Nonisothermal crystallization kinetics of polyoxymethylene/montmorillonite nanocomposite

The nonisothermal crystallization kinetics of polyoxymethylene (POM), polyoxymethylene/Na–montmorillonite (POM/Na–MMT), and polyoxymethylene/organic–montmorillonite (POM/organ–MMT) nanocomposites were investigated by differential scanning calorimetry at various cooling rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the nonisothermal crystallization process of POM/Na–MMT and POM/organ–MMT nanocomposites. The difference in the values of the exponent n between POM and POM/montmorillonite nanocomposites suggests that the nonisothermal crystallization of POM/Na–MMT and POM/organ–MMT nanocomposites corresponds to a tridimensional growth with heterogeneous nucleation. The values of half‐time and the parameter Z_c, which characterizes the kinetics of nonisothermal crystallization, show that the crystallization rate of either POM/Na–MMT or POM/organ–MMT nanocomposite is faster than that of virgin POM at a given cooling rate. The activation energies were evaluated by the Kissinger method and were 387.0, 330.3, and 328.6 kJ/mol for the nonisothermal crystallization of POM, POM/Na–MMT nanocomposite, and POM/organ–MMT nanocomposite, respectively. POM/montmorillonite nanocomposite can be as easily fabricated as the original polyoxymethylene, considering that the addition of montmorillonite, either Na–montmorillonite or organ–montmorillonite, may accelerate the overall nonisothermal crystallization process. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2281–2289, 2001     

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     

Crystallization behavior of polypropylene/polyamide 6/montmorillonite nanocomposites

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 (T_c) of PA6 was increased by ca 2–3 °C on introducing MPP or MMT alone to the PP/PA6 system, whereas T_c of PP underwent no obvious change. However, when MPP and MMT were added simultaneously, T_c 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     

Nonisothermal crystallization kinetics of flame‐sprayed polyamide 1010/nano‐ZrO2 composite coatings

Polyamide1010 (PA1010) and its composite with nanometer‐sized zirconia (PA1010/nano‐ZrO₂) coatings were deposited using a flame spray process. The kinetics of nonisothermal crystallization of PA1010/nano‐ZrO₂ composite coatings was 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 modified Avrami equation and Mo's treatment could describe the nonisothermal crystallization of the composite coatings very well. The nano‐ZrO₂ particles have a remarkable heterogeneous nucleation effect in the PA1010 matrix. The values of halftime and Z_c showed that the crystallization rate increased with increasing cooling rates for both PA1010 and PA1010/nano‐ZrO₂ composite coating, but the crystallization rate of PA1010/nano‐ZrO₂ composite coating was faster than that of PA1010 at given cooling rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Crystallization behavior of poly(vinylidene fluoride)/montmorillonite nanocomposite

The crystallization behavior of poly(vinylidene fluoride)/montmorillonite (PVDF/MMT) nanocomposite was investigated by using differential scanning calorimeter (DSC), polarizing optical microscope (POM), and X‐ray diffraction. The results showed that the crystallization behavior of PVDF was changed by adding MMT in PVDF matrix. The MMT layers in PVDF acted as effective nucleation agents. It is observed that the crystallization temperature of PVDF/MMT nanocomposite was higher than that of PVDF at various cooling rates. The value of half‐time of crystallization showed that the crystallization rate of PVDF/MMT nanocomposite was faster than that of PVDF at a given cooling rate. The addition of MMT hindered the growth of spherulite. Nonisothermal crystallization data was analyzed using Avrami, Ozawa, and Jeziorny method. The Jeziorny method successfully described the nonisothermal crystallization behaviors of PVDF/MMT nanocomposite. The MMT loading was favorable to produce the piezoelectric β phase in the PVDF matrix. The α phase coexisted with the β phase in the PVDF/MMT nanocomposite. For this polymorphic structure, a possible explanation was proposed based on the variable temperature X‐ray diffraction, DSC, and POM experiments. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Crystal morphology and crystallization kinetics of polyamide‐11/clay nanocomposites

