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1.
Development of crystallinity in NEW-TPI semicrystalline polyimide has been studied using differential scanning calorimetry (DSC), wide (WAXS), and small angle X-ray scattering (SAXS). Crystallinity of the fully imidized powder, pellet, or film processed NEW-TPI can occur from the melt, and depends upon the holding temperature of the melt. Repetitive exposure to elevated temperatures supresses the development of crystallinity from the melt state. In amorphous pellets and film, crystallinity can also develop by cold crystallization from the rubbery amorphous state. SAXS results show that during cold crystallization, NEW-TPI develops a periodic structure consistent with formation of alternating crystalamorphous stacks, but with crystals only a few molecular repeat units thick. Kinetics of nonisothermal crystallization were studied as a function of heating rate and could be described using the Ozawa analysis. Non-isothermal crystallization proceeds at a slower rate in NEW-TPI than in other high temperature thermoplastics such as PEEK, and with a much narrower processing window. The maximum degree of crystallinity that could develop during heating was 0.34, which occurred at a rate of 5°C/min. Similar degrees of crystallinity could be introduced by heating amorphous NEW-TPI film in N-methylpyrrolidone.  相似文献   

2.
The relaxation behavior of poly(phenylene sulfide) (PPS) RytonTM film has been studied as a function of annealing temperatures, Ta, ranging from 30°C to 140°C. Previously, this type of semicrystalline PPS film was shown to possess a very large fraction of constrained, or rigid, amorphous chains. Here we investigate relaxation of amorphous chains using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermally stimulated depolarization current (TSDC). DSC studies suggest that annealing causes the as-received PPS film to relax some of its rigid amorphous fraction and increase its crystallinity, for Ta > Tg. DMA results show a corresponding increase in the temperature location of the dissipation peak and a decrease in its amplitude when Ta increases above 100°C. Analysis of the TSDC p-peak due to injected space charges trapped at the crystal/amorphous interphase provides additional information about amorphous phase relaxation. This peak does not exist in amorphous film, or as-received film, or as-received films annealed at lower Ta. The p-peak does exist in cold-crystallized films and as-received films annealed at higher Ta. We suggest that crystallinity is a necessary, but not sufficient, condition for observation of a p-peak. In addition to crystallinity, the sufficient conditions for observation of a p-peak are existence of (1) a sharp and distinct crystal/amorphous interphase, to provide charge trapping, and, (2) a large fraction of liquid-like amorphous phase, to provide a pathway for charge transport. These conditions are not met in PPS semicrystalline films with very imperfect crystals and large amounts of rigid amorphous phase. In such films, the rigid amorphous phase has, like the crystal phase, a restricted molecular mobility that causes it also to restrict the mobility of space charge. The implications are that film PPS processed with a large amount of rigid amorphous phase chains will have superiour barrier properties to the build-up of interfacial space charge. © 1996 John Wiley & Sons, Inc.  相似文献   

3.
Time-resolved small-angle X-ray scattering (SAXS) measurements were carried out for PET and its copolymers undergoing isothermal crystallization. Wide-angle X-ray diffraction and differential scanning calorimetric measurements were also performed. Our data analysis of the SAXS results for PET and the copolymers clearly demonstrate that the one layer thickness l1 (derived directly from the correlation functions of the measured SAXS profiles) is the lamellar crystal thickness dc, not the amorphous layer thickness da. The observed dc values are found to be always smaller than da, regardless of polymer composition. dc is highly dependent on the crystallization temperature, showing that the degree of supercooling is the major factor determining the thickness of lamellar crystals. No thickening, however, occurs in isothermal crystallizations. The kinked isophthalate units in the copolymer are found to be mostly excluded from the lamellar crystals during the crystallization process, leading to an increase of the amorphous layer thickness. Moreover, the kinked, rigid nature of the isophthalate unit was found to restrict crystal growth along the chain axis of the copolymers and also to lower their crystallinity. Unlike dc, da decreases with crystallization time, causing a reduction of the long period in the lamellar stack. This drop in da is interpreted in this paper by taking into account several factors that could influence crystallization behavior: the da distribution in the lamellar stacks and its variation with time, the number of lamellae in the lamellar stacks and their effect on the SAXS profile, and the relaxation of polymer chains in the amorphous layers.  相似文献   

