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     

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     

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     

Effect of syndiotactic polystyrene on the crystallization behavior of isotactic polypropylene/syndiotactic polystyrene blends with and without β‐nucleating agent

Blends of isotactic polypropylene (PP) and syndiotactic polystyrene (sPS) with and without β‐nucleating agent were prepared using a twin‐screw extruder at 290 °C. Blends of PP/sPS with β‐nucleating agent mainly show β crystalline form, irrespective of high (20 °C min^?1) or low (2 °C min^?1) previous cooling rates. This suggests that the cooling rates have little effect on the polymorphic composition of PP in PP/sPS blends. The effect of sPS on the crystallization of PP is compared with that of polyamide 6 (PA6). The increase in crystallization temperature of PP is smaller in the presence of sPS than in the presence of PA6; the fold surface free energy of PP/sPS is larger than that of PP/PA6 blends. These results reveal that compared with PA6, sPS has much weaker α‐nucleation effect on the crystallization of PP. The weak α‐nucleation effect of sPS is attributed to the high lattice mismatch between PP and sPS crystals.     

Highly active thermally stable β‐nucleating agents for isotactic polypropylene

Calcium salts of suberic (Ca‐Sub) and pimelic (Ca‐Pim) acids were synthesized and implemented as in different grades of isotactic polypropylene (iPP). Propylene homopolymer, as well as random and block copolymers containing these additives, crystallized iPP into pure or nearly pure β modification in the isothermal and nonisothermal crystallization experiments. Recently, Ca‐Sub proved to be the most effective β‐nucleating agent of iPP. The Ca‐Sub nucleating agent widens the upper crystallization temperature range of pure β‐iPP formation up to 140°C. In this study the effect of the these additives on the crystallization, melting characteristics, and structure of the PP were studied. The degree of crystallinity of β‐iPP was markedly higher than that of α‐iPP. A widening in the melting peak of the samples crystallized in a high temperature range was first observed and discussed in regard to literature results of the same phenomenon for α‐iPP. The morphology of the β‐iPP samples was revealed by scanning electron microscopy. Independent of the type of polymer or nucleating agent, hedritic structures were found in the early stages of growth of the β‐spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2357–2368, 1999     

Negative effect of stretching on the development of β‐phase in β‐nucleated isotactic polypropylene

On the premise that shear in the slit die of an extruder was minimized as far as possible, β‐nucleated isotactic polypropylene (iPP) was extruded. Simultaneously, once the extrudate (in the melt state) left the die exit, it was stretched at various stretching rates (SRs). For iPP with a low content of β‐nucleating agent (β‐NA), the crystallinity of β‐phase (X_β) initially increases with increasing SR, and then decreases slightly with further increase in SR. However, for iPP containing a higher content of β‐NA, with increasing SR, X_β decreases monotonically, indicating a negative effect of SR on β‐phase formation. Small‐angle X‐ray scattering and polarized optical microscopy experiments reveal that, when SR is less than 30 cm min^?1, the increasing amount of row nuclei induced by increasing SR is mainly responsible for the increase of X_β. In contrast, when SR exceeds 30 cm min^?1, the overgrowth of shish structures unexpectedly restrains the development of β‐phase, and spatial confinement is considered as a better explanation for the suppression of β‐phase. Copyright © 2011 Society of Chemical Industry     

Effect of nucleating duality on the formation of γ‐phase in a β‐nucleated isotactic polypropylene copolymer

BACKGROUND: It is a challenge for polymer processing to promote the formation of γ‐phase under atmospheric conditions in isotactic polypropylene (iPP) copolymer containing chain errors. Incorporation of an α‐nucleator in iPP copolymer seems reasonable since it can enhance non‐isothermal crystallization. Up to now, however, the issue regarding a β‐nucleated iPP copolymer still remains unclear, which is the subject of this study. RESULTS: The results indicate that the γ‐phase indeed occurs in a β‐nucleated random iPP copolymer with ethylene co‐unit (PPR) sample and becomes predominant at slow cooling rates (e.g. 1 °C min^?1) where the formation of the β‐form is suppressed to a large extent. With detailed morphological observations the formation of γ‐phase in the β‐nucleated PPR sample at slow cooling rate is unambiguously attributed to the nucleating duality of the β‐nucleator towards α‐ and β‐polymorphs. The α‐crystals, induced by the β‐nucleator, serve as seeds for the predominant growth of the γ‐phase. Moreover, the presence of the β‐nucleator, acting as heterogeneous nuclei, promotes the formation of γ‐phase in the nucleated PPR sample, at least to some extent. CONCLUSION: The findings in this study extend our insights into the formation of γ‐phase in β‐nucleated iPP copolymer and, most importantly, provide an alternative route to obtain iPP rich in γ‐phase. Copyright © 2008 Society of Chemical Industry     

Structure and properties of a β‐nucleated polypropylene impact copolymer

The effect of a β‐nucleating agent (β‐NA) on the properties and structure of a commercial impact polypropylene copolymer (IPC) was investigated. The effect of selected β‐NAs on the impact resistance, stress and strain behaviour of the IPC is reported. In addition, the IPC was fractionated according to crystallinity by preparative temperature rising elution fractionation. Fractions with varying chemical composition and crystallinity were treated with a two‐component β‐NA to investigate the effect of the β‐NA on the various fractions. The results indicate that the efficacy of the β‐NA is dependent on the chemical composition of the polymer that crystallises, more specifically on the sequence length of crystallisable propylene units. The effect of the addition of β‐NAs on the overall morphology of the IPC was also investigated, and in particular the size and distribution of the rubbery particles in these complex reactor blends were probed. © 2014 Society of Chemical Industry     

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     

Structural characterization of α‐ and β‐nucleated isotactic polypropylene

Modification of isotactic polypropylene (iPP) with two nucleation agents, namely 1,3:24‐bis(3,4‐dimethylobenzylideno) sorbitol (DMDBS) (α‐nucleator) and N, N′‐dicyclohexylo‐2,6‐naphthaleno dicarboxy amide (NJ) (β‐nucleator), leads to significant changes of the structure, morphology and properties. Both nucleating agents cause an increase in the crystallization temperature. The efficiency determined in a self‐nucleation test is 73.4 % for DMDBS and 55.9 % for NJ. The modification with NJ induces the creation of the hexagonal β‐form of iPP. The addition of DMDBS lowers the haze of iPP while the presence of NJ increases the haze. Copyright © 2004 Society of Chemical Industry     

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     

Isothermal crystallization kinetics and subsequent melting behavior of β‐nucleated isotactic polypropylene/graphene oxide composites with different ordered structure

The effects of ordered structure on isothermal crystallization kinetics and subsequent melting behavior of β‐nucleated isotactic polypropylene/graphene oxide (iPP/GO) composites were studied using differential scanning calorimetry. The ordered structure status was controlled by tuning the fusion temperature (T_f). The results showed that depending on the variation of crystallization rate, the whole T_f range could be divided into three regions: Region I (T_f > 179 °C), Region II (170 °C ≤ T_f ≤ 179 °C) and Region III (T_f < 170 °C). As T_f decreased from Region I to Region III, the crystallization rate would increase substantially at two transition points, due to the variation of the ordered structure status. Calculation of Avrami exponent n indicated that the ordered structure induced the formation of two‐dimensional growing crystallites rather than three‐dimensional growing crystallites. Moreover, in the case of isothermal crystallization, the ordered structure effect (OSE) can also greatly increase the relative content of β‐phase (β_c). In Region II, OSE took place, resulting in evident increase of β_c, achieving 92.4% at maximum. The variation of the isothermal crystallization temperature (T_iso) had little influence on the T_f range (Region II) of the OSE. The higher T_f in Region II was more favorable for the formation of higher β_c. The ordered structure was favorable for the improvement of the nucleating efficiency of β‐nucleating agent (β‐NE), and was more effective for the improvement of lower β‐NE. © 2018 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     

成核剂对聚丙烯力学性能与结晶行为的影响

研究了两种类型的成核剂对国产共聚聚丙烯的结晶形态以及拉伸强度、冲击强度的影响。结果表明:加入TMB-5型成核剂,聚丙烯的冲击强度有一定程度改善,w(TMB-5)为0.1%时,改性聚丙烯的缺口冲击强度达到最大;TMX-2型成核剂可改善聚丙烯的拉伸性能,但抗冲击性能降低较大;TMB-5型成核剂可显著地改变聚丙烯的结晶行为,诱导聚丙烯在结晶过程中主要形成β晶;TMX-2型成核剂可诱导聚丙烯在结晶过程中主要生成α晶,与纯PP相比,α晶的形成能力增强。     

