Effect of carbon nanotube‐supported β nucleating agent on the thermal properties,morphology, and mechanical properties of polyamide 6/isotactic polypropylene blends

A new kind of β nucleating agent, multi‐wall carbon nanotube (MWCNT)‐supported calcium pimelate was introduced into polyamide 6 (PA 6)/isotactic polypropylene (iPP; 10/90 by weight) blend and the thermal properties, morphology, and mechanical properties were investigated. The results showed that β‐iPP appeared at low content of MWCNT‐supported calcium pimelate which surmounted the α‐nucleating effect of PA 6 for iPP, and the content of β‐iPP increased with increasing content of MWCNT‐supported calcium pimelate. The impact strength, elongation at break, and flexural modulus were improved with increasing content of MWCNT‐supported calcium pimelate without significantly deteriorating the tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A novel highly efficient β‐nucleating agent for polypropylene using nano‐CaCO3 as a support

In order to increase the isotactic content of β‐nucleated polypropylene (β‐iPP) and decrease the cost of its production, the investigation and development of novel highly efficient β‐nucleators are important issues. Nano‐CaCO₃ was used as a support to prepare a supported β‐nucleator, nano‐CaCO₃‐supported calcium pimelate. Fourier transform infrared spectral analysis shows that an in situ chemical reaction takes place between nano‐CaCO₃ and pimelic acid. Differential scanning calorimetry results indicate that the crystallization and melting temperatures of β‐phase in supported β‐nucleator‐nucleated iPP are higher than those of calcium pimelate‐nucleated iPP. The β‐nucleating ability of the supported β‐nucleator is little influenced by the cooling rate and crystallization temperature over a wide range. The decreased content of pimelic acid in the supported β‐nucleator slightly decreases the crystallization temperature of iPP but it has no influence on the content of β‐phase in nucleated iPP. A novel supported β‐nucleator has been successfully synthesized via pimelic acid supported on the surface of CaCO₃. The crystallization temperature of iPP and melting temperature of β‐phase in iPP nucleated using the supported β‐nucleator are higher than those of iPP nucleated using calcium pimelate. The concept of a supported nucleator will provide a new way to increase the efficiency of polymer additives and to decrease the amounts of them that need to be used by using nanoparticles as supports. Copyright © 2010 Society of Chemical Industry     

β‐Nucleation of pimelic acid supported on metal oxides in isotactic polypropylene

To investigate the nucleation of metal pimelate for isotactic polypropylene (iPP) crystallization, iPP filled with a series of metal oxides with and without metal pimelate on their surface was prepared. There was a chemical reaction between pimelic acid (PA) and metal oxides MgO, CaO, BaO or ZnO, but not TiO₂. The corresponding metal pimelate formed by the chemical reaction between PA and MgO, CaO, BaO or ZnO had a different influence on the crystallization behavior and melting characteristics of iPP. Addition of metal oxides increased the crystallization temperature of iPP and mainly formed α‐phase due to the heterogeneous α‐nucleation of metal oxides. The α‐nucleation of CaO could be easily changed into β‐nucleation using CaO‐supported PA, and 90.1% β‐phase was obtained. The β‐nucleation of BaO could be markedly enhanced by barium pimelate formed using supported PA. However, no β‐phase was observed for iPP filled with MgO‐ or ZnO‐supported PA. The various metal oxides with supported PA had a different influence on the crystallization behavior and melting characteristics of iPP due to the different structure of metal pimelate formed by chemical reaction between PA and the metal oxides. Copyright © 2012 Society of Chemical Industry     

Improved conductivity and thermal stability by the formation of a charge‐transfer complex in β‐nucleation‐agent‐nucleated and MWCNT‐filled iPP composites

