β-nucleators and β-crystalline form of isotactic polypropylene

Different levels of β-form crystallinity in isotactic polypropylene (iPP) were produced by blending a series of additives. X-ray diffraction analyses showed that the Kx values varied from 0 to 0.05. Indigosol Brown IRRD, Indigosol Red Violet IRH, Cibantine Orange HR, Indigosol Pink IR, Cibantine Blue 2B, Indigosol Golden Yellow IGK, and Indigosol Grey IBL were found to be effective β-nucleators. The respective Kx values of the iPP samples containing the above seven β-nucleators of 0.05 wt % are 0.54, 0.68, 0.82, 0.82, 0.86, 0.92, and 0.95. All the β-nucleators possess fused benzene rings or heterocycles in their molecular structures. X-ray diffraction studies on them revealed a mutual character in that the strongest or the second-strongest reflections almost locate at the d-spacing of 2.83 Å. The magnitude is about half of that of the β-spherulites possess a bright color and that their Maltese Crosses display some concentric banding of a rather spiky, jagged character. Their lamellae exhibit a correlated and dendritic structure seen by a scanning electron microscope. © 1995 John Wiley & Sons, Inc.     

Effects of mineral additives on the β‐crystalline form of isotactic polypropylene

Nineteen kinds of minerals, alone and in bicomponent mixtures with LaC (a mixed ternary complex of trivalent lanthanum stearate and stearin), were added to isotactic polypropylene (iPP). The influences of the minerals on the crystallographic forms of iPP were investigated. A wide‐angle X‐ray diffraction examination demonstrated that no mineral or LaC acting alone could induce the occurrence of the hexagonal β‐form, whereas the bicomponent mixtures could when the mineral was a calcium compound or contained calcium compounds, whether the calcium compounds had a hexagonal crystallographic form or not. We surmise that the actual β‐iPP substrate in such a system might be some binuclear complexes of calcium and rare earth elements with some specific ligands. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1742–1748, 2002     

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     

Crystal morphology and structure of the β‐form of isotactic polypropylene under supercooled extrusion

A supercooled melt of isotactic polypropylene (iPP) was extruded through a capillary die. Polarized light microscopy (PLM), wide‐angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC) were used to investigate the effects of the relatively weak wall shear stress (σ_w), extrusion temperature (T_e), and crystallization temperature (T_c) on the structure and morphology of β‐form isotactic polypropylene (β‐iPP). β‐cylindrites crystals could be observed by PLM in the extruded specimen even at a lower σ_w's (0.020 MPa), and the β‐iPP content increased with decreasing T_e. Under a given T_e of 150°C, the increase in σ_w positively influenced the β‐iPP content. The DSC and WAXD results indicate that the total crystallinity and β‐iPP content increased when T_c was set from 105 to 125°C; the other experimental parameters were kept on the same level. Although T_c was above 125°C, the β‐iPP content obviously decreased, and the total crystallinity continued to increase. On the basis of the influences of σ_w, T_e, and T_c on the β‐iPP crystal morphology and structure, a modified model is proposed to explain the growing of shear‐induced β‐iPP nucleation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

α‐ and β‐crystalline forms of isotactic polypropylene investigated by nanoindentation

Under special crystallization conditions from the melt, both α‐ and β‐forms of isotactic polypropylene were produced simultaneously. The α‐ and β‐spherulites of polypropylene were differentiated under optical microscope, allowing the nanoindentation of individual spherulites of each crystallographic form. Elastic modulus and hardness of β‐spherulites were found to be 10 and 15% respectively lower than in α‐spherulites. The higher stiffness of α may be related to the particular interlocked structure with cross‐hatched lamellae, and to a lower molecular mobility in the crystallites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 195–200, 1999     