4.
The effect of confinement onto the mechanical properties of the amorphous phase of Polyethylene terephthalate (PET) and poly(lactic acid) (PLA) was investigated. These polymers have the advantage of being in bulk amorphous or in semicrystalline state allowing mechanical and physical investigation of the amorphous phase on bulk and confined configuration. Based on small angle X‐ray scattering (SAXS), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA) experiments, the micro‐structural arrangement of the amorphous and crystalline phase, the rigid amorphous fraction, and the visco‐elastic mechanical properties of the different semicrystalline samples were investigated. DSC results help quantifying the rigid amorphous fraction dependence on the crystallinity. DMA measurements lead to quantify the viscoelastic properties of the free and confined amorphous phases for PET and PLA polymers. Indeed, based on the DMA tests, where the maximum of tan(δ) peak is usually related to the glass transition temperature, shifts upon crystallization, the mechanical properties of the restricted and mobile amorphous phase were determined. This result was correlated along with the amorphous phase thickness distribution determined by SAXS results. This observation was bolstered based on literature results about geometrical confinement configurations and their effect on the glass transition temperature of polymeric materials. POLYM. ENG. SCI., 55:397–405, 2015. © 2014 Society of Plastics Engineers  相似文献   

5.
The slow molecular mobility in the amorphous part of the semi‐crystalline polymer poly(butylene succinate) (PBS) has been studied by the thermally stimulated depolarization current (TSDC) technique. Experiments were carried out in the temperature range, which includes the glassy state, the glass transformation region, and the rubber state. A broad and low intensity secondary relaxation was observed in the temperature region from ?140°C up to the glass transition region; the activation energy of the motional modes of this secondary relaxation was in the range between 35 and 55 kJ mol?1. The glass transition temperature of PBS, provided by the TSDC technique, was Tg = ?40 °C, and the fragility index was found to be m = 43. The aging behavior of the main and of the secondary relaxations was analyzed. A strong relaxation above Tg was observed, whose molecular origin was discussed. The thermal behavior of the PBS was also characterized by differential scanning calorimetry. POLYM. ENG. SCI., 55:1873–1880, 2015. © 2014 Society of Plastics Engineers  相似文献   

6.
Modulated differential scanning calorimetry has been carried out on melt‐mixed blends of poly(ethylene oxide)/atactic‐poly(methyl methacrylate) (PEO/PMMA). Two PEO molecular weights have been used to prepare blends in the concentration range 10 to 80 wt % of PEO. Two glass transitions temperatures were observed for the fully amorphous blends, in the 10 to 30 wt % PEO range, using the differential of heat capacity with respect to temperature [dCp/dT] signal. The semicrystalline blends, 40, 60, and 80 wt % PEO, exhibited melting of PEO crystallites and the PEO‐rich phase glass transition at −30 to −50°C. A second glass transition around 30°C was detected for the 40 wt % PEO blend when a cooling run was carried out, because PEO crystallization was avoided under these conditions. Therefore, heterogeneous amorphous phases were observed not only for fully amorphous blends, but also for semicrystalline ones. Further analysis of the dCp/dT signal, obtained from the MTDSC experiments by fitting with Gaussian curves, showed that there is an interphase that varies in amount between 10 to 50 wt %. Correlation of the MTDSC observations with NMR spectroscopy and SAXS/SANS literature results are discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2034–2043, 2000  相似文献   

7.
The low‐temperature physical aging of amorphous poly(L ‐lactide) (PLLA) at 25–50°C below glass transition temperature (Tg) was carried out for 90 days. The physical aging significantly increased the Tg and glass transition enthalpy, but did not cause crystallization, regardless of aging temperature. The nonisothermal crystallization of PLLA during heating was accelerated only by physical aging at 50°C. These results indicate that the structure formed by physical aging only at 50°C induced the accelerated crystallization of PLLA during heating, whereas the structure formed by physical aging at 25 and 37°C had a negligible effect on the crystallization of PLLA during heating, except when the physical aging at 37°C was continued for the period as long as 90 days. The mechanism for the accelerated crystallization of PLLA by physical aging is discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

