Crystallization behavior of PA66/SiO2 organic‐inorganic hybrid material

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     

Non‐isothermal crystallization kinetics of polyamide 1010/montmorillonite nanocomposite

The non‐isothermal crystallization kinetics of pure polyamide 1010 (PA1010) and PA1010/montmorillonite nanocomposite (PA1010/MMT) was investigated by differential scanning calorimetry (DSC) at various cooling rates. The Avrami analysis modified by Jeziorny and a new method developed by Mo can describe the non‐isothermal crystallization process of PA1010 and PA1010/MMT nanocomposite very well. The difference in the value of exponent n between PA1010 and PA1010/MMT nanocomposite suggests that the nano‐size montmorillonite layers act as nucleation agents of PA1010. The values of half‐time of crystallization and crystallization rate coefficient (CRC) show that the crystallization rate of PA1010/MMT nanocomposite is faster than that of PA1010 at a given cooling rate. Polym. Eng. Sci. 44:861–867, 2004. © 2004 Society of Plastics Engineers.     

火焰喷涂PA1010/nano-ZrO2复合涂层的非等温结晶动力学

利用火焰喷涂法制备了聚酰胺1010 (PA1010)/纳米氧化锆（nano-ZrO₂）复合涂层。采用示差扫描量热法（DSC）研究其非等温结晶行为,对所得的数据分别用Jeziorny法、Ozawa法和Mo法进行处理。结果表明,用Jeziorny法和Mo法处理非等温结晶过程比较理想,而Ozawa法不适用。用Jeziorny法求出的参数Z_c(结晶速率常数）和n（Avrami指数)均随降温速率的增加而增加;nano-ZrO₂的加入使复合涂层的Z_c和n略大于纯PA1010涂层;并使复合涂层结晶半衰期降低、结晶速率及结晶度增大。表明nano-ZrO₂具有明显的成核剂作用,加快PA1010的结晶速率,提高涂层的结晶度。     

Nonisothermal crystallization of PP/nano‐SiO2 composites

The kinetics of nonisothermal crystallization of polypropylene (PP) containing nanoparticles of silicon dioxide (SiO₂) were investigated by differential scanning calorimetry (DSC) at various cooling rates. Several different analysis methods were used to describe the process of nonisothermal crystallization. The results showed that the Ozawa equation and Mo's treatment could describe the nonisothermal crystallization of the composites very well. The nano‐SiO₂ particles have a remarkable heterogeneous nucleation effect in the PP matrix. The rate of crystallization of PP/nano‐SiO₂ is higher than that of pure PP. By using a method proposed by Kissinger, activation energies have been evaluated to be 262.1, 226.5, 249.5, and 250.1 kJ/mol for nonisothermal crystallization of pure PP and PP/nano‐SiO₂ composites with various SiO₂ loadings of 1, 3, and 5%, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1013–1019, 2004     

Effect of zirconium dioxide on crystallization and melting behavior of flame sprayed polyamide 1010

The crystallization and melting behavior of flame sprayed Polyamide 1010 (PA1010) containing zirconium dioxide (ZrO₂) were investigated using differential scanning calorimeter (DSC). ZrO₂ has a heterogenous nucleation effect on PA1010, leading to a moderate increase in the crystallization temperature and a decrease in the supercooling temperature. A modified Avrami theory could be successfully used to well describe the early stages of non‐isothermal crystallization of PA1010 and its composite coatings. A study of the nucleation activity, which indicated the influence of the filler on the polymer matrix, revealed that the zirconium dioxide nanoparticles had a good nucleation effect on PA1010. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers.     

PE/PE‐g‐MAH/Org‐MMT nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of high‐density polyethylene (HDPE) and polyethylene (PE)/PE‐grafted maleic anhydride (PE‐g‐MAH)/organic‐montmorillonite (Org‐MMT) nanocomposite were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny, Ozawa analysis, and a method developed by Liu well described the nonisothermal crystallization process of these samples. The difference in the exponent n, m, and a between HDPE and the nanocomposite indicated that nucleation mechanism and dimension of spherulite growth of the nanocomposite were different from that of HDPE to some extent. The values of half‐time (t_1/2), K(T), and F(T) showed that the crystallization rate increased with the increase of cooling rates for HDPE and composite, but the crystallization rate of composite was faster than that of HDPE at a given cooling rate. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. It was 223.7 kJ/mol for composite, which was much smaller than that for HDPE (304.6 kJ/mol). Overall, the results indicated that the addition of Org‐MMT and PE‐g‐MAH could accelerate the overall nonisothermal crystallization process of PE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3054–3059, 2004     

