首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Extended chains and/or extended chain crystals (ECC) are important structures for improving the mechanical properties of polymer fibers. ECC have so far been produced using specially prepared materials or manufacturing methods. In our study on the production of nanofibers by carbon dioxide (CO2) laser supersonic drawing, we succeeded in producing nylon‐66 nanofibers having a high melting point near the equilibrium melting point (Tm0). Two melting points (Tm) of 260 and 276°C were observed for the nanofibers, with the latter temperature being close to the Tm0 (280°C) of nylon‐66. A nanofiber that was heat treated at 279°C for 10 min displayed a large stacked lamellar structure with an average crystal thickness of 140 nm. That value was close to the average molecular chain length of 212 nm, which was calculated from the average molecular weight of the nanofibers. It was inferred from these results that ECC corresponding to the average molecular chain length were present in the nanofibers. The CO2 laser supersonic drawing process is applicable to general purpose thermoplastic polymers and uses a simple drawing system. It is expected that this drawing method will help to improve the fundamental performance of general purpose polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40361.  相似文献   

2.
Nylon 66 nanofibers were prepared by irradiating as‐spun nylon 66 fibers with radiation from a carbon dioxide (CO2) laser while drawing them at supersonic velocities. A supersonic jet was generated by blowing air into a vacuum chamber through the fiber injection orifice. The fiber diameter depended on the drawing conditions used, such as laser power, chamber pressure, laser irradiation point, and fiber supply speed. A nanofiber obtained at a laser power of 20 W and a chamber pressure of 20 kPa had an average diameter of 0.337 μm and a draw ratio of 291,664, and the drawing speed in the CO2 laser supersonic drawing was 486 m s?1. The nanofibers showed two melting peaks at about 257 and 272°C. The lower melting peak is observed at the same temperature as that of the as‐spun fiber, whereas the higher melting peak is about 15°C higher than the lower one. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40015.  相似文献   

3.
Nylon‐6 and nanoclay/nylon‐6 composite nanofibers were prepared by electrospinning technique, in which formic acid was used as a solvent for good solubility of nylon‐6. The diameter of nylon‐6 and nanoclay/nylon‐6 nanofibers was below 350 nm and had smooth surfaces. The DSC heating curves of nylon‐6 and composites nanofibers show two endotherm behaviors, Tm1 (about 214°C) and Tm2 (about 220°C), corresponding to the melting events of γ‐form and α‐form crystals, respectively. The WAXs study showed that the γ‐crystalline phase predominantly present in both nylon‐6 and nanoclay/nylon‐6 nanofibers. The mechanical properties of the nanoclay/nylon‐6 composite nanofibers were higher than neat nylon‐6 electrospun nanofibers, which was decreased as the quantity of the clay increased. It might be due to the aggregation of nanoclay at high concentration. The thermal properties of the composite nanofibers were higher than neat nylon‐6 nanofibers. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers  相似文献   

4.
Poly(ethylene‐2,6‐naphthalate) (PEN) nanofiber was prepared by a carbon dioxide (CO2) laser supersonic drawing. The CO2 laser supersonic drawing was carried out by irradiating the laser to the as‐spun PEN fiber in a low‐temperature supersonic jet. The supersonic jet was generated by blowing off air into a vacuum chamber from a fiber supplying orifice. The flow velocity from the orifice can be estimated by applying Graham's theorem from the pressure difference between the atmospheric pressure and the pressure of the vacuum chamber. The fastest flow velocity estimated was 396 m s?1 (Mach 1.15) at a chamber pressure of 6 KPa. The nanofiber obtained at Mach 1.15 was the oriented nanofibers with an average diameter of 0.259 μm, and its draw ratio estimated from the diameters before and after the drawing reached 430,822 times. The CO2 laser supersonic drawing is a new method to make nanofiber without using any solvent or removing the second component. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

