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1.
A synthetic ureido mixture prepared from the reaction of 4,4′‐diphenylmethane disocynanate (MDI) and cyclohexylamine without using any harmful organic solvents, has been used as a nucleating agent (PNA) for polyamide 6 (PA6). The effect of PNA on the crystallization and mechanical properties of PA6 has been studied by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM), tensile test, melt flow index (MFI), and X‐ray diffraction (XRD). The results show that PNA is an effective nucleation agent for PA6. PNA affects the nucleation mechanism of PA6, and substantially accelerates the crystallization rate of PA6 and gives rise to smaller crystal size. In comparison with PA6, the crystallization temperature (Tc) of PA6/PNA (100/0.5) increases 21.3°C and the degree of sub‐cooling (ΔTc) decreases 23.7°C. Furthermore, because of the heterogeneous nucleation induced by PNA, the spherulites of PA6 become even and tiny based on POM observation. Polymorph transform has been obtained from XRD analysis. The virgin PA6 is free of γ‐phase crystals, presented as α‐phase crystals in this study, but γ‐phase crystal appears after the introduction of PNA. The mechanical and thermal properties of PA6 are obviously improved by the addition of PNA. POLYM. ENG. SCI., 55:2011–2017, 2015. © 2015 Society of Plastics Engineers  相似文献   

2.
Postconsumed polyamide 66 (PA66) short fibers derived from carpets were utilized as reinforcement in a commercial polyamide (PA12) matrix at different concentrations, ranging from 10 wt% to 30 wt%, in order to evaluate the effect of PA66 content on the mechanical and dynamic behavior of the resulting materials. DSC tests revealed that both melting and crystallization behavior of PA12 matrix was slightly affected by the presence of the fibers, showing a somewhat nucleation effect of PA66. Quasi‐static tensile tests evidenced that the introduction of PA66 fibers provided a slight stiffening effect on the resulting composites, increasing the elastic modulus with the filler content, especially at testing temperatures above Tg. On the other hand, the presence of agglomerated fibers led to an embrittlement of polyamide composites, showing a significant reduction of the tensile properties at break increasing the PA66 fibers content. Tensile dynamic tests confirmed the stiffening effect provided by the recycled fibers, increasing both dynamic moduli (E′ and E″) with PA66 content over the whole range of considered temperatures. Glass transition temperature of PA12 was substantially increased by the presence of the fibers, while the coefficient of linear thermal expansion above Tg was progressively reduced with the filler content. Interestingly, isothermal creep compliance of the material above Tg was substantially reduced by the presence of PA66 fibers. Morphological analysis on the cryofractured surfaces revealed a quite good fiber‐matrix interfacial adhesion, with the presence of some nucleating phenomena on the pulled out surfaces. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers  相似文献   

3.
The processability of single bubble polyamide 11 and polyamide 12 films was investigated. The development of crystalline structure and chain orientation of polyamide 11 and polyamide 12 films in single bubble film blowing was studied by differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXS), infrared (IR) spectroscopy, and birefringence. DSC measurements of both films revealed a spontaneous increase in glass transition temperature (Tg) and cold crystallization temperature (Tc) during aging at room conditions, with crystallinity and melting point remaining constant. Single bubble polyamide 11 and polyamide 12 films exhibited triclinic α and monoclinic γ crystals, respectively. The level of biaxial orientation was evaluated by calculating White‐Spruiell biaxial orientation factors with pole figure data. We were not able to produce biaxially oriented double bubble films with either polyamide 11 or polyamide 12.  相似文献   