In this study, the influence of β‐nucleation agent (β‐NA) on the morphology and properties of multi‐walled carbon nanotube (MWCNT) filled isotactic polypropylene (iPP) composites was explored in details. The results show that the incorporation of β‐NA has promoted the dispersion of MWCNT in the iPP matrix, which is profitable for improving the thermal stability and conductivity properties of MWCNT‐iPP composites. Besides, the 0.05 wt % β‐NA nucleated samples exhibit higher impact toughness than that of un‐β‐NA‐nucleated ones. Further SEM observations show that the morphology of MWCNT changes from large agglomerations to small clusters with doping of β‐NA. The main reason is that the incorporation of β‐NA (TMB‐5) in MWCNT filled iPP matrix has led to the formation of a charge‐transfer complex. Some of these clusters act as nucleation sites for inducing crystallization of α spherulites, which have a compete growth with β‐NA induced β crystals. Meanwhile, other clusters exist in the inter‐lamella amorphous phase of β crystals, some of them even combine two adjacent β spherulites. Accordingly, a large conductive network comes into being. Based on the investigated results, a mechanism model is proposed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Variation of non‐isothermal crystallization behavior of isotactic polypropylene with varying β‐nucleating agent content

The non‐isothermal crystallization behavior, the crystallization kinetics, the crystallization activation energy and the morphology of isotactic polypropylene (iPP) with varying content of β‐nucleating agent were investigated using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The DSC results showed that the Avrami equation modified by Jeziorny and a method developed by Mo and co‐workers could be successfully used to describe the non‐isothermal crystallization process of the nucleated iPPs. The values of n showed that the non‐isothermal crystallization of α‐ and β‐nucleated iPPs corresponded to a tridimensional growth with homogeneous and heterogeneous nucleation, respectively. The values of crystallization rate constant showed that the rate of crystallization decreased for iPPs with the addition of β‐nucleating agent. The crystallization activation energy increased with a small amount (less than 0.1 wt%) of β‐nucleating agent and decreased with higher concentration (more than 0.1 wt%). The changes of crystallization rate, crystallization time and crystallization activation energy of iPPs with varying contents of β‐nucleating agent were mainly determined by the ratio of the content of α‐ and β‐phase in iPP (α‐PP and β‐PP) from the DSC investigation, and the large size and many intercrossing lamellae between boundaries of β‐spherulites for iPPs with small amounts of β‐nucleating agent and the small size and few intercrossing bands among the boundaries of β‐spherulites for iPPs with large amounts of β‐nucleating agent from the SEM examination. Copyright © 2010 Society of Chemical Industry     

A novel highly efficient β‐nucleating agent for isotactic polypropylene

A novel highly efficient β‐nucleating agent for isotactic polypropylene (iPP), hexahydrophthalic barium (HHPA‐Ba), was found and its effects on the mechanical properties, the β‐phase content, and crystallization behavior of iPP were investigated, respectively. The results show that the β‐phase content of nucleated iPP (k_β value) can reach 80.2% with 0.4 wt % HHPA‐Ba. The impact strength and crystallization peak temperature of nucleated iPP are greatly increased. Compared with pure iPP, the impact strength of nucleated iPP can increase 2.4 times. Meanwhile, the spherulite size of nucleated iPP is dramatically decreased than that of pure iPP. The Caze method was used to investigate the nonisothermal crystallization kinetics of nucleated iPP and the crystallization active energy was achieved by Kissinger method. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Isothermal crystallization and melting behavior of polypropylene with lanthanum complex of cyclodextrin derivative as a β‐nucleating agent

A novel highly active β‐nucleating agent, β‐cyclodextrin complex with lanthanum (β‐CD‐MAH‐La), was introduced to isotactic polypropylene (iPP). Its influence on isothermal crystallization and melting behavior of iPP was investigated by differential scanning calorimeter (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized light microscopy (PLM). WAXD results demonstrated that β‐CD‐MAH‐La was an effective β‐nucleating agent, with β‐crystal content of iPP being strongly influenced by the content of β‐CD‐MAH‐La and the isothermal crystallization temperature. The isothermal crystallization kinetics of pure iPP and iPP/β‐CD‐MAH‐La was described appropriately by Avrami equation, and results revealed that β‐CD‐MAH‐La promoted heterogeneous nucleation and accelerated the crystallization of iPP. In addition, the equilibrium melting temperature (T) of samples was determined using linear and nonlinear Hoffman‐Weeks procedure. Finally, the Lauritzen‐Hoffman secondary nucleation theory was applied to calculate the nucleation parameter (K_g) and the fold surface energy (σ_e), the value of which verify that the addition of β‐CD‐MAH‐La reduced the creation of new surface for β‐crystal and then led to faster crystallization rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Nonisothermal crystallization and melting behavior of β‐nucleated isotactic polypropylene and polyamide 66 blends