5.
Three kinds of high‐molecular‐weight compatibilizers [copoly(1,4‐phenylene sulfide)‐poly(2,5‐phenylene sulfide amine)] (PPS‐NH2) containing different proportions of amino units in the side chain) were synthesized by the reaction of dihalogenated monomer and sodium sulfide via nucleophilic substitution polymerization under high pressure. The intrinsic viscosity of the obtained copolymers was 0.354–0.489 dL/g and they were found to have good thermal performance with melting point (Tm) of 271.3–281.0 °C and initial degradation temperature (Td) of 490.0–495.7 °C. There was an excellent physical compatibility between PPS‐NH2 and the pure industrial PPS. The results of dynamic mechanical analysis and macro‐ and micromechanical test showed that the selective compatibilizer PPS‐NH2 (1.0) (1.0% mol aminated ratio) can improve the mechanical and interfacial properties of polyphenylene sulfide/glass fiber (PPS/GF) composite. The macro‐optimal tensile strength, Young's modulus, bending strength, and notched impact strength of 5%PPS‐NH2 (1.0)/PPS/GF composite raised up to 141 MPa, 1.98 GPa, 203 MPa, and 6.15 kJ/m2, which increased 12.8%, 9.4%, 4.1%, and 13.8%, respectively, comparing with the pure PPS/GF composite (125 MPa, 1.81 GPa, 195 MPa, and 5.40 kJ/m2, respectively). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45804.  相似文献   

6.
Poly(ethylene terephthalate) (PET) particles were prepared by the irradiation of PET fibers with a carbon dioxide (CO2) laser while atomizing them at supersonic velocities. A supersonic jet was generated by blowing air into a vacuum chamber through a fiber injection orifice. The fibers are melted by laser heating and atomized by the supersonic jet at the outlet of the orifice. The PET particles produced by CO2 laser supersonic atomization conducted at a laser power of 34 W and at a chamber pressure of 10 kPa have an average particle size of 0.619 μm, high circularity, and a smooth surface that is not roughened by laser ablation. The novel CO2 laser supersonic atomization technique can be used to easily prepare polymeric nanoparticles of various thermoplastic polymers using only CO2 laser irradiation without the need for solvents and additives. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40909.  相似文献   

7.
The effect of thermal treatment over a wide range of temperature (130–280°C) on the crystallization behavior of nylon 6 was studied by using DSC, FTIR, and polarized light microscope equipped with a hot stage. The crystallization and the subsequent melting behavior of the nylon 6 samples treated at different temperatures (Ts) were classified into four types. When Ts was higher than 236°C or lower than 213°C, the crystallization behavior of nylon 6 was insensitive to the variation of Ts. When Ts was in the range of 213–235°C, the crystallization behavior was sensitive to the change of Ts. The polarized light microscopic experiments have demonstrated that a large amount of tiny ordered nylon 6 segments/cluster persisted when nylon 6 film are heated to 231°C. Consequently, the fastest crystallization speed was observed. As Ts was between 214 and 223°C, both the Tm and the ΔHm were higher than those of the nylon 6 samples treated at other temperature. The polarized light microscopic investigations have also demonstrated that molten nylon 6 crystallizes by using the un‐molten nylon 6 crystals as nucleation center at 220°C. Crystallization at higher temperature produces nylon 6 with thicker crystalline lamella. The above results are helpful for rational design of thermal treatment procedure to obtain nylon 6 with different crystalline features. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42413.  相似文献   

8.
The solubility and transport of toluene and carbon disulfide into amorphous and crystalline polyphenylene sulfide (PPS) was investigated. The rates of sorption, desorption, and resorption of both fluids were measured as a function of temperature. The sorption of these fluids into amorphous PPS produces a semi‐crystalline material by solvent induced crystallinity (SIC). Although the rate of diffusion of carbon disulfide (CS2) into crystalline PPS, (produced either thermally or by SIC), is several orders of magnitude slower than that observed in amorphous PPS, the solubility is only slightly reduced, by approximately 10%. The PPS films exhibit highly stressed surface regions that rapidly sorb the penetrant. Thermal annealing at temperatures as high as 100°C (note Tg of PPS is 85°C) has little or no effect on the surface stress, the diffusion process or the solubility of toluene into PPS. In addition to SIC, PPS undergoes cold crystallization at 130°–140°C; however, the degree of crystallinity induced by cold crystallization is approximately 60% of that formed by cooling from the melt. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 615–625, 2003  相似文献   

