Nonisothermal Crystallization Modeling and Simulation of Polypropylene/Nano Ca3(PO4)2 Composites with Variation in Wt.% of Loading and Reduction in Nanosize

Nonisothermal crystallization kinetics of polypropylene (PP)/Ca₃(PO₄)₂ composites was studied using differential scanning calorimetry (DSC) for various nanosizes by employing Avrami and Ozawa's combined analysis. Parameters such as Avrami's exponent (n) and composite growth rate constant (Z_t) were determined, which characterize the system of different nanosize composites and virgin PP. The relative degree of crystallinity as a function of temperature for PP-nano Ca₃(PO₄)₂ composites at the same cooling rate and sigmoidal shape of curves indicates that there is a strong interaction between PP molecule and nanolayer, which leads to greater nucleation with reduction in nanosizes. A theoretical combination of kinetic equations is found to be suitable to describe the physical phenomena of a real system. The values of parameters n, Z_t, and predicted time t for crystallization at a single cooling rate were obtained from the mathematical model.     

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     

New hyperdispersant agent for polypropylene/CaSO4 composites

A new hyperdispersant agent with Si? OH as an anchoring group and poly(butyl acrylate) as a solvatable chain was synthesized, and its effect on the properties of polypropylene (PP)/CaSO₄ composites was investigated. Fourier transform infrared spectroscopy results showed that the hyperdispersant agent reacted on the CaSO₄ surface and the modified CaSO₄ particles. The tensile strength and impact strength of the PP/CaSO₄ composites increased about 14 and 34%, respectively, versus that of PP/CaSO₄ (filled with the same unmodified fraction). According to surface analysis by scanning electron microscopy, the CaSO₄ particles were buried well in the PP matrix when CaSO₄ was coated with the hyperdispersant agent. CaSO₄ significantly increased the crystallization temperature and crystallization rate of PP by differential scanning calorimetry, but the addition of hyperdispersant‐agent‐modified CaSO₄ did not lead to the formation of crystalline PP through X‐ray diffraction. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nonisothermal thermophysical evaluation of polypropylene/natural rubber based TPEs: Effect of blend ratio and dynamic vulcanization

Ozawa macrokinetic model is applied to describe the nonisothermal melt crystallization process of polypropylene (PP), in natural rubber/polypropylene (NR/PP) thermoplastic elastomers (TPEs) as a function of blend ratio and dynamic vulcanization of the rubber phase. It was found that as cooling rate increases, the crystallization temperature T_c and half time for crystallization t_1/2 get diminished. Dynamic vulcanizates show a similar trend in crystallization as that of neat PP. Crystallization rate constant and Ozawa exponent were found out for different temperatures by linear regression method using Ozawa analysis. Ozawa exponent, n_O, showed variation in values when the conversion proceeded. For neat PP, the value of n_O changes from 1.4 (102°C) to 3 (112°C). The n_O values for NR/PP 50/50 blend were higher (e.g. 4.1 at 116°C). Crystallization rate constant K_O shows a maximum at 0.5 relative crystallinity. The highest crystallization rate constants were found for NR/PP 50/50 TPEs. The activation energy for the melt crystallization was found to vary with the degree of conversion, as well as with the concentration of NR in the TPEs. Finally, attempts have been made to correlate the crystallization process with morphology of the blend. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Isothermal and nonisothermal crystallization kinetics of isotactic polypropylene nucleated with substituted aromatic heterocyclic phosphate salts