4.
In this report, polyamides were solution blended in the formic acid with poly(vinyl pyrrolidone)(PVP), an amorphous polar polyamide. The thermal behaviors and morphological change in the blends of Nylon 6 (PA6) and PVP were investigated in details via WAXD, DSC, FT‐IR and POM methods. The equilibrium melting temperatures for PA6 in the blends were estimated based on the linear and nonlinear Hoffman‐Weeks (LHW and NLHW) extrapolative methods. With increasing the mass ratio of PVP to PA6, Tm (melting temperature) and Tc (crystallization temperature) of PA6 in blends both decreased as well as that of the spherulite size of PA6. The interaction mode between PVP and PA6 was investigated by FT‐IR spectroscopy, and the spectral changes indicated that the carbonyl groups of PVP had formed hydrogen bonding with the N? H groups of PA6 molecules in the molten state, which resulted in the variation of the morphology and thermal behaviors. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

5.
Blends of polyamide 6 (PA6) and polycarbonate (PC) have been investigated, over a full range of composition, to check interactions between them. SEM observations show that the mixtures are characterized by domains of clearly segregated homophases and voids between the two polymers. DSC and DMTA data indicate the presence of two Tg' s, corresponding to two separate phases, with the Tg of the PC phase decreasing on increasing the PA6 amount. Moreover, the crystallization kinetics of PA6 is slightly showed down by the PC. Chemical reactions between the two polymers are supposed to give rise to low molar mass compounds, as shown by GPC; these species plasticize the PC and partially dissolve into the molten polyamide, causing decrease of PC Tg and reduction of overall crystallization rate of PA6. Apparent influence of PC on melting temperature and enthalpy of PA6 is also discussed.  相似文献   

6.
The poly 2‐hydroxy propylmethacrylate‐methyl methacrylate (PHPMA‐MMA)/SiO2 composite, derived from 2‐hydroxy propylmethacrylate (HPMA), methyl methacrylate (MMA), and tetraethoxysilane (TEOS), was used to synthesize polyamide 66(PA66)/SiO2 organic‐inorganic hybrid material. X‐ray diffraction (XRD) was used to investigate the lattice spacing change of the PA66/SiO2 hybrid material. It was found that the addition of PHPMA‐MMA/SiO2 composite nearly did not change the crystal form of PA66. The nonisothermal crystallization kinetics of PA66 and PA66/SiO2 hybrid material was investigated by differential scanning calorimetry (DSC) with various cooling rates. At every given cooling rate, the start crystallization temperature of the PA66/SiO2 hybrid material was higher than that of PA66, while the crystallization temperature range was narrower than that of PA66. Avrami analysis modified by the Jeziorny method, the Ozawa method, and a method developed by Liu were employed to describe the nonisothermal crystallization process of the samples. The results showed that the Jeziorny method and the Ozawa method were not suitable to describe the nonisothermal crystallization process of PA66/SiO2 hybrid material; however, when the relative degree of crystallinity X (t) was less than 1 ? 1/e, ln [? ln (1 ? X (t))] was still linear to lnt. The Liu method was successful to describe the nonisothermal crystallization processes for both PA66 and the PA66/SiO2 hybrid material. It was confirmed that the presence of PHPMA‐MMA/SiO2 composite could increase the crystallization rate and had a hetero phase nucleation effect on the PA66 matrix. Moreover, the introduction of PHPMA‐MMA/SiO2 could improve the crystallization active energy ?E calculated by the Kissinger equation, attributing to the strong interaction between the polyamide chains and the PHPMA‐MMA/SiO2 composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 810–817, 2006  相似文献   

7.
Crystallization kinetics of the newly developed Al2O3‐Y3Al5O12 (YAG) amorphous ceramic coating fabricated by atmospheric plasma spraying (APS) were investigated via differential scanning calorimetry (DSC) under non‐isothermal conditions. The phase compositions and microstructure of the as‐sprayed coating were characterized by X‐ray diffraction (XRD) and Scanning electron microscopy (SEM). The glass transition temperature Tg, the onset temperature of crystallization Tc and the peak temperature of crystallization Tp presented heating rate dependence. The related kinetic parameters of activation energies (Eg, Ec, Ep) and Avrami exponents (n) were quantified using various methods including Kissinger, Augis–Bennett, Ozawa and Matusita–Sakka, etc., to understand the phase transition mechanism and crystallization process in depth. A series of parameters including devitrification interval ΔT, thermal stability (Tc, Ec), nucleation resistance Ec/RTg and fragility index F were quantified in order to evaluate the nucleation mechanism, crystallization behavior and thermal stability of Al2O3‐YAG amorphous ceramic coating. Excellent thermal stability was witnessed in the studied coating. Furthermore, the YAG crystalline phases can be reasonably controlled and independently precipitated from the amorphous matrix via proper annealing.  相似文献   