Polyamide‐11 (PA11)/clay nanocomposites were prepared by in situ intercalative polymerization. The crystal morphology and crystallization kinetics of these nanocomposites were investigated via polarized light microscopy (PLM), small‐angle laser scattering (SALS) and differential scanning calorimetry (DSC). PA‐11 can crystallize into well‐formed spherulites, while only very tiny crystallites were observed by PLM and SALS for the nanocomposites. Both isothermal and non‐isothermal crystallization methods were employed to investigate the crystallization kinetics by DSC. Both techniques showed an increased crystallization rate with the addition of clay. However, the Avrami exponent decreased with the addition of clay in isothermal crystallization but showed a wide range of values depending on the cooling rate in the non‐isothermal crystallization. The changes in crystal morphology and crystallization kinetics can be understood as being due to the ‘supernucleating’ effect of the nanodispersed clay layers. Copyright © 2004 Society of Chemical Industry     

Nonisothermal crystallization kinetics of poly(ethylene terephthalate)/clay nanocomposites prepared by melt processing

In this study, cold and melt crystallization behaviors of amorphous poly(ethylene terephthalate) (PET)/clay nanocomposites were investigated. Two nanocomposite samples with the same amount of inorganic content were prepared by melt processing using natural montmorillonite (Na‐MMT) and organo‐modified montmorillonite (org‐MMT). Depending on the clay structure, clay dispersion into PET and crystallization behavior of the samples were studied using X‐ray diffraction and differential scanning calorimetry methods, respectively. Effects of clay structure and organic groups between clay layers in org‐MMT on the melt crystallization kinetics of the samples were analyzed with various kinetic models, namely, the Ozawa, Avrami modified by Jeziorny, and Liu‐Mo. Crystallization activation energies of the samples were also determined by the Kissinger and Augis–Bennett models. Exfoliated structures were obtained in the nanocomposite samples prepared with both the Na‐MMT and org‐MMT. From the kinetics study, it was found that the melt‐crystallization rate of the sample prepared with the Na‐MMT was higher than that prepared with the org‐MMT at a given cooling rate. It can be concluded that organic ammonium groups in the org‐MMT decelerate the crystallization rate of PET chains possibly by affecting the chain diffusion and folding. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Crystallization behavior of carbon nanotubes‐filled polyamide 1010

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

Preparation and properties of PET/PA6 copolymer/montmorillonite hybrid nanocomposite

From in situ polycondensation, a poly(ethylene terephthalate)/Polyamide 6 copolymer/montmorillonite nanocomposite was prepared, after the treatment of montmorillonite (MMT) with a water soluble polymer. The resulting nanocomposites were characterized by X‐ray diffraction (XRD), differential scanning calorimeter (DSC), nuclear magnetic resonance (NMR), dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM). The results of DSC, ¹H NMR, and DMA proved that the nanocomposite synthesized was PET/PA6 copolymer/MMT nanocomposite, not the PET/PA6 blend/MMT nanocomposite. The results of XRD and TEM proved that the dispersion of MMT was improved observably after the introduction of PA6 molecular chain into PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2512–2517, 2006     

Crystallization kinetics of poly (L‐lactic acid)/montmorillonite nanocomposites under isothermal crystallization condition

Poly(L ‐lactic acid)/o‐MMT nanocomposites, incorporating various amounts of organically modified montmorillonite (o‐MMT; 0–10 wt %), were prepared by solution intercalation. The montmorillonite (MMT) was organically modified with dilauryl dimethyl ammonium bromide (DDAB) by ion exchange. Transmission electron microscopy (TEM) and X‐ray diffraction (XRD) reveal that the o‐MMT was exfoliated in a poly(L ‐lactic acid), (PLLA) matrix. A series of the test specimens were prepared and subjected to isothermal crystallization at various temperatures (T₁–T₅). The DSC plots revealed that the PLLA/o‐MMT nanocomposites that were prepared under nonisothermal conditions exhibited an obvious crystallization peak and recrystallization, but neat PLLA exhibited neither. The PLLA/o‐MMT nanocomposites (2–10 wt %) yielded two endothermic peaks only under isothermal conditions at low temperature (T₁), and the intensity of Tm₂ (the higher melting point) was proportional to the o‐MMT content (at around 171°C). The melting point of the test samples increased with the isothermal crystallization temperature. In the Avrami equation, the constant of the crystallization rate (k) was inversely proportional to the isothermal crystallization temperature and increased with the o‐MMT content, especially at low temperature (T₁). The Avrami exponent (n) of the PLLA/o‐MMT nanocomposites (4–10 wt %) was 2.61–3.56 higher than that of neat PLLA, 2.10–2.56, revealing that crystallization occurred in three dimensions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of alkane chain segment length on the crystallization kinetics of nylon 1010, 1013 and 1014