A highly novel nano‐CaCO₃ supported β‐nucleating agent was employed to prepare β‐nucleated isotactic polypropylene (iPP) blend with polyamide (PA) 66, β‐nucleated iPP/PA66 blend, as well as its compatibilized version with maleic anhydride grafted PP (PP‐g‐MA), maleic anhydride grafted polyethylene‐octene (POE‐g‐MA), and polyethylene‐vinyl acetate (EVA‐g‐MA), respectively. Nonisothermal crystallization behavior and melting characteristics of β‐nucleated iPP and its blends were investigated by differential scanning calorimeter and wide angle X‐ray diffraction. Experimental results indicated that the crystallization temperature (T) of PP shifts to high temperature in the non‐nucleated PP/PA66 blends because of the α‐nucleating effect of PA66. T of PP and the β‐crystal content (K_β) in β‐nucleated iPP/PA66 blends not only depended on the PA66 content, but also on the compatibilizer type. Addition of PP‐g‐MA and POE‐g‐MA into β‐nucleated iPP/PA66 blends increased the β‐crystal content; however, EVA‐g‐MA is not benefit for the formation of β‐crystal in the compatibilized β‐nucleated iPP/PA66 blend. It can be relative to the different interfacial interactions between PP and compatibilizers. The nonisothermal crystallization kinetics of PP in the blends was evaluated by Mo's method. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A novel β‐nucleating agent for isotactic polypropylene

The nucleating ability of p‐cyclohexylamide carboxybenzene (β‐NA) towards isotactic polypropylene (iPP) was investigated by differential scanning calorimetry, X‐ray diffraction, polarized optical microscopy and scanning electron microscopy. β‐NA is identified to have dual nucleating ability for α‐iPP and β‐iPP under appropriate kinetic conditions. The formation of β‐iPP is dependent on the content of β‐NA. The content of β‐phase can reach as high as 96.96% with the addition of only 0.05 wt% β‐NA. Under non‐isothermal crystallization the content of β‐iPP increases with increasing cooling rate. The maximum β‐crystal content is obtained at a cooling rate of 40 °C min^–1. The supermolecular structure of the β‐iPP is identified as a leaf‐like transcrystalline structure with an ordered lamellae arrangement perpendicular to the special surface of β‐NA. Under isothermal crystallization β‐crystals can be formed in the temperature range 80–140 °C. The content of β‐crystals reaches its maximum value at a crystallization temperature of 130 °C. © 2012 Society of Chemical Industry     

A highly active and selective β‐nucleating agent for isotactic polypropylene and crystallization behavior of β‐nucleated isotactic polypropylene under rapid cooling

Zinc adipate (Adi‐Zn) was observed to be a highly active and selective β‐nucleating agent for isotactic polypropylene (iPP). The effects of Adi‐Zn on the mechanical properties and the β‐crystals content of nucleated iPP were investigated. The impact strength of iPP nucleated with 0.2 wt % Adi‐Zn was 1.8 times higher than that of neat iPP. In addition, wide‐angle X‐ray diffraction analysis indicated that the content of β‐crystals in nucleated iPP (k_β value) reached 0.973 with 0.1 wt % Adi‐Zn, indicating that Adi‐Zn is a highly active and selective β‐nucleating agent for iPP. Furthermore, fast scanning chip calorimetry (FSC) studies using cooling rates from 60 to 13,800 °C min^?1 revealed that the formation of β‐crystals significantly depended on the cooling rates. At cooling rates below 3000 °C min^?1, only β‐crystals existed. However, at cooling rates above 6000 °C min^?1, β‐crystals failed to form. Moreover, a lower critical crystallization temperature that corresponded to the generation of β‐crystals was investigated using cooling‐induced crystallization, and the results are in good agreement with those of a previous study. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43767.     