The crystallization kinetics of isotactic polypropylene (iPP) and nucleated iPP with substituted aromatic heterocyclic phosphate salts were investigated by means of a differential scanning calorimeter under isothermal and nonisothermal conditions. During isothermal crystallization, Avrami equation was used to describe the crystallization kinetics. Moreover, kinetics parameters such as the Avrami exponent n, crystallization rate constant Z_t, and crystallization half‐time t_1/2 were compared. The results showed that a remarkable decrease in t_1/2 as well as a significant increase in overall crystallization rate was observed in the presence of monovalent salts of substituted aromatic heterocyclic phosphate, while bivalent and trivalent salts have little effect on crystallization rate of iPP. The addition of monovalent metal salts could decrease the interfacial free energy per unit area perpendicular to PP chains σ_e value of iPP so that the nucleation rate of iPP was increased. During nonisothermal crystallization, Caze method was used to analyze the crystallization kinetics. It also showed that monovalent metal salts had better nucleation effects than bivalent and trivalent metal salts. From the obtained Avrami exponents of iPP and nucleated iPP it could be concluded that the addition of different nucleating agents changed the crystal growth pattern of iPP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3307–3316, 2006     

Studies on crystal morphology and crystallization kinetics of polypropylene filled with CaCO3 of different size and size distribution

Changes in the crystal morphology, crystallinity, and the melting temperature of thermoplastics resulted in significant changes in the mechanical behavior of composites containing them. For this reason, the research of crystal morphology and crystallization kinetics in thermoplastic composites became an important requirement. The thermoplastic filled with the filler of different size gradation was a new method for improving processability of thermoplastic composites. We have previously reported that the melt viscosity of polypropylene (PP) composites, which were filled with 30 wt % CaCO₃ of effective size gradation, could be evidently declined. In this study, two sizes of CaCO₃, 325 meshes and 1500 meshes, were blended by different proportions and filled into PP matrix with 30 wt %. Crystal morphology and isothermal crystallization kinetics of a series of composites were characterized by differential scanning calorimeter (DSC) and polarizing microscope. The results showed that composites filled with CaCO₃ of effective size gradation leaded to a well‐crystalline order and a large crystal size, while their isothermal crystallization kinetics and crystallization rate constant (k) were declined, and their Avrami exponents (n) and crystallization half‐life (t_1/2) were increased compared with the composites filled with single size CaCO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2437–2444, 2006     

Nonisothermal crystallization behavior of highly exfoliated polypropylene/clay nanocomposites prepared by in situ polymerization

Polypropylene/clay nanocomposites (PPCNs) were prepared via an in situ polymerization method with a Ziegler–Natta/clay compound catalyst in which the MgCl₂/TiCl₄ catalyst was embedded in the clay galleries. The wide‐angle X‐ray diffraction and transmission electron microscopy results showed that the clay particles were highly exfoliated in the polypropylene (PP) matrix. The nonisothermal crystallization kinetics of these PPCNs were investigated by differential scanning calorimetry at various cooling rates. The nucleation activity were calculated by Dobreva's method to demonstrate that the highly dispersed silicate layers acted as effective nucleating agents. The Avrami, Jeziorny, Ozawa, and Mo methods were used to describe the nonisothermal crystallization behavior of the PP and PPCNs. Various parameters of nonisothermal crystallization, such as the crystallization half‐time, crystallization rate constant, and the kinetic parameter F(t), reflected that the highly exfoliated silicate layers significantly accelerated the crystallization process because of its outstanding nucleation effect. The activation energy values of the PP and PPCNs determined by the Kissinger method increased with the addition of the nanosilicate layers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Nonisothermal crystallization kinetics of linear bimodal–polyethylene (LBPE) and LBPE/low‐density polyethylene blends

Nonisothermal crystallization kinetics of linear bimodal–polyethylene (LBPE) and the blends of LBPE/low‐density polyethylene (LDPE) were studied using DSC at various scanning rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the nonisothermal crystallization process of LBPE and LBPE/LDPE blends. The theory of Ozawa was also used to analyze the LBPE DSC data. Kinetic parameters such as, for example, the Avrami exponent (n), the kinetic crystallization rate constant (Z_c), the crystallization peak temperature (T_p), and the half‐time of crystallization (t_1/2) were determined at various scanning rates. The appearance of double melting peaks and double crystallization peaks in the heating and cooling DSC curves of LBPE/LDPE blends indicated that LBPE and LDPE could crystallize, respectively. As a result of these studies, the Z_c of LBPE increases with the increase of cooling rates and the T_p of LBPE for LBPE/LDPE blends first increases with increasing LBPE content in the blends and reaches its maximum, then decreases as the LBPE content further increases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2431–2437, 2003     