9.
The effect of the final melting temperature (Tf) on the crystallization of poly(l ‐lactide) (PLLA)/poly(d ‐lactide) (PDLA) was studied via a combination of differential scanning calorimetry, wide‐angle X‐ray scattering, polarized optical microscopy, and Fourier transform infrared (FTIR) spectroscopy. We observed that a residual stereocomplex (SC) crystal induced the formation of SC crystals during cooling from a Tf (230°C) just above the melting peak of the SC crystals. On cooling from a Tf (240°C) just above the endset temperature of SC crystal melting [Tm(S)(E)], the possible order structure and the strong interchain interaction promoted the preferential crystallization of SC crystals; this enhanced the formation of α crystals. During cooling from a Tf (≥250°C) far above Tm(S)(E), the crystallization peaks of α and SC crystals converged. The FTIR results indicated that the residual SC crystals, possible ordered structure, and interchain interactions in the melt might have been the key factors for the different crystallization of PLLA/PDLA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43015.  相似文献   

10.
The thermal transition behavior of poly[bis(trifluoroethoxyphosphazene)] (I) and two samples of poly[bis(p-chlorophenoxyphosphazene)] (II) have been studied as representative alkoxy- and aryloxy-substituted polyorganophosphazenes. Several of the polymers of this class are reported to exhibit two first-order transitions, denoted herein as T (1) for the transition from a crystalline to mesomorphic state and Tm for the true melt. Studies of these two polymers were undertaken to gain a further understanding of this behavior. Optical microscopy on a solution-cast film of I showed that the details of spherulitic morphology persist through T(1) = 90°C and remain undisturbed through the temperature interval up to Tm = 240°C. The study of II by x-ray diffraction reveals that two sharp lines are observed above T(1) = 165°C and that orientation is not randomized upon heating to temperatures as high as 238°C. Considerable improvement in the crystalline diffraction pattern results from the thermal treatment. A detailed examination was also made by differential scanning calorimetry (DSC) of the effects of cycling through T(1), annealing in the temperature interval between T(1) and Tm and for I, the influence of controlled crystallization from the melt. The results indicate that the organization in the mesomorphic state, as influenced by thermal history, has a profound affect on the peak position, area, and sharpness of the endotherm at T(1). For I, the apparent heat of fusion at T(1) is about ten times greater than at Tm, whereas for II, no DSC peak is observed at Tm = 365°C, suggesting that the ratio of the heats of fusion at T(1) and Tm is greater than 50. However, estimated volume changes at the two transitions are nearly equal. These results are compared with those of other polymers which exhibit an intermediate state of order and with molecular liquid crystals.  相似文献   

11.
Thermal properties of Fortron®
  • 1 ®Registered trademark of Hoechst Celanese Corporation.
  • poly(phenylene sulfide) (PPS) polymers of different molecular weights were studied by DSC. Crystallization studies revealed that the ability of these polymers to crystallize decreases with increasing molecular weight. The Avrami equation poorly describes the isothermal crystallization of PPS. Lamellar crystallization was observed for the lowest molecular weight sample. For the other, higher molecular weight polymers the Avrami exponent is always between 2 and 3, suggesting development of distorted spherulites with heterogeneous nucleation. The temperature dependence of the solid and melt heat capacities have been determined. The solid specific heat capacity did not exhibit a molecular weight dependence. The heat capacity increase at the glass transition, Tg, has been calculated to be 28.1 J°C?1 mole?1. The equilibrium melting point of PPS has been estimated to be 348.5°C using the Hoffman–Weeks method. The Tg of PPS increases with molecular weight. The Tg of the highest molecular weight evaluated is 92.5°C. A DMA relaxation peak corresponding to the onset of the phenylene ring rotation occurs at ?92°C. Only the highest molecular weight could be quenched to a completely amorphous state.  相似文献   

