Crystallization and melting behavior of amorphous poly(iminosebacoyl iminodecamethylene)

Multiple melting behavior was observed in the differential scanning calorimetry (DSC) scans for the isothermally crystallized poly(iminosebacoyl iminodecamethylene) (PA1010) samples. Coexistence of crystal populations with different lamellar thickness in PA1010 was discussed by means of DSC, wide‐angle X‐ray diffraction (WAXD), and small‐angle X‐ray scattering techniques. During crystallization of the polymer, a major lamellar crystal population developed first, which possessed a higher melting temperature. However, a small fraction of the polymer formed minor crystal population with thinner lamellae, which was metastable and, upon post‐annealing, could grow into more stable and thicker lamellae through melting and recrystallization process. Lamellae insertion or stacks would develop during the post‐annealing at a lower temperature for the isothermally crystallized samples; thus, multiple crystal populations with different thickness could be produced. It is the multiple distribution of lamella thickness that gives rise to multiple melting behavior of crystalline polymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 993–1002, 2000     

Blends of polyamide1010 with unmodified and maleic‐anhydride‐grafted high‐impact polystyrene

The crystallization behaviors, dynamic mechanical properties, tensile, and morphology features of polyamide1010 (PA1010) blends with the high‐impact polystyrene (HIPS) were examined at a wide composition range. Both unmodified and maleic‐anhydride‐(MA)‐grafted HIPS (HIPS‐g‐MA) were used. It was found that the domain size of HIPS‐g‐MA was much smaller than that of HIPS at the same compositions in the blends. The mechanical performances of PA1010–HIPS‐g‐MA blends were enhanced much more than that of PA1010–HIPS blends. The crystallization temperature of PA1010 shifted towards higher temperature as HIPS‐g‐MA increased from 20 to 50% in the blends. For the blends with a dispersed PA phase (≤35 wt %), the T_c of PA1010 shifted towards lower temperature, from 178 to 83°C. An additional transition was detected at a temperature located between the T_g's of PA1010 and PS. It was associated with the interphase relaxation peak. Its intensity increased with increasing content of PA1010, and the maximum occurred at the composition of PA1010–HIPS‐g‐MA 80/20. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 857–865, 1999     

Effect of glycerin on structure transition of PVA/SF blends

Blend films of silk fibrion (SF) and poly(vinyl alcohol) (PVA), with glycerin as an additive, were made, and the structure and properties of the blends were investigated by scanning electron microscopy (SEM), Fourier transform infrared (FT‐IR) spectroscopy, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD) and with an Instron Material Tester. The results showed that SF and PVA are principally incompatible and the blends made by the two polymers were phase‐separated. The results, however, also demonstrated that the blend structure could be changed to some extent by addition of 3–8% glycerin. The boundary of the PVA and SF phases became indistinct, as reported by SEM, a new peak appeared in the WAXD curves, the width of the OH absorption peak in the FT‐IR spectra increased, and the melting points changed in the DSC curves. In particular, the mechanical properties obviously increased, from 350 kg/cm² and 10% of PVA/SF (80/20) film to 832 kg/cm² and 39% of PVA/SF (80/20) film because of the increase in glycerin. It was suggested that glycerin plays a role in building the relationship between PVA and SF, strengthening the interaction between them and improving their compatibility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2342–2347, 2002     

Improvement of polyamide 1010 with silica nanospheres via in situ melt polycondensation

Polyamide 1010 (PA1010) had been prepared by in situ melt polycondensation in presence of silica nanospheres with amine groups on the surfaces (SiO₂ NH₂). Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), and thermal gravimetric analysis (TGA) measurements demonstrated that the nanosphere surface was grafted with PA1010 chains. Wide angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC) measurements showed that the PA1010/SiO₂ NH₂ nanocomposites had a lower degree of crystallinity (χ_c) in comparison with PA1010 and PA1010/SiO₂ nanocomposites. Dynamic mechanical analysis (DMA) indicated that SiO₂ NH₂ nanospheres improved glass transition temperature (T_g), tensile strength and storage modulus of PA1010 since SiO₂–NH₂ nanospheres limited the mobility of PA1010 chains. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Crystallization behavior of carbon nanotubes‐filled polyamide 1010