Detecting crystallization structure evolution of polypropylene injection‐molded bar induced by nucleating agent

The crystallization structures of Polypropylene (PP) injection‐molded bars nucleated by nucleating agent were detected from the skin layer to the core zone, layer by layer. α‐phase nucleating agent 1,3:2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988), β‐phase nucleating agent aryl amides compounds (TMB‐5), and their compounds were introduced into PP matrix, respectively. The relative content of β‐phase PP in the different zones of an injection‐molded bar was characterized and calculated by Wide angle X‐ray diffraction (WAXD) and Differential scanning calorimetry (DSC). The results show that, whether in pure PP or in nucleated PP, both β‐phase PP and α‐phase PP grow in the skin layer of the injection‐molded bar. However, in the intermediate layers and the core zone, the crystallization structures of PP are dependent on the used nucleating agent. β‐phase is the main crystallization structure of TMB‐5 (0.1 and 0.2 wt%) nucleated PP, and α‐phase in DMDBS (0.1 and 0.2 wt%) nucleated PP. Compounding nucleating agents with 0.1 wt% DMDBS and 0.1 wt% TMB‐5 induces PP crystallization almost in β‐phase; however, PP nucleated by 0.2 wt% DMDBS and 0.2 wt% TMB‐5 crystallizes exclusively in α‐phase. The crystallization mechanism of PP nucleated by compounding nucleating agents was further studied in this work. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

The effects of crystallization condition on the microstructure and thermal stability of istactic polypropylene nucleated by β‐form nucleating agent

This article deals with the crystallization behaviors of original (prepared in a torque rheometer), DSC crystallization and mold crystallization (quenching and slow nonisothermal crystallization) of isotactic polypropylene (iPP) mixed with β‐form nucleating agent. The microstructure and thermal stability of these samples were investigated. The wide angle X‐ray diffraction (WAXD) results indicate that fast cooling is favorable for β‐form iPP formation. With slower cooling rate and higher concentration of nucleating agent, the lamellar thickness and stability of crystal0s were enhanced. Polarized optical microscopy (POM) and scanning electron microscopy (SEM) both showed that rapid crystallized samples gave rise to tiny spherulites, whereas under slow crystallization condition, nucleated samples could be fully developed in the form of dendritic or transcrystalline structures, depending on the nucleating agent concentration. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of injection rate on crystallization of injection‐molded β‐nucleated isotactic polypropylene

It is widely believed that β ‐nucleating agent is beneficial for effectively toughening isotactic polypropylene (iPP). However, for the injection molding process, the shearing and thermo‐mechanical conditions make the nucleation and crystallization process complicated. In this paper, the effects of injection rate on crystallization of β ‐nucleated iPP were studied by scanning electron microscope (SEM), two‐dimensional wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). It is observed that with increasing injection rate, the content of β ‐crystals exhibits different tendencies in the skin, intermediate layers, and core zone. Specifically, for the intermediate layer, the β ‐crystals content first increases with increasing injection rate to 85 cm·s^?1, and begins to decrease afterward. By simulating the injection process, the most likely explanation for the β ‐crystal change is the comparatively high shear rate and low shearing time that the melt experienced. Variations in β ‐form content are mainly responsible for the mechanical properties of β ‐nucleated iPP. The results of this study provide a valuable way to control the iPP toughness in the injection molding process. POLYM. ENG. SCI., 57:172–182, 2017. © 2016 Society of Plastics Engineers     

Melting characteristic and β‐crystal content of β‐nucleated polypropylene/polyamide 6 alloys prepared using different compounding methods