    12.
    Blends of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐4,4′‐ bibenzoate) (PETBB) are prepared by coextrusion. Analysis by 13C‐NMR spectroscopy shows that little transesterification occurs during the blending process. Additional heat treatment of the blend leads to more transesterification and a corresponding increase in the degree of randomness, R. Analysis by differential scanning calorimetry shows that the as‐extruded blend is semicrystalline, unlike PETBB15, a random copolymer with the same composition as the non‐ random blend. Additional heat treatment of the blend leads to a decrease in the melting point, Tm, and an increase in glass transition temperature, Tg. The Tm and Tg of the blend reach minimum and maximum values, respectively, after 15 min at 270°C, at which point the blend has not been fully randomized. The blend has a lower crystallization rate than PET and PETBB55 (a copolymer containing 55 mol % bibenzoate). The PET/PETBB55 (70/30 w/w) blend shows a secondary endothermic peak at 15°C above an isothermal crystallization temperature. The secondary peak was confirmed to be the melting of small and/or imperfect crystals resulting from secondary crystallization. The blend exhibits the crystal structure of PET. Tensile properties of the fibers prepared from the blend are comparable to those of PET fiber, whereas PETBB55 fibers display higher performance. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1793–1803, 2004  相似文献   

    13.
    The glass transition temperature (Tg) of polyphenylene sulfide (PPS), and of several commercial and model PPS prepregs with aramid, carbon, and glass fibers was studied by means of differential scanning calorimetry. The Tg of unreinforced PPS was found to range between 83–90°C, depending on source and molecular weight. The Tg of the commercial prepregs was depressed by about 3–5°C from that of the corresponding unfilled PPS, an effect that was ascribed to the plasticization of the PPS by one or more components of the fiber finish (size) that was assumed to have diffused into the PPS polymer. In the case of model prepregs prepared with finish-free reinforcing fibers, an expected increase in Tg was observed. In model prepregs prepared with finished (sized) aramid fibers, the Tg was depressed as in the case of the commercial prepregs. With sized AS-4 carbon fibers, the Tg was increased, but significantly less so than with unsized AS-4 fibers. With sized glass fibers, the same slight increase in Tg was observed as with unsized glass fibers. The increase or decrease of Tg in all cases was a function of the fiber content in the model PPS prepregs.  相似文献   

    14.
    In this study, poly(l ‐lactic acid) (PLLA) was prepared by four typical approach systems, namely, solid–liquid phase‐separation processes from PLLA–dioxane at ?80°C, PLLA–dioxane–water at ?80°C, PLLA–tetrahydrofuran (THF) at ?80°C, and PLLA–THF at 18°C. The microstructural characteristics and crystallization behaviors of PLLA were investigated by scanning electron microscopy, differential scanning calorimetry, X‐ray diffraction, and Fourier transform infrared spectroscopy. In the PLLA–dioxane binary system and PLLA–dioxane–water ternary system, the solvent froze immediately after quenching to a low temperature, and this restricted the PLLA chain arrangement. Thus, the PLLA amorphous phase dominated in the scaffolds, and solid‐walled structures were produced. THF was liquid throughout the entire process, which enabled free PLLA chain arrangement and further crystallization. Single crystals aggregated by crystal nucleation and growth at a critical temperature (Tc) of 18°C; this resulted in its most common and stable polymorph, the α form. However, α′‐form crystals, which were assumed to be limit‐disordered crystals of the α form, were produced at a low Tc (?80°C). Scaffolds with a plateletlike structure were produced at a Tc of 18°C, whereas a nanofibrous network was obtained at ?80°C. PLLA crystallization competed with phase separation; thus, the crystal structure and scaffold morphology depended on the codevelopment of these two processes. Finally, the effects of the scaffold morphologies on the cell behaviors were studied, and the nanofibrous scaffold was found to have better cell adhesion and viability than the other three scaffolds. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39436.  相似文献   