The nanocomposites of polyamide1010 (PA1010) filled with carbon nanotubes (CNTs) were prepared by melt mixing techniques. The isothermal melt‐crystallization kinetics and nonisothermal crystallization behavior of CNTs/PA1010 nanocomposites were investigated by differential scanning calorimetry. The peak temperature, melting point, half‐time of crystallization, enthalpy of crystallization, etc. were measured. Two stages of crystallization are observed, including primary crystallization and secondary crystallization. The isothermal crystallization was also described according to Avrami's approach. It has been shown that the addition of CNTs causes a remarkable increase in the overall crystallization rate of PA1010 and affects the mechanism of nucleation and growth of PA1010 crystals. The analysis of kinetic data according to nucleation theories shows that the increment in crystallization rate of CNTs/PA1010 composites results from the decrease in lateral surface free energy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3794–3800, 2006     

Crystallization and morphology of polyamide 1010/single‐walled carbon nanotube nanocomposites under elevated pressure

Polyamide 1010/single‐walled carbon nanotube (PA1010/SWNT) nanocomposites prepared by melt compounding were treated under a pressure of 2.0 GPa and at three different temperatures (250, 300 and 350 °C) for 30 min. Then, all the samples were naturally cooled to room temperature from the melt prior to release of the applied pressure. The melting temperature and crystallinity of high pressure crystallized samples were shifted to a high value after the treatment temperatures under pressure. The infrared spectrum of the high pressure crystallized samples showed a considerable improvement of crystalline order, a closer packing of the polymer chains due to the shorter N? C bond length, and the presence of a large proportion of free N? H groups resulting from antiparallel chains in flat zigzag conformation. Wide‐angle X‐ray diffraction measurements indicated that the high pressure gave rise to an increase in crystallite dimensions as well as to a decrease of the distance between the crystal planes bonded by the hydrogen bond (100) planes and by the van der Waals force (010) planes. Scanning electron microscope images showed that denser texture, thicker covering layers on the tubes and regular cubic sugar‐like crystals with a lateral length of about 1.5 µm could be detected on the fracture surface of PA1010/SWNT nanocomposites crystallized under pressure. Copyright © 2012 Society of Chemical Industry     

Influence of the fold surface of the lamellae on radiation effects—research on irradiated polyamide-1010 containing heterogeneous nuclei

Irradiated polyamide-1010 (PA 1010) and PA 1010 containing 0.5% (wt) heterogeneous nuclei were studied by ESR, WAXD, DSC and the determination of gel fractions. The fold surface of the lamellae plays an important role in the effects of radiation on crystalline PA1010. The results show that the direct radiation effects on both samples vary, while after being heated to 220°C, the final radiation effects are identical, regardless of the difference in the amount of the fold surface of the lamellae. The post-radiation effects result predominantly from the fold surface.     

Chemosynthesis and characterization of fully biomass‐based copolymers of ethylene glycol, 2,5‐furandicarboxylic acid,and succinic acid

Poly(ethylene 2,5‐furandicarboxylate‐co‐ethylene succinate) (PEFS) copolymers of 2,5‐furandicarboxylic acid (FDCA) and succinic acid with 11.98–91.32 mol % FDCA composition were synthesized via melt polycondensation in the presence of ethylene glycol using tetrabutyl titanate as a catalyst. PEFSs' molecular weight, thermal properties, and molar composition were determined by Fourier transform infrared spectroscopy, gel permeation chromatography, intrinsic viscosity, ¹H NMR, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and wide‐angle X‐ray diffraction (WAXD) measurements. From experimental conditions, we obtained random copolymers with number‐average molecular weights exceeding 25,600, determined by GPC and ¹H NMR analyses. DSC analysis revealed that PEFS copolymers' melting temperatures differed depending on EF units' percentage. TGA studies confirmed that all PEFS copolymers' thermal stability exceeded 300°C. From WAXD analysis, it is observed that the PEFS copolymer crystal structure was similar to that of PES when EF unit was 11.98 mol % and to that of PEF when EF units were 74.35 and 91.32 mol %. These results benefit this novel biodegradable copolymer to be used as a potential biomaterial. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1415‐1420, 2013     

Effect of clay addition on the morphology and thermal behavior of polyamide 6

The nanostructure, morphology, and thermal properties of polyamide 6 (PA6)/clay nanocomposites were studied with X‐ray scattering, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). The wide‐angle X‐ray diffraction (WAXD) and TEM results indicate that the nanoclay platelets were exfoliated throughout the PA6 matrix. The crystallization behavior of PA6 was significantly influenced by the addition of clay to the polymer matrix. A clay‐induced crystal transformation from the α phase to the γ phase for PA6 was confirmed by WAXD and DSC; that is, the formation of γ‐form crystals was strongly enhanced by the presence of clay. With various clay concentrations, the degree of crystallinity and crystalline morphology (e.g., spherulite size, lamellar thickness, and long period) of PA6 and the nanocomposites changed dramatically, as evidenced by TEM and small‐angle X‐ray scattering results. The thermal behavior of the nanocomposites was investigated with DSC and compared with that of neat PA6. The possible origins of a new clay‐induced endothermic peak at high temperature are discussed, and a model is proposed to explain the complex melting behavior of the PA6/clay nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1191–1199, 2007     

Thermally reversible and self‐healing novolac epoxy resins based on Diels–Alder chemistry

The modified novolac epoxy resins with furan pendant groups were prepared by novolac epoxy resin and furfuryl alcohol and then crosslinked by bifunctional maleimide via Diels–Alder (DA) chemistry to obtain the thermally reversible and self‐healing novolac epoxy resins. The as‐prepared crosslinked novolac epoxy resins were characterized by FT‐IR, NMR, TGA, and DMA. The results indicate that the novel crosslinked novolac epoxy resins present higher storage modulus (2.37 GPa at 30°C) and excellent thermal stability (348°C at 5% mass loss). Furthermore, the thermal reversible and self‐healing properties were studied in detail by DSC, SEM, thermal re‐solution, and gel–solution–gel transition experiments. All the results reveal that the crosslinked novolac epoxy resins based on DA reaction can be used as smart material for the practical application of electronic packaging and structural materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42167.     

γ‐Crystalline form of nylon‐10,10 in nylon‐10,10–montmorillonite nanocomposite

Wide‐angle X‐ray diffraction (WAXD) and variable temperature WAXD spectroscopy and Fourier‐transform infrared (FTIR) spectrometry were used to identify the γ‐crystalline form of nylon‐10,10 in the nanocomposite of nylon‐10,10 and montmorillonite. A new diffraction peak at 2θ = 22° was observed in the WAXD pattern of the nanocomposite as compared with nylon‐10,10, and the data of variable temperature WAXD indicated that it was the characteristic peak of γ‐crystalline form of nylon‐10,10. The amide VI band at 624 cm^?1 was also observed in the FTIR spectrum of the nanocomposite, which is characteristic of γ‐crystalline nylon. In addition, the shoulder peak at 1553 cm^?1 can be assigned to the amide II band of γ‐crystalline form of nylon‐10,10. Copyright © 2003 Society of Chemical Industry     

PA11/PA1010共混物的性能研究

采用熔体共混的方法制备了聚酰胺11/聚酰胺1010(PA11/PA1010)共混物,通过力学性能和差示扫描量热(DSC)测试,研究了PA11/PA1010共混物的力学与结晶性能。测试结果表明:PA1010对PA11同时具有增韧、增强作用;当PA11/PA1010为70/30时,共混物开始出现两个结晶峰和低温熔融峰;共混物的结晶和熔融以PA11为主,兼具有PA11和PA1010的优良性能;断裂伸长率、拉伸强度与缺口冲击强度均达到极大值。     

Interaction of anhydrous ferric chloride with nylon 6

The interaction of anhydrous ferric chloride with nylon 6 has been inferred from Fourier transform infrared spectroscopy (FTIR), wide-angle x-ray diffraction (WAXD), thermal (DSC and TGA), and rheological (Rheometrics) measurements. At very low additive concentration of ～0.25 wt %, an about 50-fold melt viscosity increase of nylon 6 was observed. However, progressive decrease in melt viscosity was also observed with increasing additive concentrations indicative of degradation as confirmed by the enhancement of weight loss with TGA at a lower temperature. Decrease in crystallinity content of the filled nylon samples is inferred from the reduction of the melting endotherms with DSC, pronounced reduction in diffraction intensity with WAXD, an increase in amorphous CH₂ bending band (1400 cm^?1) with FTIR. The above results can be attributed to the strong complex formation between the FeCl₃ and the N? H groups as suggested by the subtraction spectra of FTIR where decreased intensities of the 690, 1200, and 1265 cm^?1 bands were observed.     