β‐Polypropylene/wood flour composites: Effects of specific β‐nucleation and coupling agent on mechanical behavior

Polypropylene/wood flour composites were prepared by melt compounding. To improve their mechanical performance, the matrix polypropylene was modified with a specific nucleation agent based on an amide of dicarboxylic acid, which promotes crystallization predominantly in the β‐phase. The resulting material was used as a matrix for composites containing 10%, 20%, and 30% of wood flour. Uniform dispersion of the filler and improved interfacial adhesion was ensured by compatibilization with a small amount of maleic anhydride‐grafted polypropylene. A beneficial effect of application of the nucleation agent together with a compatibilizer on the resulting mechanical behavior was shown. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 506–511, 2007     

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     

A highly efficient β‐nucleating agent for impact‐resistant polypropylene copolymer

In this work, we reported calcium tetrahydrophthalate as a high efficient β‐nucleating agent (β‐NA) for impact‐resistant polypropylene copolymer (IPC). The relative fraction of the β‐crystal can reach as high as 93.5% when only 0.03% β‐NA is added. The non‐isothermal and isothermal crystallization behaviors, morphology, lamellar structure and mechanical properties of IPCs with various β‐NA contents were studied. During non‐isothermal crystallization, the cooling rate has an important influence on the relative fraction of the β‐crystal, which decreases remarkably as the cooling rate increases. The β‐NA also greatly accelerates crystallization rate of IPC, resulting from both more crystal nuclei and larger Avrami exponent. The small angle X‐ray scattering characterization shows that more amorphous components are included into the inter‐lamellae after addition of β‐NA. Dynamical mechanical analysis (DMA) reveals that the storage modulus at low temperature and the loss factor above 0 °C from the PP component can be enhanced upon addition of β‐NA and reach a maximum at the β‐NA content of 0.05 wt %. Impact test shows that the impact strength of the IPC at 0°C can be improved as much as 40% when the content of calcium tetrahydrophthalate is 0.10 wt %. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40753.     

Effects of rosin‐type nucleating agent on polypropylene crystallization

In this investigation the effects of a rosin‐type nucleating agent, which was prepared from cocrystallizing of dehydroabietic acid and Na‐dehydroabietate, on polypropylene (PP) crystallization were studied. The results of differential scanning calorimetry and X‐ray diffraction proved that a cocrystal of dehydroabietic acid and Na‐dehydroabietate was formed. The lower melting point of the cocrystal caused it to be uniformly dispersed in PP. When cocrystals were added as nucleating agent, the mechanical properties, heat distortion temperature, and crystallization temperatures of PP were obviously improved, and the size of spherulites was also decreased. This proved that the cocrystals of dehydroabietic acid and Na‐dehydroabietate could act as an effective nucleating agent for PP. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1069–1073, 2002     

Crystalline morphology and dynamical crystallization of antibacterial β‐polypropylene composite

The crystalline morphology and dynamical crystallization of antibacterial polypropylene composite and pure polypropylene were investigated via differential scanning calorimeter (DSC), wide angle X‐ray diffraction (WAXD), and real‐time hot‐stage optical microscopy (OM). The results reveal that the crystalline morphology of antibacterial PP composites changes with variations of the crystallization conditions and compositions. The crystalline phase consists of both α‐PP and β‐PP crystals. The content of β‐PP decreases with the increase in antibacterial agent content and cooling rate. With the addition of β‐nucleating agent, the morphologies of all dynamically crystallized antibacterial PP composites show no obvious spherulitic morphology, and the decrease of crystal perfection and the increase of nucleation density of antibacterial PP composite system could be observed. With the increase of antibacterial agent content, the overall crystallization rates of the antibacterial PP composite increase dramatically, while the content of β‐PP in all antibacterial PP composite decrease distinctly under given cooling conditions. These results can be explained by the interruptive effect of antibacterial agent on interactions of β‐nucleating agent components and the obstructing effect of antibacterial agent on the mobility of PP chains in melts. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008