8.
The dielectric response of poly [(R)‐3‐hydroxybutyrate] (PHB) was investigated as a function of time after quenching a film from the melt to a crystallization temperature of 20 °C. In the frequency range investigated (20 to 106 Hz) a relaxation maximum was observed–attributable to the glass transition–which could be analysed by the Havriliak–Negami relation. Changes in the complex dielectric constant were monitored both during spherulite growth (primary crystallization) and subsequently during a period of progressive crystallization (secondary crystallization) at room temperature. The relaxation strength changed only slightly during primary crystallization and its peak position remained at a constant frequency. Subsequently a continuous decrease in relaxation strength occurred, indicating considerable changes in molecular mobility after spherulite growth had been completed. The results provide further evidence that molecular mobility in the amorphous regions decreases significantly with time, and that this would be the reason why PHB shows embrittlement on ageing at room temperature. Copyright © 2004 Society of Chemical Industry  相似文献   

9.
B. Kalb  A.J. Pennings 《Polymer》1980,21(6):607-612
A study has been made of the general crystallization behaviour of poly(L-lactic acid), PLLA, and is intended to be the basis for further work on fibre formation processes. PLLA is shown to be a semicrystalline polymer that may crystallize from the melt and from solution, and that may form fibres. Spherulites grown from the melt were negatively birefringent and grew at a rate similar to that for polypropylene. The equilibrium melting point and the glass transition temperature were found to be about 215°C and 55°C, respectively. Solution crystallization resulted in lamellar crystals about 10 nm thick and electron diffraction revealed a hexagonal unit structure with dimensions smaller than reported earlier. The equilibrium dissolution temperature in p-xylene and the end surface free energy at the fold surface amounted to 126.5°C and about 0.075 J m?2 respectively. Fibres of PLLA were formed by precipitation in a non-solvent; some of the fibres were highly porous with a pore size in the range 0.1–0.6 μm.  相似文献   

10.
DSC and time‐resolved WAXS and SAXS are used to study the structure development during isothermal crystallization of poly(glycolic acid) (PGA) in the temperature range 180–195°C. It is shown that the crystallization rate increases with degree of supercooling in the temperature range of consideration. WAXS and DSC crystallinity measurements agree well and a final crystallinity of 50% is found independently of the crystallization temperature. In‐situ SAXS measurements indicate that for PGA the final crystal thickness approaches a limiting value of 70 Å independent of the crystallization temperature in the range 195–180°C. The material develops a well‐defined lamellar structure during crystallization at the highest crystallization temperature under study (195°C). We show that by increasing the degree of supercooling it is possible to hinder the formation of the lamellar structure and crystals, resulting in a less ordered structure. We report that PGA fibers with elastic modulus in the range 20–25 GPa can be prepared by adequate control of the structure before solid‐state plastic deformation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

11.
The melting behavior of semicrystalline poly(ether ether ketone ketone) (PEEKK) has been studied by differential scanning calorimetry (DSC). When PEEKK is annealed from the amorphous state, it usually shows two melting peaks. The upper melting peaks arise first, and the lower melting peaks are developed later. The upper melting peaks shown in the DSC thermogram are the combination (addition) of three parts: initial crystal formed before scanning; reorganization; and melting-recrystallization of lower melting peaks in the DSC scanning period. In the study of isothermal crystallization kinetics, the Avrami equation was used to analyze the primary process of the isothermal crystallization; the Avrami constant, n, is about 2 for PEEKK from the melt and 1.5 for PEEKK from the glass state. According to the Lauritzen-Hoffman equation, the kinetic parameter of PEEKK from the melt is 851.5 K; the crystallization kinetic parameter of PEEKK is higher than that of PEEK, and suggests the crystallizability of PEEKK is less than that of PEEK. The study of crystallization on PEEKK under nonisothermal conditions is also reported for cooling rates from 2.5°C/min to 40°C/min, and the nonisothermal condition was studied by Mandelkern analysis. The results show the nonisothermal crystallization is different from the isothermal crystallization. © 1996 John Wiley & Sons, Inc.  相似文献   