BACKGROUND: The distribution of nucleating agents in different phases is still an open question in general, and how to control conditions to prepare alloys rich in β‐crystals of polypropylene (PP) is hardly reported. The main goal of this study was to find out the factors influencing the β‐crystal content in β‐nucleated PP/polyamide 6 (PA6) alloys and determine the best preparation conditions to obtain β‐nucleated PP/PA6 alloys rich in β‐crystals. RESULTS: The compounding methods had little influence on the crystallization temperature of both PP and PA6. However, the melting characteristic and β‐crystal content in β‐nucleated PP/PA6 alloys not only depended upon the compounding methods, but also on the temperature at which the nucleating agent was added. A higher β‐crystal content can be obtained by adding the nucleating agent at a temperature below 190 °C, which is also dependent on the mixing time. CONCLUSION: It is proved by etching the alloys with sulfuric acid that the nucleating agent mainly disperses in the PA6 phase and/or the interface between PP and PA6 when blended at high temperature. Copyright © 2009 Society of Chemical Industry     

Comparative study on the crystallization behavior of β‐isotactic polypropylene nucleated with different β‐nucleation agents —effects of thermal conditions

In this study, the crystallization behavior of the β‐isotactic polypropylene (β‐iPP) samples nucleated by a rare earth based β‐nucleating agent (β‐NA) WBG‐II and a metal salts compound β‐NA NAB83 (denoted as WPP and NPP, respectively) under different cooling conditions were comparatively investigated. The thermal conditions such as the cooling rate, isothermal crystallization temperature, isothermal crystallization time, and the subsequent cooling to room temperature. The results of WAXD, SEM, and nonisothermal crystallization reveal that under the same processing conditions, the crystallite size of NPP is smaller, which arrange more compactly as compared with WPP. Meanwhile, NPP has shorter crystallization rate and higher β‐nucleation selectivity, but WPP can crystallization at wider temperature range. The results of isothermal crystallization showed that NPP has higher selectivity and higher β‐nucleation efficiency, which favors the formation of high proportion of β‐phase at the isothermal crystallization temperature of 110–130°C with and without subsequent cooling; WPP has lower selectivity, which can only induce high content of β‐phase under isothermal crystallization without subsequent cooling to 25°C. In tuning the crystallization behavior and the properties of β‐PP, the joint influence of the efficiency and selectivity of the β‐NA, and the thermal conditions should be taken into consideration. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40115.     

Calcium dicarboxylates nucleation of β‐polypropylene

Seven dicarboxylates of calcium were synthesized. The effect of dicarboxylate on the formation of β‐form polypropylene was investigated by X‐ray diffraction. Calcium pimelate, calcium suberate, calcium phthalate, and calcium terephthalate have been found to be an effective β‐nucleator. The K_x values of the isotatic propylene samples with 0.5 wt % of the nucleators above are 0.95, 0.96, 0.93, and 0.62, respectively. Calcium succinate, calcium adipate, and calcium sebacate behave invalidly on the nucleating of the β‐phase. We conducted an investigation on the affect of particle shape, crystal form, and crystallinity upon the level of the β‐form. The X‐ray diffraction of the effective nucleators reveals a common character that their first reflection locate at the d‐spacing between 10 to 13 Å, indicating structural similarity of the nucleators with β‐polypropylene. The nucleation mechanism is explained by the cooperative effect of the nonpolar and polar part of nucleating agents in the crystallization of polypropylene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 633–638, 2002     

Effect of oscillatory shear field on the morphology and mechanical properties of β‐nucleated isotactic polypropylene