Poly(propylene)–poly(propylene)‐grafted maleic anhydride–organic montmorillonite (PP–PP‐g‐MAH–Org‐MMT) nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of poly(propylene) (PP), PP–organic‐montmorillonite (Org‐MMT) composite, and PP–PP‐grafted maleic anhydride (PP‐g‐MAH)–Org‐MMT nanocomposites were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny and a method developed by Mo well‐described the nonisothermal crystallization process of these samples. The difference in the exponent n between PP and composite (either PP–Org‐MMT or PP–PP‐g‐MAH–Org‐MMT) indicated that nonisothermal kinetic crystallization corresponded to tridimensional growth with heterogeneous nucleation. The values of half‐time, Z_c; and F(T) showed that the crystallization rate increased with the increasing of cooling rates for PP and composites, but the crystallization rate of composites was faster than that of PP at a given cooling rate. The method developed by Ozawa can also be applied to describe the nonisothermal crystallization process of PP, but did not describe that of composites. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The results showed that the activation energy of PP–Org‐MMT was much greater than that of PP, but the activation energy of PP–PP‐g‐MAH–Org‐MMT was close to that of pure PP. Overall, the results indicate that the addition of Org‐MMT and PP‐g‐MAH may accelerate the overall nonisothermal crystallization process of PP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3093–3099, 2003     

Nonisothermal crystallization behavior of biodegradable poly(butylene terephthalate‐co‐butylene adipate‐co‐ethylene terephthalate‐co‐ethylene adipate) copolyester

A series of biodegradable aliphatic‐aromatic copolyester, poly(butylene terephthalate‐co‐butylene adipate‐co‐ethylene terephthalate‐co‐ethylene adipate) (PBATE), were synthesized from terephthalic acid (PTA), adipic acid (AA), 1,4‐butanediol (BG) and ethylene glycol (EG) by direct esterification and polycondensation. The nonisothermal crystallization behavior of PBATE copolyesters was studied by the means of differential scanning calorimeter, and the nonisothermal crystallization kinetics were analyzed via the Avrami equation modified by Jeziorny, Ozawa analysis and Z.S. Mo method, respectively. The results show that the crystallization peak temperature of PBATE copolyesters shifted to lower temperature at higher cooling rate. The modified Avrami equation could describe the primary stage of nonisothermal crystallization of PBATE copolyesters. The value of the crystallization half‐time (t_1/2) and the crystallization parameter (Z_c) indicates that the crystallization rate of PBATE copolyesters with more PTA content was higher than that with less PTA at a given cooling rate. Ozawa analysis was not suitable to study the nonisothermal crystallization process of PBATE copolyesters, but Z.S. Mo method was successful in treatingthis process. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Tribological behavior of the polyamide composite coating filled with different fillers under dry sliding

The polyamide (PA) composite coating filled with the particles of microsized MoS₂, microsized graphite, and nano‐Al₂O₃, respectively, were prepared by flame spraying. The friction and wear characteristics of the PA coating and composite coating filled with the varied content of filler under dry sliding against stainless steel were comparatively investigated using a block‐ring tester. The morphologies of the worn surfaces and transfer films on the counterpart steel ring were observed on a scanning electron microscope. The result showed that the addition of fillers to the composite coatings changed significantly the friction coefficient and wear rate of the coatings. The composite coatings filled with a low level content of fillers showed lower wear rate than did pure PA coating under dry sliding; especially the MoS₂/PA composite coating had the lowest wear rate among these composite coatings. The composite coatings with a high level content of fillers had higher wear rate than did pure PA coating, except of the Al₂O₃/PA composite coating. The bonding strengths between the polymer matrix and fillers changed with the content of the fillers, which accounted for the differences in the tribological properties of the composite coatings filled with the varied content fillers. On the other hand, the difference in the friction and wear behaviors of the composite coatings and pure coating were attributed to the difference in their worn surface morphologies and transfer film characteristics. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Crystallization behavior of poly(N‐methyldodecano‐12‐lactam). IV. Nonisothermal crystallization

Nonisothermal crystallization of poly(N‐methyldodecano‐12‐lactam) (MPA) was investigated using DSC method at cooling rates of 2–40 K/min. With increasing cooling rate, crystallization exotherms decreased in magnitude and shifted toward lower temperatures. Subsequent heating runs (10 K/min) showed an exotherm just above T_g, which increased in magnitude with the rate of preceding cooling run, corresponding to the continuation of primary crystallization interrupted as the system crossed T_g on cooling. Kinetic evaluation by the Avrami method gave values of exponent n close to 2.0, suggesting two‐dimensional crystal growth combined with heterogeneous nucleation. The Tobin method, covering the intermediate range of relative crystallinities, provided n ? 2.20, suggesting possible partial involvement of homogeneous nucleation at later stages of nonisothermal crystallization. The crystallization rate parameter k^1/n showed a linear dependency on cooling rate for both methods, the Tobin values being slightly higher. The Ozawa approach failed to provide reasonable values of the kinetic exponent m of MPA. The Augis–Bennet method was used to determine the effective activation energy of the entire nonisothermal crystallization process of MPA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 564–572, 2005     

Effect of the ionic liquid [bmim]PF6 on the nonisothermal crystallization kinetics behavior of poly(ether‐b‐amide)

Blending ionic liquid with crystalline polymer permits the design of new high‐performance composite materials. The final properties of these materials are critically depended on the degree of crystallinity and the nature of crystalline morphology. In this work, nonisothermal crystallization behavior of poly(ether‐b‐amide) (Pebax®1657)/room temperature ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate, [bmim]PF₆) was investigated by differential scanning calorimetry. The presence of [bmim]PF₆ can retard the nucleation of Pebax®1657 and lead to the crystallization depression of the PA block and the crystalline disappearance of the PEO block. However, the dilution effect of the IL results in a higher growth rate of crystallization of PA block. The influence of [bmim]PF₆ content and cooling rate on crystallization mechanism and spherulitc structures was determined by the Avrami equation modified by Jeziorny and Mo's methods, whereas the Ozawa's approach fails to describe the nonisothermal crystallization behavior of Pebax®1657/[bmim]PF₆ blends. In the modified Avrami analysis, the Avrami exponent of PA blocks, n > 3, for pure Pebax®1657, while 3 > n > 2 for Pebax®1657/[bmim]PF₆ blends testifies the transformation of crystallization growth pattern induced by [bmim]PF₆ from three‐dimensional growth of spherulites to a combination of two‐ and three‐dimensional spherulitic growth. Further, lower activation energy for the nonisothermal crystallization of PA blocks of Pebax®1657 can be observed with the increase of [bmim]PF₆ content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42137.     

Study on electrochemical behavior of Nano‐ZnO modified alkyd‐based waterborne coatings

A nano‐composite coating was formed using nano‐ZnO as pigment in different concentrations, to a specially developed alkyd‐based waterborne coating. The nano‐ZnO modified composite coatings were applied on mild steel substrate by dipping. The dispersion of nano‐ZnO particles in coating system was investigated by scanning electron microscopic and atomic force microscopic techniques. The effect of the addition of these nano‐pigments on the electrochemical behavior of the coating was investigated in 3.5% NaCl solution, using electrochemical impedance spectroscopy. Coating modified with higher concentration of nano‐ZnO particles showed comparatively better performance as was evident from the pore resistance (R_po) and coating capacitance (C_c) values after 30 days of exposure. In general, the study showed an improvement in the corrosion resistance of the nano‐particle modified coatings as compared with the neat coating, confirming the positive effect of nano‐particle addition in coatings. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

热喷涂LDPE/n-SiO2复合涂层非等温结晶动力学

采用火焰喷涂法制备了低密度聚乙烯（LDPE）涂层和LDPE/纳米二氧化硅（n-SiO₂）复合涂层。利用差示扫描量热法（DSC）对涂层的非等温结晶行为进行研究,并用Jeziorny法和Mo法进行处理。结果表明,Jeziorny法和Mo法处理涂层的非等温结晶过程比较合理;Jeziorny法得到的结晶速率常数和Avrami指数均随冷却速率的增加而增加,且n-SiO₂的加入使复合涂层的结晶速率常数和Avrami指数略有升高、半结晶时间降低,结晶速率增大,表明n-SiO₂相似文献   

Water‐dispersible conducting polyaniline/nano‐SiO2 composites without any stabilizer

A water‐dispersible conducting polyaniline/ nano‐SiO₂ composite, with a conductivity of 0.071 S cm^?1 at 25°C, was prepared by the oxidative polymerization of aniline in the presence of amorphous nano‐SiO₂ particles. And the structure, morphology, thermal stability, conductivity, and electroactivity of this composite were also investigated. This composite has been steadily dispersed in the aqueous solution for about 10–36 h without the need for any stabilizer. It would significantly impulse the commercial applications of conducting polyaniline/nano‐SiO₂ composite as fillers for antistatic and anticorrosion coatings. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nonisothermal crystallization of metallocene propylene–decene‐1 copolymers