Kinetics and crystal structure of poly(lactic acid) crystallized nonisothermally: Effect of plasticizer and nucleating agent

The kinetics of neat poly(lactic acid) (PLA) and its composites with triphenyl phosphate (TPP) and/or talc crystallized nonisothermally at different cooling rates of 1, 2.5, 5, 7.5, and 10°C/min was analyzed by differential scanning calorimetry and described by Avrami equation and combined Avrami‐Ozawa equation. The results showed that talc acted as PLA nucleating agent accelerated crystallization rate by decreasing the crystallization half‐time t_1/2 or rate parameter F(T), whereas TPP acted as PLA plasticizer decreased crystallization rate. For neat PLA and plasticized PLA, the average values of Avrami exponent n were almost close to each other, but added TPP decreased crystallization rate constant k. As for PLA composites with talc, the crystallization process was relatively complex, and was divided into three regimes. At a given cooling rate, the value of n₂ was almost larger than that that of n₁ or n₃, whereas the value of k₂ was less than that of k₁ or k₃. The effective activation energy ΔE_x calculated from Friedman formula increased with the increase of relative crystallinity and TPP content, whereas decreased with the presence of talc. Wide angle X‐ray diffraction verified that all samples crystallized nonisothermally in cooling rate range of 1–10°C/min form α‐form. POLYM. COMPOS., 31:2057–2068, 2010. © 2010 Society of Plastics Engineers     

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     

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.     

Effect of molecular weight on crystallization and melting of poly(trimethylene terephthalate). 1: Isothermal and dynamic crystallization

The crystallization behavior of poly(trimethylene terephthalate) as a function of molecular weight was investigated under isothermal and dynamic cooling conditions using a differential scanning calorimeter (DSC) and polarized light optical microscopy (POM). THe overall rate of bulk crystallization increased with molecular weight. An Avrami analysis of the isothermal crystallization kinetics indicated that the crystallization rate constant increased with increasing molecular weight. The Avrami exponent, n, approached 2 and was nearly independent of both molecular weight and temperature. The modified Avrami analysis developed by Jeziorny and Ozawa was applied to the dynamic crystallization data. At the same cooling rate, higher molecular weight resulted in a narrower crystallization peak, higher onset crystallization temperature, and larger rate constant (Z_t)^1/n. Higher molecular weight resulted in larger cooling function of dynamic crystallization K(T) and lower Ozawa exponent m. For dynamic crystallization, the average value of the Avrami exponent varied from 3.4 to 3.8 and the average value of the Ozawa exponent changed from 2.3 to 2.6 as the number‐average molecular weight changed from 13,000 to 67,000. Morphology studies indicated that both the isothermal crystallization and the dynamic crystallization of PTT from the melt were thermal nucleation processes, and for a fixed temperature between 190°C and 210°C, the nucleation density increased with increasing the molecular weight.     

Investigation on β‐polypropylene/PP‐g‐MAH/ surface‐treated calcium carbonate composites

β‐Polypropylene composites containing calcium carbonate treated by titanate coupling agent (T‐CaCO₃) and maleic anhydride grafted PP (PP‐g‐MAH) were prepared by melt compounding. The crystallization, morphology and mechanical properties of the composites were investigated by means of differential scanning calorimetry, wide‐angle X‐ray diffraction, polarized light microscopy, scanning electron microscopy and mechanical tests. It is found that both T‐CaCO₃ and NT‐C are able to induce the formation of β‐phase, and NT‐C greatly increases the β content and decreases the spherulitic size of PP. PP‐g‐MAH facilitates the formation of β‐form PP and improves the compatibility between T‐CaCO₃ and PP. Izod notched impact strength of β‐PP/T‐CaCO₃ composite is higher than that of PP/T‐CaCO₃ composite, indicating the synergistic toughening effect of T‐CaCO₃ and β‐PP. Incorporation of PP‐g‐MAH into β‐PP/T‐CaCO₃ composite further increases the content of β‐crystal PP and improves the impact strength and tensile strength when T‐CaCO₃ concentration is below 5 wt%. The nonisothermal crystallization kinetics of β‐PP composites is well described by Jeziorny's and Mo's methods. It is found that NT‐C and T‐CaCO₃ accelerate the crystallization rate of PP but the influence of PP‐g‐MAH on crystallization rate of β‐PP composite is marginal. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Investigation on multiple-melting behavior of nano-CaCO3/polypropylene composites

The multiple melting-peak behavior of polypropylene (PP) in nano-CaCO₃/PP composites and modified nano-CaCO₃/PP composites were investigated under the condition of isothermal crystallization and nonisothermal crystallization. The result indicated that the addition of nano-CaCO₃ markedly increased the crystallization temperatures of PP and induced the formation of the β-crystal of PP. The crystallization temperatures of nano-CaCO₃/PP composites modified by reactive monomers were further increased, but the melting-peak intensity of the β-crystal of PP was not greatly influenced. While in the presence of dicumyl peroxide, nano-CaCO₃/PP composites modified by reactive monomers led to the significant increase in the melting-peak intensity of the β-crystal of PP. The double melting-peak of PP was observed, which was attributed to the formation of two kinds of different crystallization forms of α-crystal or β-crystal during the crystallization of PP. With the increase of crystallization temperatures, the double melting-peak moved toward the high-temperature side. The intensity of high-temperature melting peak was higher than that of low-temperature melting peak in nano-CaCO₃/PP composites. While in modified nano-CaCO₃/PP composites crystallized at higher temperature, the intensity of high-temperature melting peak was lower than that of low-temperature melting peak. The isothermal crystallization time had little effect on the melting temperatures. Translated from Acta Scientiarum Naturalium Universitatis Sunyatseni, 2006, 45(2): 41–45 [译自: 中山大学学报 (自然科学版)]     

Crystallization and melt behavior of magnesium hydroxide/polypropylene composites modified by functionalized polypropylene

The crystallization and melting behavior of Mg(OH)₂/polypropylene (PP) composites modified by the addition of functionalized polypropylene (FPP) or acrylic acid (AA) and the formation of in situ FPP were investigated by DSC. The results indicated that addition of FPP increased crystallization temperatures of PP attributed to the nucleation effect of FPP. The formation of in situ FPP resulted in a reduced crystallization rate, melting point, and degree of crystallization because of the decreased regularity of the PP chain. For the Mg(OH)₂/PP composites, addition of Mg(OH)₂ increased the crystallization temperatures of PP attributed to a heterogeneous nucleation effect of Mg(OH)₂. Addition of FPP into Mg(OH)₂/PP composites further enhanced the crystallization temperatures of PP. It is suggested that there is an activation of FPP to the heterogeneous nucleation effect of Mg(OH)₂ surface. The addition of AA also increased the crystallization temperatures of PP in Mg(OH)₂/PP composites, but crystallization temperatures of PP were not influenced by the AA content, a phenomenon explained by the heterogeneous nucleation effect of the Mg(OH)₂ surface activated by FPP and AA. A synergistic effect on crystallization of PP in Mg(OH)₂/PP composites further increased the crystallization temperatures of PP. However, the crystallization temperatures of Mg(OH)₂/PP composites modified by in situ FPP were lower than those of Mg(OH)₂/PP composites modified by the addition of FPP or AA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:3899–3908, 2004     

