hydrophilic because the hydrophilic groups of gelatin could be shielded by OS. Meanwhile, the acid–base and salt sensitivity of the MGF samples were very obvious; therefore, the MGF samples could potentially be used as biomedical materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3809–3815, 2013     

Preparation of segmented semifluorinated poly(aryl ether)s from aromatic trifluorovinyl ethers and oligo(ethylene glycol)s

A series of new segmented semifluorinated polyaryl ethers (PAEs) containing a biphenyl segmented by semifluorinated oligoethylene (SFE) units were prepared by nucleophilic addition of a commercial oligo(ethylene glycol)s to 4,4′‐bis(4‐trifluorovinyloxy)biphenyl. These new thermoplastics were characterized by ¹H and F¹⁹ nuclear magnetic resonance (NMR) and attenuated total reflectance Fourier transform infrared (ATR‐FTIR). Gel permeation chromatography (GPC) analysis displayed number average molecular weights (M_ns) from 9000 to 13,000. Thermal properties of the polymers were studied by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). DSC chromatograms displayed glass transition temperatures (T_gs) from 11 to 1°C. The onsets of degradations were observed by TGA analysis between 313 to 333°C in air and 326 to 363°C in nitrogen, respectively. A second onset of degradation was observed from 452 to 470°C for all polymers. In addition, crystalline morphologies were studied by tapping mode atomic force microscopy (TM‐AFM) and showed needle‐like crystallites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41798.     

Binary mixtures of polyethylene and oxidized wax: Dependency of thermal and mechanical properties upon mixing procedure

The influence of the preparation procedure on the thermal and mechanical properties of linear low‐density polyethylene (LLDPE)– and LDPE–oxidized wax blends was investigated. It was found that mechanically mixed blends show reduced thermal stability as well as ultimate mechanical properties (stress and strain at break) compared to that of extrusion mixed blends. However, the structure of the blend and consequently its thermal and mechanical behavior also depend on the initial morphology of polyethylene. DSC measurements show miscibility up to high wax contents in both blend types, but increasing the amount of wax in LDPE blends induces increasing crystallinity. As a result, the LDPE/wax blends show improved thermal stability of between 20 and 50°C at low wax concentrations. Although the elasticity modulus of the blends increases, increasing the amount of wax generally degrades the mechanical properties. The main reason for this is the reduced number of tie chains. Changes in the average concentration of tie chains with increasing wax content were calculated and a correlation was made with the ultimate properties of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2446–2456, 2003     

Influence of various reaction media on the thermal and rheological properties of poly(acrylamide‐co‐N‐hexadecylacrylamide)

A hydrophobically modified polyacrylamide (PAM) was synthesized by the copolymerization of acrylamide (Am) and N‐hexadecylacrylamide (hAm) through solution copolymerization in a polar organic solvent. Polymer synthesis was performed in three nonaqueous media, including dimethyl sulfoxide (DMSO), a mixture of DMSO and an anionic surfactant such as sodium dodecyl sulfate, and a mixture of DMSO and an acidic surfactant such as dodecyl benzene sulfonic acid. The obtained copolymer, poly(acrylamide‐co‐N‐hexadecylacrylamide) [poly(Am‐co‐hAm)], was characterized by ¹H‐NMR. The physical properties of poly(Am‐co‐hAm)s synthesized in different media were compared with those of PAM and with each other by viscosity measurement, X‐ray diffraction, thermogravimetric analysis, and differential scanning calorimetry. We investigated the ways in which the polymerization medium affected the hydrophobic distribution within the resulting copolymer structure. This aspect, in turn, should have altered the solution properties and the microstructure of the copolymer. For this purpose, we studied the viscometric behavior in diluted solutions, the thermal behavior and thermal stability of the copolymers, and finally, the crystalline structure of the copolymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39939.     

Charge dynamics and thermal properties of epoxy based micro and nano hybrid composites at high temperatures

This paper presents the effects of the filler type and testing temperature on the charge dynamics and thermal properties of the epoxy resin. The micro-nano hybrid composites with different content of the micro and nano aluminum nitride (AlN) fillers are fabricated. The morphology of micro-nano hybrid composites is characterized. Electrical testing and thermal analysis methods are adopted to analyze its electrical and thermal performance. The results show that the space charge accumulation is suppressed and the charge decay process is facilitated in the hybrid composites. The electrical performances of the hybrid composites are enhanced by the nano-fillers. The apparent mobility and activation energy are decreased with nano-AlN fillers in the composites at the high temperature. The glass transition temperature and thermal stability of the materials is improved with the nano-AlN. A hypothetical mechanism is proposed to explain the charge carrier injection and transport of the composites at different temperatures.     

Fire‐retardant properties of the viscose rayon containing alkoxycyclotriphosphazene

The viscose rayon containing cyclotriphosphazene were prepared by the method of blending spinning. The combustibility and thermal stability of the fire‐retardant viscose rayon were evaluated by 45 ° slope burning method, limit oxygen index (LOI), differential scanning calorimetry, thermogravimetry analysis. The results indicated that the LOI of the modified fiber could reach LOI ≥ 28, and the combustibility of the modified fiber could reach the fire‐retardant standard of Japan industry standard JIS 10 91–77 (times of ignition ≥ 3 times). The analysis of the fiber's thermal degradation suggested that the flame retardant plays a multirole of heat absorption, catalytic dehydration and carbonization, condensation‐phase and gas‐phase flame retardation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 698–702, 2006     

Thermal properties of extruded/injection‐molded poly(lactic acid) and biobased composites

To determine the degree of compatibility between poly(lactic acid) and different biomaterials (fibers), poly(lactic acid) was compounded with sugar beet pulp and apple fibers. The fibers were added in 85 : 15 and 70 : 30 poly(lactic acid)/fiber ratios. The composites were blended by extrusion followed by injection molding. Differential scanning calorimetry and thermogravimetric analysis were used to analyze the extruded and extruded/injection‐molded composites. After melting in sealed differential scanning calorimetry pans, the composites were cooled through immersion in liquid nitrogen and aged (stored) at room temperature for 0, 7, 15, and 30 days. After storage, the samples were heated from 25 to 180°C at 10°C/min. The neat poly(lactic acid) showed a glass‐transition transition at 59°C with a change in heat capacity (ΔC_p) value of 0.464. The glass transition was followed by crystallization and melting transitions. The enthalpic relaxation of the poly(lactic acid) and composites steadily increased as a function of the storage time. Although the presence of fibers had little effect on the enthalpic relaxation, injection molding reduced the enthalpic relaxation. The crystallinity percentage of the unprocessed neat poly(lactic acid) dropped by 95% after extrusion and by 80% for the extruded/injection‐molded composites. The degradation was performed in air and nitrogen environments. The degradation activation energy of neat poly(lactic acid) exhibited a significant drop in the nitrogen environment, although it increased in air. This meant that the poly(lactic acid) was more resistant to degradation in the presence of oxygen. Overall, injection molding appeared to reduce the activation energy for all the composites. Sugar beet pulp significantly reduced the activation energy in a nitrogen environment. In an air environment, both sugar beet pulp and apple fibers increased the activation energy. The enzymatic degradation of the composites showed a higher degradation rate for the extruded samples versus the extruded/injection‐molded composites, whereas the apple composites exhibited higher weight loss. The thermogravimetric analysis data showed that the degradation of unprocessed and extruded neat poly(lactic acid) followed a one‐step mechanism, whereas extruded/injection‐molded composites showed two‐step degradation. A higher fiber content resulted in up to three‐step degradation mechanisms. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Protection of high‐density polyethylene–silicon composites from ultraviolet–visible photodegradation

The extent of the ultraviolet–visible (UV–vis) photoirradiation effect on high‐density polyethylene (HDPE) and HDPE–silicon (Si) composites is reported in terms of the addition of Si microparticles at contents of 0.1, 1, and 5 wt %. A standard accelerated UV–vis exposure was applied over 2750 h, corresponding to 22 months in Florida. Thermogravimetry, differential scanning calorimetry, and Fourier transform infrared spectroscopy were used as reliable techniques for monitoring the quality of the HDPE–Si composites. The increasing addition of Si microparticles delayed the photodegradation of the HDPE–Si composites. Because of their strong light‐scattering effects, Si microparticles blocked the degradation of tertiary carbons of the HDPE backbone and reduced the apparition of vinyl groups; this prevented the structural impoverishment of HDPE–Si composites. Consequently, variations in the crystallization temperature (T_c) and melting temperature (T_m), which were indicators of photodegradation, were not modified. In general, the HDPE–Si composite formulation with 5 wt % Si microparticles was useful for protecting the material from photodegradation and, thus, should be an environmentally friendly, reliable alternative UV–vis blocker. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45439.     

Recovery of heavy metals from aqueous solution by using radiation crosslinked poly(vinyl alcohol)

Crosslinked poly(vinyl alcohol) (PVA) and PVA/acrylic acid hydrogels, prepared by γ‐irradiation, were used in the removal of heavy metals from aqueous solution. Comparative studies of the properties of the two hydrogels were made. The application of the prepared hydrogels as adsorbent materials for Cu²⁺, Co²⁺, and Ni²⁺ from aqueous solution was studied. The chemical and physical properties of the hydrogels, before and after adsorption of the heavy metal ions, were investigated by means of thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy. The efficiency of such hydrogels for the recovery of metal ions was determined by atomic absorption and UV spectroscopic analysis. The effect of changing pH on the metal uptake was also studied. It was found that the prepared hydrogels have a substantial ability to adsorb metal ions from their solution. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1649–1656, 2004