Electrical β-relaxation of die-drawn isotactic polypropylene

Measurements of a.c. impedance were carried out in the frequency range 1 Hz to 10⁶ Hz at room temperature on isotropic and die-drawn isotactic polypropylene. It was found that the a.c. impedance decreases with increasing draw ratio in the frequency range 1 Hz to 10⁴ Hz and then becomes independent of draw ratio with increasing frequency. A dramatic drop in the a.c. impedance was observed in the frequency range 10⁴ to 10⁶ Hz, which is associated with a β-relaxation process. The intensity of the β-relaxation peak decreases with increasing draw ratio and nearly disappears for a draw ratio of 16·8. The Cole Cole plots show good semicircles for isotropic and die-drawn samples indicating that a certain polarization mechanism is dominant in polypropylene.     

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     

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     

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     

The formation of β‐polypropylene crystals in a compatibilized blend of isotactic polypropylene and polyamide‐6

Compatibilized polypropylene (PP)/polyamide (PA6) blends with and without β nucleating agent (β‐NA) are prepared, and are designated as Blend‐0.3 and Blend‐0, respectively. The melting and crystallization characteristic of the blends crystallized under different cooling rates and different crystallization temperatures are studied. It is observed that high β‐PP content can be developed in Blend‐0.3 only at slow cooling rates (<5°C/min), whereas high α‐PP content is formed at fast cooling rates. Isothermal crystallization analysis of Blend‐0 indicates that PA6 is an effective NA for α‐PP in the lower temperature range, whereas the α‐nucleating effect disappears in the higher temperature range. Blend‐0.3 can, therefore, be viewed as a system containing both α‐ and β‐NAs, simultaneously. PA6 is competing with β‐NA in inducing PP crystallization. Under the normal injection of Blend‐0.3, the melt will be cooled through the higher temperature that favors the effectiveness of β‐NA rapidly because of the faster cooling rate. However, the α‐nucleation effect from PA6 predominate at the lower temperature. This explains the difficulty in obtaining high β‐PP content in Blend‐0.3 from injection molding. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

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     

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     

A biaxial stretched β‐isotactic polypropylene microporous membrane for lithium‐ion batteries

In this article, microporous polypropylene (PP) membranes were produced with TMB‐5 as β‐crystal nucleating agent by biaxial stretching. Influences of different concentration of TMB‐5 were studied using differential scanning calorimetry and X‐ray diffraction. It was found that the highest crystallinity was reached when the nucleating agent content was 0.5 wt %. The effect of stretching temperature and stretching ratio on pore size distribution and porosity of the membranes were investigated by scanning electron microscopy and mercury porosimeter, respectively. And physical properties, such as tensile strength, permeability, and puncture resistance of the microporous membrane prepared at the optimized conditions, were evaluated. Compared with commercial PP separator membrane, the as‐prepared microporous membrane shows similar uniform pore size distribution and exhibits slightly higher porosity and ionic conductivities. When used as lithium‐ion separator, the experimental film shows more stable cycling performance than the commercial one. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45825.     

Shear‐induced shish‐kebab structures in isotactic polypropylene using acicular precipitated calcium carbonate as whisker

It has been reported in the technical literature that whiskers of rodlike single crystals can be used in order to generate shish‐kebab structures or other different lamellae morphologies during isothermal or dynamic crystallization of sheared or presheared polymer melts. The expected advantage of the changed crystalline structure is a reinforcing effect of the composite. A lot of papers reported about the application of inorganic and organic whiskers such as cellulose and chitin whiskers. This study reports on an attempt to use acicular PCC as appropriate whisker for improving mechanical properties of polypropylene. In this article special attention is given to demonstrate the effect of flow induced crystallization under varying shear conditions in order to improve the mechanical properties. The effects were demonstrated using rheology, thermal analysis, tensile testing, and transmission electron microscopy. POLYM. ENG. SCI., 54:2057–2063, 2014. © 2013 Society of Plastics Engineers     

Effect of N,N′‐diphenyl adipamide on the formation of the β‐crystalline form in isotactic polypropylene