Isothermal and non‐isothermal crystallization kinetics of long alkane chain segment nylon 1010, 1013 and 1014 were investigated by differential scanning calorimetry. The commonly used Avrami equation and that modified by Jeziorny were employed to fit the isothermal and non‐isothermal crystallizations of nylon 1010, 1013 and 1014, respectively. It was found that the crystallization rate of nylon with a longer alkane chain segment was slower than that of nylon with a shorter one at a given cooling rate. The activation energies for the isothermal and non‐isothermal crystallizations determined by the Arrhenius and the Kissinger methods, respectively, decreased with increase of the alkane chain segment length of nylon 1010, 1013 and 1014. Furthermore, the activation energy of the non‐isothermal crystallization process of these nylons, determined by the isoconversional methods of Flynn and Wall and Ozawa, was found to be a decreasing function of the relative degree of crystallinity. © 2014 Society of Chemical Industry     

Investigation on Unusual Crystallization Behavior in Polyamide 6/Montmorillonite Nanocomposites

The crystallization behavior and crystal structure of polyamide 6/montmorillonite (PA6/MMT) nanocomposites were investigated by differential scanning calorimetry and X‐ray diffraction, and an interesting behavior was observed. The material was prepared via melt compounding using an organophilic clay obtained by co‐intercalation of epoxy resin and quaternary ammonium into Na‐montmorillonite. A maximum in degree of crystallinity was obtained at 5 wt.‐% MMT and the reasons for this, based on the MMT layer distribution, were discussed. The degree of crystallinity showed a strong dependence on the cooling rates. In contrast with typical behavior, a higher cooling rate resulted in a higher degree of crystallinity. In nanocomposites, the γ‐crystalline phase was dominant.     

Study on the Crystallization Properties of Polypropylene/Montmorillonite Composites

The crystalline size of polypropylene (PP) filled with montmorillonite (MMT) was studied by X-ray diffraction (XRD). The isothermal crystallization behavior of polypropylene was studied by means of differential scanning calorimetry (DSC). The Avrami equation was used to describe the isothermal crystalline kinetics of PP/MMT composites. The result showed that the addition of MMT decreased the crystalline size L _hkl of the polymer. MMT was used as nucleating agent during isothermal crystallization process of polypropylene. The addition of montmorillonite decreased the crystallization time of the polypropylene and the melt point was raised. The value of Avrami exponent n was related with the crystallization temperature. The value of Avrami pre-index factor k of PP/MMT composite was decreased with increasing crystallization temperature. The value of half crystallization time t _1/2 of PP/MMT composite was less than that of PP at a given crystallization temperature, signifying that montmorillonite acted as nucleating agent, accelerated the overall crystallization process.     

Crystalline morphology and isothermal crystallization kinetics of poly(ethylene terephthalate)/clay nanocomposites

A poly(ethylene terephthalate) (PET)/montmorillonite clay nanocomposite was synthesized via in situ polymerization. Microscopic studies revealed that in an isothermal crystallization process, some crystallites in the nanocomposite initially were rod‐shaped and later exhibited three‐dimensional growth. The crystallites in the nanocomposite were irregularly shaped, rather than spherulitic, being interlocked together without clear boundaries, and they were much smaller than those of neat PET. With Avrami analysis, the isothermal crystallization kinetic parameters (the Avrami exponent and constant) were obtained. The rate constants for the nanocomposite demonstrated that clay could greatly increase the crystallization rate of PET. The results for the Avrami exponent were consistent with the observation of the rodlike crystallites in the PET/clay nanocomposite during the initial stage. Wide‐angle X‐ray scattering and Fourier transform infrared studies showed that, in comparison with neat PET, the crystal lattice parameters and crystallinity of the nanocomposite did not change significantly, whereas more defects may have been present in the crystalline regions of the nanocomposite because of the presence of the clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1381–1388, 2004     

Isothermal and nonisothermal crystallization kinetics of syndiotactic polystyrene/clay nanocomposites