The aim of this study is to investigate the effects of extra oscillatory shear field on morphology and mechanical properties of β‐nucleated isotactic polypropylene by using a homemade vibration‐assisted extrusion apparatus, in which oscillatory shear field was introduced into the extrusion head driven by crank and link mechanism. The results show that the extra oscillatory shear filed induces a significantly enhanced orientation of β‐crystal besides causing a better homogeneous dispersion of β‐nucleant, and the oriented β‐crystal has a high ratio of daughter lamellae to parent lamellae orientation, which was rarely reported in other literatures. The vibration increased the overall crystallinity and changed the relative content of β‐crystal. For the higher level nucleation agent content iPP(0.4 wt%), the relative contents of β‐crystal just changed a little or basically unchanged after vibration. However, for iPP contenting 0.2 wt% nucleation agent, the content of β‐crystal decreased. All the changes in the morphology, crystallinity, dispersion of β‐nucleant and β‐crystal content had a great influence on the mechanical properties, and that result was the improvement of yield stress and decrement of the elongation at break. POLYM. ENG. SCI., 57:838–845, 2017. © 2016 Society of Plastics Engineers     

Activity of a β‐nucleating agent for isotactic polypropylene and its influence on polymorphic transitions

The influence of a nonpigmenting β‐nucleating additive in the crystallization of isotactic polypropylene (iPP) is investigated by differential scanning calorimetry and X‐ray diffraction. It is found that this additive induces the formation of a very high level of the trigonal modification of iPP. The crystallization and melting behavior of the nucleated systems are studied as a function of the cooling and heating rates and the control of the final temperature during the cooling process. The nucleating agent exerts an important effect on the crystallization temperatures and the polymorphic transitions of iPP, delaying the β–α recrystallization process through an increase in the stability of the trigonal crystals. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 531–539, 2002     

The effect of bicyclo[2.2.1]hept‐5‐ene‐2,3‐dicarboxylate on the mechanical properties and crystallization behaviors of isotactic polypropylene

The mechanical and optical properties of iPP nucleated with bicyclo[2.2.1]heptenedicarboxylate salts (BCHED) have been investigated. The results showed that aluminum bicyclo[2.2.1]heptenedicarboxylate (BCHE13) is the most effective nucleating agent to improve the mechanical and optical properties. Then the effects of the BCHE13 concentration on mechanical and optical properties and crystallization behaviors were studied. The results indicated that the saturated concentration of BCHE13 is about 0.2 wt %, at which nucleated iPP showed the better comprehensive mechanical and optical properties and high crystallization peak temperature. Nonisothermal crystallization kinetics of iPP nucleated with different BCHE13 contents have been investigated by Caze method. The results indicated Avrami exponents of nucleated iPP gradually increased with the increasing of BCHE13 concentration. The results can be explained that crystallization and growth model of nucleated iPP is heterogeneous nuclei followed by more than three‐dimension spherical growth during nonisothermal crystallization, which can be proved by agglomeration of BCHE13 in melt iPP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical and thermal characteristics and morphology of polyamide 6/isotactic polypropylene blends in the presence of a β‐nucleating agent

The mechanical and thermal characteristics and morphology of polyamide 6 (PA6)/isotactic polypropylene (iPP) blends (10/90 w/w) prepared with different processing procedures and incorporated with an aryl amide nucleating agent, a kind of β‐nucleating agent (β‐NA) for iPP, were investigated. The yield strength and flexural modulus of the blends decreased as β‐NA was introduced into the blends, whereas the impact strength and elongation at break improved. The crystalline structures of the blends closely depended on (1) the processing conditions and (2) competition between the β‐nucleating effect of β‐NA and the α‐nucleating effect of PA6 for iPP. Scanning electron microscopy, differential scanning calorimetry, and X‐ray diffraction were adopted to reveal the microstructures of the blends. At a low β‐NA content (<0.1 wt %), the α‐phase iPP dominated the blends, whereas the relative content of the β‐phase iPP increased remarkably when the β‐NA content was not less than 0.1 wt %. The processing conditions also showed profound influences on the supermolecular structures of iPP; this resulted in different mechanical properties of the blends. As for PA6, the crystallization behavior and crystalline structure did not exhibit obvious changes, but PA6 did play an important role in the epitaxial crystallization of iPP on PA6. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011