The polymorphic compositions and mechanical properties of isotactic polypropylene (iPP) samples nucleated by a selective β‐nucleating agent [N,N′‐diphenyl adipamide (DPA)] were investigated with wide‐angle X‐ray diffraction, polarized light microscopy, scanning electron microscopy, and mechanical tests. It was found that β‐phase crystals emerged with the addition of DPA, and the relative proportion of the β‐crystalline form reached the maximum value of 0.97 with the addition of 0.1 wt % DPA. The curved lamellae in the β spherulites were like flowers. The β spherulites were etched more easily than α spherulites because amorphous regions were distributed inside the β spherulites. The Izod notched impact strength increased sharply with the addition of DPA and attained the maximum value of 7.30 kJ/m² (the value of blank iPP was 3.13 kJ/m²) with the addition of 0.1 wt % DPA. An analysis of the misfit factors between DPA and β‐iPP showed that β‐iPP could epitaxially crystallize on the DPA crystal well. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Shear‐induced crystallization of isotactic polypropylene studied by simultaneous light intensity and rheological measurements

We investigate the effects of high shear rate and a melt‐insensitive, organophosphate nucleating agent on shear‐induced crystallization of four isotactic polypropylenes using a sliding plate rheometer under isothermal, low‐supercooling conditions. We used a bifurcated optical fiber probe to measure light intensity and a shear stress transducer to monitor the simultaneous viscoelastic response to small‐amplitude oscillatory shear. The two techniques complement each other; at early times of crystallization, large attenuation in the light intensity is observed, whereas during the later stages, a major change in the viscoelastic response occurs due to the growing volume fraction of spherulites. In contrast to quiescent crystallization, the nucleation pathway of nucleated polymers after a brief, strong shear is little influenced by the nucleating agent but strongly affected by molecular weight. The early kinetics of non‐nucleated polymers is more strongly enhanced by shear than that of nucleated polymers. Increasing either shear rate or strain accelerates crystallization, and we found the product of shear rate and strain to be useful for correlating our data. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Effect of magnesium malonate on the formation of the β crystalline form in isotactic polypropylene

Magnesium malonate (MgMt) is used to induce the β crystalline form in isotactic polypropylene (iPP) for the first time. It is shown by wide angle X‐ray diffraction, differential scanning calorimetry, and polarized light microscopy that the content of the β crystalline form increases markedly with the addition of MgMt and attains the maximum value at an MgMt content of 0.10wt%. The tensile strength and flexural modulus of the doped iPP sample decrease somewhat; the tensile strain at break increases slightly; and the Izod notched impact strength increases significantly with the addition of MgMt, as compared with the values for the blank iPP sample. The β‐nucleation mechanism of MgMt is analyzed by the dimensional lattice match criterion. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers.     

Crystallization behavior and crystallization kinetic studies of isotactic polypropylene modified by long‐chain branching polypropylene

In this article, we discuss the crystallization behavior and crystallization kinetics of isotactic polypropylene (iPP) modified by long‐chain‐branching (LCB) high‐melt‐strength iPP over a wide composition range, that is, LCB‐iPP from 10 to 50 wt %. Over the entire range we investigated, the presence of LCB‐iPP accelerated crystallization in both the isothermal crystallization process and nonisothermal crystallization process, even when the LCB‐iPP content was as low as 10%, and both crystallization processes were enhanced more significantly as the LCB‐iPP content increased. Hoffman–Lauritzen theory analysis revealed that the fold‐free energy decreased effectively with the occurrence of the LCB structure, although the growth rate of spherulites was depressed, as shown by polarized optical microscopy. Meanwhile, the regime III–regime II transition temperature was about 15° higher for all of the LCB‐iPP compositions than that of iPP because the LCB structure reduced the mobility of the polypropylene chains. Furthermore, the γ‐form crystal structure was favored by LCB compared to the β form, which was supported by wide‐angle X‐ray diffraction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009