    15.
    The physical and elastomeric properties of several DEXSIL 300 (10-SiB-3) samples were investigated. Modulus—temperature studies were used to determine the glass transition temperature Tg, the melting temperature Tm, and the oxidative crosslinking temperature Tox. Stress relaxation in air at elevated temperatures was used to compare the oxidative stability of the various formulations. It was found that the Tg of DEXSIL 300 is some 30°C lower than that of DEXSIL 200 (10-SiB-2) polymers, extending the elastomeric properties of DEXSIL 300 to lower temperatures. At high temperatures, both silica filler and ferric oxide are found to increase Tox to an ultimate value of 320°C. The effects of cure were also investigated, and γ-radiation-cured samples exhibit a slight degree of crystallinity with a melting temperature Tm = +40°C. No crystallinity was detected in similar peroxide-cured samples. Stress relaxation results are presented in support of the modulus—temperature studies. Formulations with a low Tox show oxidative effects earlier than those with a higher oxidation temperature. Silica-and ferric oxide-filled samples exhibit improved oxidative stability, as do samples filled with diphenylsilanediol.  相似文献   

    16.
    A novel aromatic diamine‐based benzoxazine (P‐mPDA) is successfully synthesized from m‐phenylenediamine (m‐PDA), 2‐hydroxybenzaldehyde, and formaldehyde. The polymerization behavior of P‐mPDA and the properties of its thermoset are studied. The results indicate that P‐mPDA owns favorable processability including low polymerization temperature, low liquefying temperature, and wide processing window. Even lower polymerization temperature (polymerization onset temperature as low as 80 °C) can be achieved by the promotion of catalysts. The ring‐opening polymerization of P‐mPDA first generates polybenzoxazine with N, O‐acetal‐type structure and arylamine Mannich‐type structure, following which rearrangement from N, O‐acetal‐type structure to phenolic Mannich‐type structure proceeds at elevated temperature. Furthermore, the polymerized P‐mPDA shows outstanding performance such as extremely high glass transition temperature (Tg) of 280 °C, high char yield above 53% at 800 °C under nitrogen and excellent mechanical property. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43368.  相似文献   

    17.
    This work was concerned with investigating the processing behavior of thermoplastics reinforced with a melt processable phosphate glass under extensional flows at temperatures used for forming and shaping operations. Injection molded blends consisting of polyetherimide (PEI) and polyphenylene sulfide (PPS) reinforced with 30‐60 wt% phosphate glass were exposed to uniaxial and planar deformation at temperatures above the Tg of the phosphate glass (234°C) to evaluate the effects on the morphology and mechanical properties of the composites. Tensile testing at elevated temperatures (250‐300°C) was used to evaluate the forming behavior and ascertain the conditions most suited for the deformation of the composite blends. A temperature approximately 35°C above the Tg of the P‐glass was found to offer conditions most conducive to the deformation of the PEI/P‐glass blends. The phosphate glass reinforced PEI was found to offer greater retention of properties and smoother surfaces than an E‐glass filled material when exposed to shearfree deformation similar to that seen in a process such as thermoforming. For PPS based composites, the application of planar shearfree deformation near the melting point of the PPS (≈︁ 283°C) resulted in the elongation of the phosphate glass phase which served to enhance the stiffness of the composite blends along the principal deformation direction.  相似文献   

    18.
    Aryloxycarbonylphenyl acrylates and methacrylates were prepared by reacting 4‐acryloyloxybenzoyl chloride and 4‐methacryloyloxybenzoyl chloride with different phenols. They were homopolymerized using benzoyl peroxide as the initiator at 65°C in dimethylformamide. The polymers were characterized by IR and 1H–NMR spectra and size exclusion chromatography. Differential scanning calorimetry and polarizing optical microscopy studies revealed that the phenyl esters of poly(4‐acryloyloxybenzoic acid) and poly(4‐methacryloyloxybenzoic acid) did not show any liquid crystalline properties, but, the para‐aryl–substituted phenyl esters did exhibit mesophase properties in the temperature range of 98–265°C depending on the nature of the aryl substituent. Polymethacrylates exhibit higher Tg, and lower Tm and Ti than the polyacrylates having the same pendant mesogen. Thermogravimetric analyses have shown that the initial decomposition temperatures of the polymers are above 230°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 465–474, 2000  相似文献   

    19.
    The synthesis and properties of soluble, high Tg and transparent aromatic polyimides containing 4,5‐diazafluorene and trifluoromethyl units in the polymer backbone on the basis of a novel diamine monomer, 9,9‐di[4‐(4‐amino‐2‐trifluoromethyl phenoxy)phenylene]‐4,5‐diazafluorene, are described. Incorporation of 4,5‐diazafluorene and trifluoromethyl groups into rigid polyimides improves their solubility and transparency without decreasing their physical properties. All of the thermal imidization polyimides are soluble at room temperature in aprotic and protic polar solvents such as N,N‐dimethylacetamide, N,N′‐dimethylformamide, dimethylsulfoxide, pyridine and m‐cresol and can be solution cast into transparent, flexible and tough films. These films have a UV–visible absorption cutoff wavelength at 386–407 nm and light transparencies of 73%–84% at a wavelength of 550 nm. In addition, the polymers exhibit high thermal stability with a glass transition temperature (Tg) of 305 to 362 °C and 5% weight loss at temperatures ranging from 525 to 543 °C in nitrogen and from 521 to 538 °C in air. The polyimide films possess tensile strengths in the range 79 ? 113 MPa, a tensile modulus of 1.75 – 2.10 GPa and elongations at break of 7% ? 16%. © 2014 Society of Chemical Industry  相似文献   

    20.
    We present a strategy for stabilizing the morphological integrity of electrospun polymeric nanofibers by heat stimuli in situ crosslinking. Amorphous polymer nanofibers, such as polystyrene (PS) and its co‐polymers tend to lose their fiber morphology during processing at temperatures above their glass transition temperature (Tg) typically bound to happen in nanocomposite/structural composite applications. As an answer to this problem, incorporation of the crosslinking agents, phthalic anhydride (PA) and tributylamine (TBA), into the electrospinning polymer solution functionalized by glycidylmethacrylate (GMA) copolymerization, namely P(St‐co‐GMA), is demonstrated. Despite the presence of the crosslinker molecules, the electrospinning polymer solution is stable and its viscosity remains unaffected below 60 °C. Crosslinking reaction stands‐by and can be thermally stimulated during post‐processing of the electrospun P(St‐co‐GMA)/PA‐TBA fiber mat at intermediate temperatures (below the Tg). This strategy enables the preservation of the nanofiber morphology during subsequent high temperature processing. The crosslinking event leads to an increase in Tg of the base polymer by 30 °C depending on degree of crosslinking. Crosslinked nanofibers are able to maintain their nanofibrous morphology above the Tg and upon exposure to organic solvents. In situ crosslinking in epoxy matrix is also reported as an example of high temperature demanding application/processing. Finally, a self‐same fibrous nanocomposite is demonstrated by dual electrospinning of P(St‐co‐GMA) and stabilized P(St‐co‐GMA)/PA‐TBA, forming an intermingled nanofibrous mat, followed by a heating cycle. The product is a composite of crosslinked P(St‐co‐GMA)/PA‐TBA fibers fused by P(St‐co‐GMA) matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44090.  相似文献   

    设为首页 | 免责声明 | 关于勤云 | 加入收藏

    Copyright©北京勤云科技发展有限公司  京ICP备09084417号