12.
The morphology and melt crystallization of zinc catalyzed poly(L ‐lactide) (PLLA) were investigated by using differential scanning calorimetry (DSC), polarized optical microscopy, and scanning electron microscopy. Isothermal melt crystallization performed at 95–135°C showed that the morphology depends on the degree of supercooling, as illustrated by crystallite perfection and lamellar thickening behaviors. Double melting peak was observed on DSC thermograms and attributed to the melt‐recrystallization mechanism, small and imperfect crystals becoming gradually more stable ones. Circumferential and hexagonal cracks were detected in PLLA spherulites, which were formed during melt‐crystallization at 135°C and quenching in liquid nitrogen. Rhythmic growth and thermal shrinkage are suggested to be the two main factors accounting for the formation of periodic cracks. Spherulite growth rates of PLLA were evaluated by using combined isothermal and nonisothermal procedures, and were analyzed by the secondary nucleation theory. The maximum growth rate reached 9.1 μm/min at 130°C. The temperature range investigated (120–155°C) belongs to the Regime II of crystallization. The value of U* was found to be 1890 cal/mol, instead of 1500 cal/mol commonly used in literature, and Kg and σ were estimated to be 3.03 × 105 K2 and 1.537 × 10?4 J/m2, respectively. As a result, no distinct difference between PLLA catalyzed by zinc metal and those prepared with stannous octoate catalyst exists in this work. POLYM. ENG. SCI., 46:1583–1589, 2006. © 2006 Society of Plastics Engineers.  相似文献   

13.
The effect of multiwall carbon nanotubes (MWNT) concentration and cooling rate on the morphological, structural and electrical properties of non‐isothermally crystallized Poly(ethylene naphthalate) nanocomposites (PEN/MWNT) was studied. PEN/MWNT nanocomposites containing 1 and 2 wt % of nanotubes were prepared by melt blending in a mini twin screw extruder. Nanocomposite samples with different degree of crystallinity (Xc) were obtained via non‐isothermally crystallization at cooling rates of 2, 10, 20, and 300°C min?1. In this study it was demonstrated that carbon nanotubes and cooling rate strongly influence morphological and structural characteristics of PEN. Calorimetric results showed that the peak crystallization temperature (Tc) of PEN nanocomposites was increased ~9° through heterogeneous nucleation with respect to pure PEN. X‐ray diffraction revealed that carbon nanotubes modify the crystalline structure of PEN favoring the formation of β‐crystals, and this effect increases with the nanotubes content. On the basis of X‐ray scattering analysis, the variation of lamellar thickness revealed that nanotubes promote the formation of lamellar crystals with average thickness of 20 nm at different cooling rates. These structural and morphological changes play an important role on the electrical properties of nanocomposites. It was found that higher concentration of nanotubes and crystallinity promotes electrical conductivity of nanocomposites in the order of semiconductors (until 1 × 10?4 S cm?1) as well as permittivity of 20 at different tested frequencies. This may due to the interconnected networks of nanotubes throughout the crystalline structure formed in PEN nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41765.  相似文献   

14.
The deformation induced structure evolutions of polyamide 6 (PA6) during uniaxial tension at high tensile temperatures (60 °C and 90°C) were investigated with in situ wide- and small-angle X-ray scattering (WAXS and SAXS) technologies. The obtained data on structure evolutions revealed that they were different from the results measured at low temperature (30 °C). The α-phase got oriented once upon the beginning of deformation. After yielding the γ-phase started to be oriented following the α-phase. While, the breakdown of PA6 crystals along a and c axis overcame partial crystalline orientation at the high tensile temperatures (60 and 90 °C). The competition between stretch of amorphous phase and slippage of lamellae after yielding affected the deformation behavior of PA6. The collapse of lamellae was also confirmed from SAXS analysis and such disrupted lamellar structure resulted in the decrease of long spacing of PA6. The results showed that PA6 materials may show higher ductility at high temperatures. Therefore the crystals could be broken more easily and the formed lamellar fragments of PA6 could be preserved at larger strain at 90 °C. In addition, the yielding of PA6 and γ-phase orientation depended on the lamellar slippage during the deformation. POLYM. ENG. SCI., 60:581–586, 2020. © 2019 Society of Plastics Engineers  相似文献   

15.
Ya-Sen Sun 《Polymer》2006,47(23):8032-8043
Temperature-resolved small-angle X-ray scattering (SAXS) on poly(hexamethylene terephthalate) (PHT) samples crystallized from the melt yields direct information about the morphological changes in lamellar crystals and interlamellar amorphous layers upon melt-crystallization and subsequent heating to melting. Absolute intensities of these SAXS patterns were further analyzed via one-dimensional correlation and interface distribution functions. These analyses indicate that melt-crystallization at low temperature produces lamellar crystals having diverse thicknesses whereas crystallization at high temperature tends to favor growth of thick lamellar crystals with a nearly uniform distribution of thickness. When heating the PHT samples in the melting temperature region, the melting of the lamellar crystals was found to correlate well with the sequential-melting features. When these crystals are heated to higher temperatures, structural alterations from stacked lamellae to isolated lamellar crystals evolve with increasing extent of sequential melting, but, upon re-crystallization during extended annealing, the isolated lamellar crystals can pass through a reversible transition back to stacked lamellae.  相似文献   

16.
The melting, isothermal and nonisothermal crystallization behaviors of poly(3‐hydroxybutyrate) (PHB) have been studied by means of temperature modulated differential scanning calorimetry (TMDSC) and conventional DSC. Various experimental conditions including isothermal/annealing temperatures (80, 90, 100, 105, 110, 120, 130, and 140°C), cooling rates (2, 5, 10, 20, and 50°C/min) and heating rates (5, 10, 20, 30, 40, and 50°C/min) have been investigated. The lower endothermic peak (Tm1) representing the original crystals prior to DSC scan, while the higher one (Tm2) is attributed to the melting of the crystals formed by recrystallization. Thermomechanical analysis (TMA) was used to evaluate the original melting temperature (Tmelt) and glass transition temperature (Tg) as comparison to DSC analysis. The multiple melting phenomenon was ascribed to the melting‐recrystallization‐remelting mechanism of the crystallites with lower thermal stability showing at Tm1. Different models (Avrami, Jeziorny‐modified‐Avrami, Liu and Mo, and Ozawa model) were utilized to describe the crystallization kinetics. It was found that Liu and Mo's analysis and Jeziorny‐modified‐Avrami model were successful to explain the nonisothermal crystallization kinetic of PHB. The activation energies were estimated in both isothermal and nonisothermal crystallization process, which were 102 and 116 kJ/mol in respective condition. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42412.  相似文献   

17.
The influences of the glass fiber (GF) content and the cooling rate for nonisothermal crystallization process of poly(butylene terephthalate)/poly(ethylene terephthalate) (PBT/PET) blends were investigated. The nonisothermal crystallization kinetics of samples were detected by differential scanning calorimetry (DSC) at cooling rates of 5°C/min, 10°C/min, 15°C/min, 20°C/min, 25°C/min, respectively. The Jeziony and Mozhishen methods were used to analyze the DSC data. The crystalline morphology of samples was observed with polarized light microscope. Results showed that the Jeziony and Mozhishen methods were available for the analysis of the nonisothermal crystallization process. The peaks of crystallization temperature (Tp) move to low temperature with the cooling rate increasing, crystallization half‐time (t1/2) decrease accordingly. The crystallization rate of PBT/PET blends increase with the lower GF contents while it is baffled by higher GF contents. POLYM. COMPOS. 36:510–516, 2015. © 2014 Society of Plastics Engineers  相似文献   