8.
Xiaohua Huang  Baoli Shi  Liping Li 《Polymer》2008,49(4):1049-1055
The interfacial interaction of flame retarded and glass fiber reinforced PA66 composites is a very important issue due to one of the key factors influencing the mechanical properties of materials. In this article, the interfacial interaction among the components in the composites has been studied by IGC/DSC/SEM techniques. The experimental data demonstrated that Zn2+-modified melamine polyphosphate (Zn-MpolyP) flame retardant could obviously enhanced the mechanical properties of the composites compared with melamine polyphosphate (MpolyP). SEM results proved that Zn-MpolyP could well disperse in the composites, and effectively improve the interfacial compatibility of the composites. Based on DSC results, Zn-MpolyP and MpolyP promoted the crystallization enthalpy (ΔHc) and temperature (Tc) of PA66 to increase. Zn-MpolyP showed more effect in increasing the crystallization degree of PA66 than MpolyP. They exhibited the nucleating effect in PA66. The Lewis acid-base numbers (Ka and Kb) and their ratio (Kb/Ka) obtained by inverse gas chromatography (IGC) further proved that the strongest Lewis acid-base interaction between PA66 and Zn-MpolyP existed in the composites. This result is probably due to the strong complex between Zn2+ in Zn-MpolyP and lone pair electrons at O and N atoms of PA66 and glass fiber. Therefore, the all results of IGC/DSC/SEM techniques demonstrated that the interfacial compatibility of components in composites was better improved by Zn-MpolyP than MpolyP.  相似文献   

9.
The crystallization and melting behavior of neat nylon‐6 (PA6) and multi‐walled carbon nanotubes (MWNTs)/PA6 composites prepared by simple melt‐compounding was comparatively studied. Differential scanning calorimetry (DSC) results show two crystallization exotherms (TCC, 1 and TCC, 2) for PA6/MWNTs composites instead of a single exotherm (TCC, 1) for the neat matrix. The formation of the higher‐temperature exotherm TCC, 2 is closely related to the addition of MWNTs. X‐ray diffraction (XRD) results indicate that only the α‐phase crystalline structure is formed upon incorporating MWNTs into PA6 matrix, independently of the cooling rate and annealing conditions. These observations are significantly different from those for PA6 matrix, where the increase in cooling rate or decrease in annealing temperature results in the crystal transformation from α‐phase to γ‐phase. The crystallization behavior of PA6/MWNTs composites is also significantly different from those reported in PA6/nanoclay systems, probably due to the difference in nanofiller geometry between one‐dimensional MWNTs and two‐dimensional nanoclay platelets. The nucleation sites provided by carbon nanotubes seem to be favorable to the formation of thermodynamically stable α‐phase crystals of PA6. The dominant α‐phase crystals in PA6/MWNTs composites may play an important role in the remarkable enhancement of mechanical properties. Copyright © 2005 Society of Chemical Industry  相似文献   

10.
Polymer blended materials such as polyamide 6 (PA6)/polypropylene (PP) blends have received considerable attention in recent years. To improve the compatibility of PA6 and PP, compatibilizers like maleic anhydride‐g‐polypropylene (MPP) are often added. In addition, organically modified montmorillonite (MMT) is also used to improve the properties of various materials. In this work, the crystallization behavior of PP/PA6/MMT nanocomposites with MPP compatibilizer was investigated systematically. The annealing process effectively improved the crystallization of α‐PP. The crystallization temperature (Tc) of PA6 was increased by ca 2–3 °C on introducing MPP or MMT alone to the PP/PA6 system, whereas Tc of PP underwent no obvious change. However, when MPP and MMT were added simultaneously, Tc of PP and PA6 increased by 6.6 and 4.2 °C, respectively, and a new crystallization peak corresponding to PP‐g‐PA6 copolymer phase was observed at 162.5 °C. The combined effect of MPP and MMT led to better compatibility of PP with PA6. Moreover, the results of a non‐isothermal crystallization kinetics experiment revealed that the simultaneous introduction of MPP and MMT markedly shortened the crystallization time. Copyright © 2010 Society of Chemical Industry  相似文献   