The nonisothermal crystallization behavior of one metallocene‐based isotactic polypropylene and three propylene–decene‐1 copolymers was studied. The effects of comonomer content and cooling rate were investigated. It was found that comonomer units enchained systematically reduce the crystallization temperature (T_c), melting temperature (T_m), fusion enthalpy (ΔH_f), and crystallinity (X_c). Such an effect becomes more evident at a faster cooling rate. With increasing comonomer content, the supercooling required for crystallization increases and the overall crystallization rate is reduced. The Avrami equation is applicable to describe the nonisothermal crystallization kinetics of propylene–decene‐1 copolymer. It was shown that, although the reduced crystallization rate constant Z_c increases with comonomer content, the Avrami exponent decreases with comonomer content and cooling rate, leading to the smaller overall crystallization rate and larger crystallization half‐time of the copolymer with higher comonomer content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1724–1730, 2004     

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     

Nonisothermal crystallization behavior and crystals morphology of poly(trimethylene terephthalate)/nano‐calcium carbonate composites

Nonisothermal crystallization behavior and crystal morphology of poly(trimethylene terephthalate) (PTT) composites filled with modified nano‐calcium carbonate (CaCO₃) had been investigated by using differential scanning calorimetry and polarized optical microscopy. The modified Avrami equation and Ozawa theory were used to investigate the nonisothermal crystallization, respectively. The particles of nano‐CaCO₃, acting as a nucleation agent in composites, accelerated the crystallization rate by decreasing the half‐time of crystallization or increasing the parameters of Z_c and K(T). Moreover, the nano‐composite with 2 wt% nano‐CaCO₃ exhibited the highest crystallization rate. The Avrami and the Ozawa exponents, n and m of the nano‐composites, were higher than those of neat PTT, suggesting more complicated interaction between molecular chains and the nanoparticles that cause the changes of the nucleation mode and the crystal growth dimension. The effective activation energy calculated from the Friedman formula was reduced as nano‐CaCO₃ content increased, suggesting that the nano‐CaCO₃ made the molecular chains of PTT easier to crystallize during the nonisothermal crystallization process. The optical micrographs showed that much smaller or less perfect crystals were formed in composites because of the presence of the nano‐CaCO₃ particles. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Nonisothermal crystallization kinetics and morphology of self‐seeded syndiotactic 1,2‐polybutadiene

Subsequent melting behavior after isothermal crystallization at different temperatures from the isotropic melt and nonisothermal crystallization kinetics and morphology of partially melting sPB were carried out by differential scanning calorimetry (DSC), polarized light microscopy (POM), respectively. Triple melting‐endothermic peaks were observed for the polymer first isothermally crystallized at temperatures ranging from 141 to 149°C, respectively, and then followed by cooling at 10°C/min to 70°C. Comparing with the nonisothermal crystallization from the isotropic melt, the nonisothermal crystallization for the partially melting sPB characterized the increased onset crystallization temperature, and the sizes of spherulites became smaller and more uniform. The Tobin, Avrami, Ozawa, and the combination of Avrami and Ozawa equations were applied to describe the kinetics of the nonisothermal process. Both of the Tobin and the Avrami crystallization rate parameters (K_T and K_A, respectively) were found to increase with increase in the cooling rate. The parameter F(T) for the combination of Avrami and Ozawa equations increases with increasing relative crystallinity. The Ziabicki's kinetic crytallizability index G_Z for the partially melting sPB was found to be 3.14. The effective energy barrier Δ? describing the nonisothermal crystallization of partially melting sPB was evaluated by the differential isoconversional method of Friedman and was found to increase with an increase in the relative crystallinity. At the same time, Hoffman‐Lauritzen parameters (U and K_g) are evaluated and analyzed from the nonisothermal crystallization data by the combination of isoconversional approach and Hoffman‐Lauritzen theory. The K_g value obtained from DSC technique was found to be in good agreement with that obtained from POM technique. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1479–1491, 2006     

Crystallization and melting behavior of multi‐walled carbon nanotube‐reinforced nylon‐6 composites

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 (T_{CC, 1} and T_{CC, 2}) for PA6/MWNTs composites instead of a single exotherm (T_{CC, 1}) for the neat matrix. The formation of the higher‐temperature exotherm T_{CC, 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