18.
By using thermally stimulated depolarization current (TSDC) technique, and coupling it with the thermal sampling (TS) method, the relaxation behavior of Poly(vinyl chloride-co-vinylacetate-co-2-hydroxypropyl acrylate) (PVVH) has been investigated in the vicinity of its glass transition temperature, Tg. The global TSDC spectra of amorphous PVVH with varying the poling field and poling temperature revealed the presence of two TSDC peaks. The first peak at about 347 K and is ascribed to the glass transition temperature and can be referred as α-relaxation. The second one is obtained in the temperature range 353–383 K and is attributed to the space charge relaxation and can be referred as ρ-relaxation. Fine structure of α-relaxation peak was obtained using the thermal sampling method. All the molecular parameters, such as activation energy (Ea) and preexponential factor (τ0), have been estimated. In addition, the compensation law was found to be valid; and the compensation parameters such as compensation temperature (Tc) and compensation time (τc) have been determined.  相似文献   

19.
The microstructure and morphology of an olefinic blocky copolymer (OBC) and an ethylene‐hexene copolymer prepared by conventional Ziegler‐Natta catalysis (ZNEH) are compared. It is found that these two samples have similar melting temperatures, but the overall comonomer content in OBC is slightly higher. The crystallization temperature and crystallinity of OBC are markedly lower than those of ZNEH. A successive self‐nucleation annealing experiment reveals that OBC has a more uniform distribution of crystal thickness, indicating a more homogeneous composition distribution in its hard blocks. Small‐angle X‐ray scattering (SAXS) results show that the long period of OBC hardly changes with temperature in the low‐temperature range, whereas that of ZNEH increases gradually with temperature due to melting of the less perfect crystals. The average lamellar thickness of crystals is larger for OBC than for ZNEH, but the thickness of the thickest crystals is comparable in the two. The SAXS profiles were analyzed using a one‐dimensional correlation function. The result reveals that the partially ordered interphases in OBC are mainly located at the interface of the crystalline and amorphous phases. In contrast, the interface of the crystalline and amorphous phases in ZNEH is quite sharp and it is inferred that the partially ordered interphases are distributed in the bulk as separated domains. Scattered tiny crystals are formed in ZNEH, but OBC exhibits a macroscopic morphology of large spherulites. It is also observed that more amorphous phases are rejected outside of the lamellar stacks and spherulites in OBC. © 2012 Society of Chemical Industry  相似文献   

20.
WAXD, SAXS, FTIR, DSC and density techniques have been used to investigate the crystal structure, crystal density ρc, amorphous density pa equilibrium heat of fusion δH°m and equilibrium melting temperature T°m. By extrapolating the straight lines in the FTIR absorbance against density plot to zero intensity. ρc and ρa were estimated to be 1.098 and 1.003 g/cm3 respectively. The ρc obtained was too low in value. From X-ray diffraction patterns of uniaxially oriented fibres, the crystal structure of Nylon-1010 was determined. The Nylon-1010 crystallized in the triclinic system, with lattice dimensions: a = 4.9 Å, b = 5.4 Å, c = 27.8 Å, α = 49°, β = 77°, γ = 63.5°. The unit cell contained one monomeric unit, the space group was P1 , and the correct value of ρc was 1.135 g/cm3. The degree of crystallinity of the polymer was determined as about 60% (at RT) using Ruland's method. SAXS has been used to investigate the crystalline lamellar thickness, long period, transition zone, the specific inner surface and the electron density difference between the crystalline and amorphous regions for Nylon-1010. The analysis of data was based upon a one-dimensional electron-density correlation function. δ H°m was estimated to be 244.0 J/g by extrapolation of δH°m in the plot of heat of fusion against specific volume of semicrystalline specimens to the completely crystalline condition (V = 1/ρc). Owing to the ease of recrystallization of melt-crystallized Nylon-1010 specimens, the well-known Hoffman's Tm-Tc method failed in determining T°m and a Kamide double extrapolation method was adopted. The T°m value so obtained was 487 K.  相似文献   

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