11.
The isothermal crystallization kinetics, the morphology, and the melting behavior of melt‐processed composites of poly(phenylene sulfide) (PPS) with a thermotropic liquid crystalline copolyester, Vectra A950, (TLCP) were studied by differential scanning calorimetry (DSC) and optical microscopy. The crystallization behavior of PPS in PPS/TLCP composites is observed to be highly sensitive to Tc and immiscible TLCP content in the composites. The spherulite growth rate, the overall crystallization rate, and the activation energy of PPS in PPS/TLCP composites are markedly depressed by the presence of TLCP. The analysis of the Avrami kinetic parameters (n and k) indicates that blending of TLCP with PPS causes heterogeneous growth process and nucleation mechanisms. At low Tcs, the PPS crystallization rate is faster than that neat PPS with ≤30 wt% TLCP loading whereas at high Tcs it remains almost unchanged. The analysis of the melting behavior of these composites indicates that the stability of PPS crystals and their reorganization is influenced both by the Tcs and the composite compositions. The sizes and the number of spherulites change a great extent with composite composition with a drop of spherulite rapid growth rate, at constant Tc, with increasing content of TLCP in composites. The analysis based on the Lauritzen‐Hoffmann secondary nucleation theory, using present DSC data, indicates that present data predominantly follow a linear growth trend over a present range of Tcs and PPS crystallization in composites still occurs according to regime II kinetics, whereby multiple surface nuclei form on the substrate with multiple nucleation acts commencing before initially formed growth layer is completed. The fold surface free energy of PPS chains in composites is found higher than that of neat PPS, leading to an average higher work of chain folding and is ascribed to a general development of the PPS chain mobility in the composite melt. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers  相似文献   

12.
In situ compatibilized melt blends of polyamide 6 (PA‐6) with polyester elastomer (PEL) were prepared in a corotating twin‐screw extruder using two types of coupling agent (CA): diglycidyl ether of bisphenol A (DGEBA) and 1,4‐phenylene bis(2‐oxazoline) (PBO). The notched impact strength of PA‐6 and PA‐6/PEL blends increased with the addition of coupling agent, especially DGEBA, and the maximum impact toughening of the blend was obtained with 0.6 mol % DGEBA, the composition of minimum domain size observed from SEM. Viscosities of the untreated blends increased over those of the base resins at low frequencies. Viscosities of both the base resins and the blends increased with the addition of CA, and the effect was much more pronounced with DGEBA, especially for PA‐6 and PA‐6–rich blends. The crystallization temperature (Tc) of PEL increased over 10°C, whereas the Tc of PA‐6 decreased by 2–3°C in the blends. With the addition of coupling agents, the crystallization melting temperature (Tm) and Tc of PA‐6 decreased by up to 5°C with DGEBA, implying that the crystallization of PA‐6 is disturbed by the in situ formed PA‐6–CA–PEL or PA‐6–CA–PA‐6 type copolymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3966–3973, 2004  相似文献   

13.
A new method to prepare low melting point polyamide‐6 (LPA6) by complex reaction of calcium chloride (CaCl2) and polyamide‐6 (PA6) in a co‐rotating twin screw extruder was reported. We employed a new rheological method to study the crystallization behavior of PA6/CaCl2 complex and the mechanism of confined crystallization of PA6. Compared with differential scanning calorimetry (DSC), this method was more capable of detecting crystalline information. What's more, it was also an effective method for studying mechanism of confined crystallization. From the results of X‐ray diffraction, DSC, infrared spectroscopy, rheology, and mechanical properties, the complex reaction of CaCl2 with the carbonyl oxygen atom in the amide group disrupted the intermolecular hydrogen bonding and confined the mobility of PA6 molecules. This could significantly reduce the crystallinity and melting temperature of PA6, and improve tensile strength and notched Izod impact strength. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41513.  相似文献   

14.
This work examined how pre‐melting temperature (Tmax) affects the isothermal melt crystallization kinetics, the resulting melting behavior and crystal structure of syndiotactic polystyrene (sPS) by using differential scanning calorimetry (DSC), polarized light microscopy (PLM) and the wide angle X‐ray diffraction (WAXD) technique. Experimental results indicated that raising Tmax decreased the nucleation rate and the crystal growth rate of sPS. The Avrami equation was also used to analyze the overall crystallization kinetics. The Avrami exponent n and rate constant K were determined for different Tmax specimens at various crystallization temperatures (Tc's). Our results indicated that the nucleation type of sPS is Tmax and Tc dependent as well. Evaluation of the activation energy for the isothermal crystallization processes revealed that it increases from 375 kJmol?1 to 485 kjmol ?1 with an increase of Tmax. From the melting behavior study, we believe that the Tmax and Tc‐dependent multiple melting peaks are associated with different polymorphs as well as recrystallized crystals formed during heating scans. Moreover, the percentage content of α form in the crystals formed under different crystallization conditions was estimated through WAXD experiments.  相似文献   

15.
Polypropylene/polypropylene‐grafted‐maleic anhydride/glass fiber reinforced polyamide 66 (PP/PP‐g‐MAH/GFR PA 66) blends‐composites with and without the addition of polypropylene‐grafted‐maleic anhydride (PP‐g‐MAH) were prepared in a twin screw extruder. The effect of the compatibilizer on the thermal properties and crystallization behavior was determined using differential scanning calorimetry analysis. The hold time was set to be equal to 5 min at 290°C. These conditions are necessary to eliminate the thermomechanical history in the molten state. The crystallization under nonisothermal conditions and the plot of Continuous‐Cooling‐Transformation of relative crystallinity diagrams of both PP and PA 66 components proves that PP is significantly affected by the presence of PP‐g‐MAH. From the results it is found that an abrupt change is observed at 2.5 wt % of PP‐g‐MAH as a compatibilizer and then levels off. In these blends, concurrent crystallization behavior was not observed for GFR PA66. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1620–1626, 2007  相似文献   

16.
R.T. Tol 《Polymer》2005,46(9):2955-2965
Crystallization kinetics and crystallinity development of PA6 droplets having sizes from 0.1 to 20 μm dispersed in immiscible uncompatibilized PS/PA6 and reactively compatibilized (PS/Styrene-maleic anhydride copolymer=SMA2)/PA6 blends are reported. These blend systems show fractionated crystallization, leading to several separate crystallization events at different lowered temperatures. Isothermal DSC experiments show that micrometer-sized PA6 droplets crystallizing in an intermediate temperature range (Tc∼175 °C) below the bulk crystallization show a different dependency on cooling rate compared to bulk crystallization, and an athermal crystallization mechanism is suggested for PA6 in this crystallization temperature region. The crystallinity in these blends decreases with PA6 droplet size. Random nucleation, characteristic for a homogeneous nucleation process, is found for sub-micrometer sized PA6 droplets crystallizing between Tc 85 and 110 °C using isothermal DSC experiments. However, crystallization in the PA6 droplets is most likely initiated at the PA6-PS interface due to vitrification of the PS matrix during crystallization. Very imperfect PA6 crystals are formed in this low temperature crystallization region, leading to a strongly reduced crystallinity. These crystals show strong reorganization effects upon heating.  相似文献   

17.
The effects of α‐form and β‐form nuclei on polymorphic morphology of poly(butylene adipate) (PBA) upon recrystallization from the molten state up to various Tmax values were examined by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD) and polarized light microscopy (PLM). In this study, PBA with complex melting and polymorphism behaviour was used as a model for examining different types and extents of residual nuclei. As the PBA initially containing the sole α‐crystal was brought to a molten state of various Tmax, the extents of trace α‐form crystal nuclei varied and were dependent on Tmax. Furthermore, it did not matter whether, initially, the PBA contained α‐ or β‐form crystals (or both) because only a single type of α‐nuclei could be left upon treatment to the molten liquid state at Tmax. Therefore, only the α‐crystal in PBA had ‘memory capacity’ in the molten liquid state while the β‐crystal did not. This was so because the latter had been completely transformed into the solid state prior to being heated into a liquid. PBA crystallized before α‐nuclei could be packed into α‐crystal, regardless of the crystallization temperature (Tc). For recrystallization from molten PBA without any nuclei, the crystalline polymorphism was correspondingly influenced by Tc. Copyright © 2005 Society of Chemical Industry  相似文献   

18.
Nonisothermal crystallization of polylactide (PLA)/silica composites prepared by (i) directly blending the PLA with nanoscale colloidal silica sol and by (ii) a sol–gel process are studied by differential scanning calorimeter (DSC) at various heating rates. Samples quenched from the molten state exhibited two melting endotherms (Tml and Tmh) due to melt‐recrystallization during the DSC scans. Lower heating rate and the presence of silica particles generate a lower peak intensity ratio of Tml /Tmh. The nonisothermal crystallization kinetics is analyzed by modified Avrami model, Ozawa model, and Liu‐Mo models. The modified Avrami and Liu‐Mo models successfully described the nonisothermal cold crystallization processes, but Ozawa is inapplicable. The nucleation constant (Kg) is calculated by modified Lauritzen‐Hoffman equation and the activation energy by Augis‐Bennett, Kissinger, and Takhor models. These calculated parameters indicate consistently that the nanoscale silica particles seem to form more heterogeneous nucleation to increase crystallization, but microscale one form hindrance to retard crystallization. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

19.
The thermal behavior and morphology of multicomponent blends based on PA6, polyamide 6 (PA6)/styrene–acrylonitirle copolymer (SAN), PA6/acrylonitrile–butadiene–styrene terpolymer (ABS), and their compatibilized blends with styrene–acrylonitrile–maleic anhydride copolymer (SANMA) were studied using DSC and SEM. The blends were prepared in a twin‐screw extruder under similar processing conditions, keeping the PA6 content fixed at 50 wt %. It was found that, in all the blends, the second component had a nucleating effect and improved the overall degree and rate of crystallization of PA6, whereas addition of a compatibilizer slightly diminished these effects and resulted in significant changes in the blend morphology. The nucleating effect and consequent changes in the crystallization behavior was attributed to the presence of SAN, which is a common component in all the blends. The Tg of PA6 in the blends with a cocontinuous morphology, due to the connectivity between the phases, is higher than in the blends with a disperse‐type morphology. The compatibilized blends have a lower crystallization rate and nucleation ability with a cocontinuous morphology, whereas the uncompatibilized blends have a higher crystallization rate with a higher nucleation ability and a disperse and/or a coarse cocontinuous morphology. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2753–2759, 2002  相似文献   

20.
The crystallization behavior and morphology of polyoxymethylene (POM) and POM with polyamide (PA) were studied by polarized light microscopy (PLM), isothermal and nonisothermal differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). The isothermal crystallization kinetics were analyzed with the Avrami equation. Compared with the virgin POM, the addition of PA can reduce the spherulites size and improve the crystallization growth rate and crystallinity (Xc) of POM, which demonstrates that the nucleation effect of PA as the high‐molecular nucleus is favorable to the mechanical properties and dimension stability of POLYM. ENG. SCI., 45:1174–1179, 2005. © 2005 Society of Plastics Engineers  相似文献   

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