Crystallization and melt behavior of Mg(OH)2/PP composites modified by functionalized polypropylene

The crystallization and melting behavior of Mg(OH)₂/PP composites modified by the addition of functionalized polypropylene (FPP) or acrylic acid (AA) and the formation of in situ FPP were investigated by DSC. The results indicated that addition of FPP increased the crystallization temperatures of PP because of the nucleation effect of FPP. The formation of in situ FPP resulted in a reduced crystallization rate, melting point, and degree of crystallization attributed to the decreased regularity of the PP chain. For Mg(OH)₂/PP composites, the addition of Mg(OH)₂ increased the crystallization temperatures of PP resulting from a heterogeneous nucleation effect of Mg(OH)₂. The addition of FPP into Mg(OH)₂/PP composites further enhanced the crystallization temperatures of PP. It is suggested that there is an activation of FPP to the heterogeneous nucleation effect on the Mg(OH)₂ surface. The addition of AA also increased the crystallization temperatures of PP in Mg(OH)₂/PP composites, although the crystallization temperature of PP was not influenced by the AA content, which is explained by the heterogeneous nucleation effect of the Mg(OH)₂ surface activated by FPP and AA. A synergistic effect on the crystallization of PP in Mg(OH)₂/PP composites further increased the crystallization temperatures of PP. However, The crystallization temperatures of Mg(OH)₂/PP composites modified by in situ FPP were lower than those of Mg(OH)₂/PP composites modified by addition of either FPP or AA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3610–3621, 2004     

Nonisothermal crystallization kinetics of poly(ethylene terephthalate) and poly(methyl methacrylate) blends

The nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) and poly(methyl methacrylate) (PMMA) blends were studied. Four compositions of the blends [PET 25/PMMA 75, PET 50/PMMA 50, PET 75/PMMA 25, and PET 90/PMMA 10 (w/w)] were melt‐blended for 1 h in a batch reactor at 275°C. Crystallization peaks of virgin PET and the four blends were obtained at cooling rates of 1°C, 2.5°C, 5°C, 10°C, 20°C, and 30°C/min, using a differential scanning calorimeter (DSC). A modified Avrami equation was used to analyze the nonisothermal data obtained. The Avrami parameters n, which denotes the nature of the crystal growth, and Z_t, which represents the rate of crystallization, were evaluated for the four blends. The crystallization half‐life (t_½) and maximum crystallization (t_max) times also were evaluated. The four blends and virgin polymers were characterized using a thermogravimetric analyzer (TGA), a wide‐angle X‐ray diffraction unit (WAXD), and a scanning electron microscope (SEM). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3565–3571, 2006     

Isothermal crystallization kinetics of in situ Nylon 6/graphene composites by differential scanning calorimetry

The isothermal crystallization kinetics of nylon 6/graphene (NG) composites prepared by in situ polymerization was investigated by differential scanning calorimetry. The Avrami equation was used to study the crystallization kinetics. Comparing with nylon 6, it is found that the NG composites (NG‐0.1, NG‐0.5, and NG‐1.0, where the number describes the wt% content of graphene) had higher crystallization rates; the crystallization rate increased remarkably with 0.1 wt% graphene. However, too many crystallization nuclei could not accelerate the crystallization process effectively. The t_max values obtained from the plots of heat flow versus time were in agreement with the t_max values calculated from the half time of crystallization when the graphene content was lower than 1.0 wt%, which means that the values of the Avrami parameters calculated from the half time of crystallization might be in better agreement with the actual crystallization mechanism than that determined from the Avrami plots. The n values of the NG composites ranged between 1.1 and 1.8, which can be interpreted as meaning both one‐dimensional and two‐dimensional crystallization growth occurred during isothermal crystallization process. The activation energies, which were determined by the Arrhenius' method, varied within the range from ?188 to ?142 kJ/mol. POLYM. ENG. SCI., 54:2610–2616, 2014. © 2013 Society of Plastics Engineers