Characterization of poly(lactic acid) multifilament yarns. I. The structure and thermal behavior

The structure and thermal behavior of poly(lactic acid) (PLA) multifilament yarns were studied by complementary techniques of differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, and wide angle X‐ray diffraction (WAXD). As for PLA filaments, notable differences in the WAXD patterns, DSC curves, and FTIR spectra were observed. The combination of the WAXD and FTIR results showed that PLA samples with different crystallinity contain α‐form crystal structure. The FTIR spectra of the filaments were analyzed to study their crystallinity and crystal structure. The total crystallinity of the PLA filaments was obtained from the percent area loss of the skeletal amorphous band at 955 cm^?1. Crystalline fraction from FTIR and DSC were comparable with each other. The C?O stretching region, which is sensitive to crystallization and dipole–dipole interactions, was evaluated to provide information about chain conformers and crystallinity of the samples. Depending on the processing conditions, double melting peaks were observed in the DSC curves of the samples. This exhibited the structural reorganization of the crystal phase during heating affected by heating and cooling rate. In the DSC curves of the nearly amorphous multifilament yarn, the exothermic peak observed right above the glass transition temperature (T_g) indicated two relaxed and deformed amorphous regions. However, the multifilament yarn with higher crystallinity showed just endothermic melting peak after its glass transition. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structure and properties of isotactic polypropylene functionalized by ultraviolet irradiation

The structural, crystalline, thermal, morphological, and mechanical properties of isotactic polypropylene (iPP) functionalized by lower energy ultraviolet (UV) irradiation are studied by means of infrared spectroscopy (IR), differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), thermogravimetry (TG), thermomechanical analysis (TMA), polariscope, and mechanical measurements. After the UV irradiation in less than a few hours, the oxygen containing polar groups have been introduced onto iPP chains. DSC analysis shows that a new melting peak is observed around 150°C for the UV irradiated iPP, indicating that there is a α‐phase to β‐phase transition during UV irradiation process. Under polariscope, the morphology of the UV irradiated iPP is changed, and the deformed α‐phase morphology can be observed. DSC and WAXD analysis reveal for the crystallinity of the UV‐irradiated iPP increase with UV time, but the relative level and the order of β‐phase increase and then decrease with increasing UV time. Under the controlled UV time, the thermomechanical deformation of iPP decrease, and the initial and final thermal degradation temperature of iPP rises up by 70 to 125°C higher, respectively, indicating that the UV‐irradiated iPP has higher thermal stability than the non‐UV irradiated iPP. The tensile and impact strength, the elongation at break, and the Young's modulus of the UV‐irradiated iPP are enhanced, exhibiting the toughened and strengthened effects. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1456–1466, 2001     

Novel crosslinked AB‐type polyphenylquinoxaline membranes for high‐temperature proton exchange membrane fuel cells

AB‐type polyphenylquinoxaline (ABPPQ) membranes exhibit great mechanical properties and thermal properties for high‐temperature proton exchange membranes (PEMs). However, they dissolve in high‐concentration phosphoric acid (PA) during acid doping. In order to improve the PA resistant of ABPPQ, crosslinked ABPPQ membranes were prepared using sulfuric acid. The crosslinked ABPPQ membranes showed high PA resistance. The acid content of PA‐doped membranes decreased slightly with crosslinking, but the crosslinked polyphenylquinoxaline (CPPQ)‐20 membrane could reach 2.5 × 10^?2 S/cm proton conductivity at 160°C. Membrane electrode assemblies were fabricated with an active area of 4 cm² and Pt loading of 1 mg/cm². A startup and shutdown test (operated at 150°C with 0.2 A/cm² for 12 h and then 12 h off at room temperature) and a 30‐day long‐term durability test (150°C with 0.2 A/cm²) were conducted. In the startup and shutdown test, the crosslinked membranes showed a low open‐circuit voltage decay rate of 0.15 mV/h. In the 30‐day long‐term durability test, the voltage decay rate was 0.039 mV/h. In both tests, the crosslinked membranes showed a stable performance. Therefore, the crosslinked ABPPQ membranes can be regarded as a novel material for high‐temperature PEM fuel cells. POLYM. ENG. SCI., 59:2169–2173, 2019. © 2019 Society of Plastics Engineers     

Synthesis,characterization, and thermal properties of copolymers of behenyl acrylate and behenyl fumarate

Radical copolymerization of behenyl (systematic IUPAC nomenclature: n‐docosyl) acrylate and behenyl fumarate has been carried out in toluene at 70°C using benzoyl peroxide as initiator. Gel permeation chromatography was used to determine molecular weights (MW) and molecular weight distribution (MWD) of behenyl acrylate–behenyl fumarate (BA‐BF) copolymers. ¹H NMR and carbon analysis was used to determine the composition of BA‐BF copolymers. Monomer reactivity ratios for high conversion polymerization were calculated by conversion‐extended Kelen‐Tudos plot. Differential scanning calorimetric (DSC) measurements shows sharp melting peaks at about 64°C. Thermal stability studies were performed with thermogravimetric analyzer (TGA). By using these DSC and TGA data in several nonisothermal methods, the activation energies were calculated. X‐ray diffraction studies show the linearity of the copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2721–2726, 2003     

Crystalline structure and morphology of poly(L‐lactide) formed under high pressure

The poly(l ‐lactide) (PLLA) samples were prepared by the annealing under 100 MPa at 75–145^°C and 200 MPa at 105–145^°C for 6 h, respectively. The crystalline structures, thermal properties and morphology were investigated using differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and scanning electron microscopy (SEM). On the basis of the DSC and WAXD results, it can be seen that the α′ form was formed by the annealing under 100 MPa at 85–95°C but not found under 200 MPa at 105–145°C. A phase diagram of PLLA crystal form under high pressure was constructed under the given experimental conditions, which displayed the α′ form was formed at limited temperature and pressure range. Besides, SEM suggested that the PLLA samples annealed under 100 MPa crystallize to form lamellar‐like crystals due to the low growth rate and the confined crystallization behavior under high pressure. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40637.     

Rheological,thermal, and morphological properties of ABS–PA1010 blends

Noncompatibilized and compatibilized ABS–nylon1010 blends were prepared by melt mixing. Polystyrene and glycidyl methacrylate (SG) copolymer was used as a compatibilizer to enhance the interfacial adhesion and to control the morphology. This SG copolymer contains reactive glycidyl groups that are able to react with PA1010 end groups ( NH₂ or  COOH) under melt conditions to form SG‐g‐Nylon copolymer. Effects of the compatibilizer SG on the rheological, thermal, and morphological properties were investigated by capillary rheometer, DSC, and SEM techniques. The compatibilized ABS–PA1010 blend has higher viscosity, lower crystallinity, and smaller phase domain compared to the corresponding noncompatibilized blend. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 683–688, 1999     

Enhanced thermal conductivity of PE/BN composites through controlling crystallization behavior of PE matrix

In this article, in order to enhance the thermal conductivity of the polyethylene (PE)/boron nitride (BN) composites through controlling the crystallization behavior of the PE matrix, the crystallization and melting behavior of the PE in the PE/BN composites was investigated. When the BN content was more than 10 wt%, an extra weak exothermic peak (T _h) at 130°C was observed. Moreover, after the annealing of the PE/BN composites at 130°C, the extra weak melting peaks (T _mh) of the PE in the PE/BN composites were also observed and shifted to the high temperature with increasing annealing time, which proved that the T _h was induced by PE crystallization. Meanwhile, the results of temperature‐dependent absorbance IR spectra of the PE/BN composites showed that the crystallization peak (729 cm⁻¹) remarkably appeared at 130.2°C, indicating that the crystallization of the PE in the PE/BN composites can occur at 130.2°C. When the annealing time and temperature were 20 min and 130°C, the thermal conductivity of the PE/BN composite was 16% higher than that of the unannealed PE/BN composites. In addition, the results of the wide angle X‐ray diffraction (WAXD) showed that the BN particles had no influence on the PE crystalline form in the PE/BN composites. POLYM. COMPOS., 38:2806–2813, 2017. © 2015 Society of Plastics Engineers