Differential scanning calorimeter (DSC) and X‐ray diffraction methods were used to investigate the isothermal and nonisothermal crystallization behavior and crystalline structure of syndiotactic polystyrene (sPS)/clay nanocomposites. The sPS/clay nanocomposites were prepared by mixing the sPS polymer solution with the organically modified montmorillonite. DSC isothermal results revealed that introducing 5 wt% of clay into the sPS structure causes strongly heterogeneous nucleation, inducing a change of the crystal growth process from mixed three‐dimensional and two‐dimensional crystal growth to two‐dimensional spherulitic growth. The activation energy of sPS drastically decreases with the presence of 0.5 wt% clay and then increases with increasing clay content. The result indicates that the addition of clay into sPS induces the heterogeneous nucleation (a lower ΔE) at lower clay content and then reduces the transportation ability of polymer chains during crystallization processes at higher clay content (a higher ΔE). We studied the non‐isothermal melt‐crystallization kinetics and melting behavior of sPS/clay nanocomposites at various cooling rates. The correlation among crystallization kinetics, melting behavior and crystalline structure of sPS/clay nanocomposites is discussed. Polym. Eng. Sci. 44:2288–2297, 2004. © 2004 Society of Plastics Engineers.     

Study on the dynamic self‐organization of montmorillonite in two phases

Polycarbonate (PC)/acrylonitrile–butadiene–styrene (ABS) polymer alloy/montmorillonite (MMT) and nylon 6 (PA6)/ABS polymer alloy/MMT nanocomposites were prepared using the direct melt intercalation technique. Their structures were characterized by XRD and TEM. The results of TEM show that the silicate layers dispersed differently in two phases. In the PC/ABS/MMT nanocomposite, the silicate layers were self‐organized in the ABS phase, whereas in the PA6/ABS/MMT nanocomposite, the silicate layers were dispersed in both phases but mainly in the PA6 phase. Furthermore, the PC/MMT nanocomposite was melt‐mixed with pure ABS, and the changed morphology of the hybrid with the change of melt‐mixing time was characterized by XRD and TEM, to study the dynamic self‐assembly of clay layers in two phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1457–1462, 2004     

Thermal–oxidative degradation and accelerated aging behavior of polyamide 6/epoxy resin‐modified montmorillonite nanocomposites

Polyamide 6 (PA6) nanocomposites based on epoxy resin‐modified montmorillonite (EP‐MMT) were prepared by melt processing using a typical twin‐screw extruder. X‐ray diffraction combined with transmission electron microscopy was applied to elucidate the structure and morphology of PA6/EP‐MMT nanocomposites, suggesting a nearly exfoliated structure in the nanocomposite with 2 wt % EP‐MMT (PA6/2EP‐MMT) and a partial exfoliated‐partial intercalated structure in PA6/4 wt %EP‐MMT nanocomposite (PA6/4EP‐MMT). The thermogravimetric analysis under air atmosphere was conducted to characterize the thermal–oxidative degradation behavior of the material, and the result indicated that the presence of EP‐MMT could inhibit the thermal‐oxidative degradation of PA6 effectively. Accelerated heat aging in an air circulating oven at 150°C was applied to assess the thermal–oxidative stability of PA6 nanocomposites through investigation of reduced viscosity, tensile properties, and chemical structure at various time intervals. The results indicated that the incorporation of EP‐MMT effectively enhanced the thermal–oxidative stability of PA6, resulting in the high retention of reduced viscosity and tensile strength, and the low ratio of terminal carboxyl group to amino group. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40825.     

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。     

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     

Effects of silane grafting on the morphology and thermal stability of poly(ethylene terephthalate)/clay nanocomposites

An alkylammonium intercalated montmorillonite (A‐MMT) was modified by edge grafting with 3‐glycidoxypropyltrimethoxysilane. In comparison with poly(ethylene terephthalate) (PET)/A‐MMT, the resultant grafted clay, S‐A‐MMT, exhibited improved miscibility with PET matrix and revealed better dispersion state in the melting compounded PET/S‐A‐MMT nanocomposites. As a result, the PET/S‐A‐MMT nanocomposite had slower degradation rate owing to the enhanced clay barrier effect. Meanwhile, the nanocomposite exhibited lower degradation onset temperature under nitrogen because of the clay catalysis effect, which can be explained by the decreasing degradation reaction energy calculated from Coats–Redfern method of degradation kinetics. In the other hand, nanocomposite with better clay dispersion state exhibited increasing thermal oxidative stability due to clay barrier effect of hindering oxygen to diffuse in, which accorded with the continuous and compact char surface formed during polymer degradation. The clay catalysis and barrier effect of silicate layers were presented directly in isothermal oxidative TGA experiment. Furthermore, the mechanical and crystallization properties of PET/clay nanocomposites were investigated as well. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers