The effect of specific nucleation on molecular and supermolecular orientation in isotactic polypropylene

The molecular and supermolecular orientation, morphology and structural changes observed during cold drawing of injection moulded isotactic polypropylene modified by specific α, and β nucleating agents were studied by polarised photoacoustic FTIR spectroscopy, wide-angle X-ray diffraction and differential scanning calorimetry. Significantly lower molecular orientation was found in the core of the β-nucleated injection moulded specimens as compared to unmodified and α-nucleated materials. This has been ascribed to the fast growth of the β-crystallites which inevitably dislocates the flow-induced orientation within the crystalline regions and in their vicinity. Moreover, it was found that the presence of the developed β-crystallites distinctly diminishes the efficiency of the orientational solid-state drawing assessed on both levels of the hierarchical structure (molecular and crystalline). This structural observation is directly connected with macroscopic softening effect of the β-phase: lowering the yield stress and flattening the neck shoulder. Thus, the interrelation between the microstructural and macroscopic effects of the β-phase could be described as a feedback process.     

Mechanical enhancement of melt-stretched β-nucleated isotactic polypropylene: The role of lamellar branching of β-crystal

Melt-stretched isotactic polypropylene (iPP) filled with different weight fractions (0, 0.1, 0.2 and 0.4 wt %) of β-nucleating agent (β-NA) was extruded via a single screw extruder with a slit die and immediately melt-stretched at the die exit. The microstructure and mechanical properties (i.e., monotonic tensile, step-cycle and stress relaxation behavior) of these samples were analyzed. Unexpectedly, the lamellar branching of β-crystal, which is similar to lamellar branching of α-crystal, is observed in melt-stretched β-nucleated iPP. More interestingly, it is found that, compared with other samples, iPP containing 0.2 wt % of β-NA has the best mechanical properties. Through thorough analysis of various structural characterizations, the improved tensile strength obtained from step-cycle tests and viscous force obtained from stress relaxation measurements for iPP with 0.2 wt% of β-NA is ascribed to lamellar branching of β-crystal. The study is an example of preparing high performance polymers via practical polymer processing methods.     

Injection-moulded α- and β-polypropylenes: I. Structure vs. processing parameters

The paper studies the effects of mould temperature and holding pressure on the structure of neat and β-nucleated isotactic polypropylenes. Commercially available isotactic polypropylene was modified with a β-specific nucleator based on N,N′-dicyclohexylnaphthalene-2,6-dicarboxamide in the concentration of 0.03 wt.%. From both the original material (α-iPP) and the β-nucleated material (β-iPP), dog bone-shaped test specimens were injection-moulded, using two sets of processing parameters. In the T-set the mould temperature was varied within the range of 40-120 °C in 10 °C steps, while in the P-set the holding pressure was changed from 5 to 13 MPa in 1 MPa steps. Other processing parameters were kept on the same level. Polarized-light microscopy showed a strong effect of mould temperature on the morphology of α-iPP specimens; the skin thinned out and the spherulite size increased with mould temperature rise. On the other hand, in the case of β-iPP only the skin thickness was correspondingly affected, while the spherulite size remained virtually constant, independent of the mould temperature changes. At the same structure level, both α-iPP and β-iPP specimens were insensitive to holding pressure variations. Polymorphic composition derived from wide-angle X-ray scattering displayed similar range of changes induced by variations of the processing parameters for both materials. The increase of mould temperature positively influenced the crystallinity and the β-form content, particularly in the skin of specimens. On the contrary, higher holding pressure depressed the crystallinity proportionally within the bulk of specimens.     

Morphology – Property Correlations of PP Materials by Means of Microhardness

The present work deals with the influence of crystallization temperature, cooling rate and annealing conditions on microhardness, indentation modulus and creep behaviour of ethylene/propylene (E/P) random copolymers with 4, 6 and 8 mol% ethylene as well as α- and β-spherulites in a homopolymer and an E/P random copolymer. The materials are unnucleated, the formation of β-spherulites occurs sporadically. Additionally the indentation creep behaviour of α- and β-nucleated PP is investigated. A nearly linear correlation between hardness as well as indentation modulus and crystallintity of the E/P copolymers can be proved. An increasing cooling rate leads to decreasing hardness and modulus values due to the hindered crystallization. For the investigation of the α- and β-phases different crystallization and annealing temperatures are used. Independent of these conditions, microhardness and modulus determined by indentation testing are lower for the β-phase in both materials. Increasing crystallization temperature and annealing lead to an increasing hardness and modulus in both phases. However, an effective annealing effect takes place only at short times and elevated temperatures above 100 °C. The increasing of microhardness and modulus is correlated with an increasing in lamellae thicknesses. Additionally, indentation creep experiments were carried out on nucleated materials that show the stronger creep tendency of the β-phase PP and the stronger influence of annealing on this phase.     

Effects of polyamide 6 on the crystallization and melting behavior of β-nucleated polypropylene

Non-nucleated polypropylene alloy with polyamide 6 (PP/PA6) and β-nucleated polypropylene (β-PP)/PA6 alloy, as well as its compatibilized version with maleic anhydride grafted PP (PP-g-MA) were prepared with an internal mixer. In the all alloys, PP formed a continuous phase with a dispersive PA6. Effects of PA6 on the non-isothermal crystallization behavior, melting characteristics and the β-PP content of alloys were investigated by differential scanning calorimeter (DSC) and wide angle X-ray diffraction (WAXD). The results indicated that the crystallization temperature () of PP shifts to high temperature in the non-nucleated PP/PA6 alloys due to the α-nucleating effect of PA6. However, in the β-nucleated PP/PA6 alloys, PA6 hardly has an effect on the of PP. The β-PP content in the alloys not only depends on the content of the PA6, but also on the melting temperatures. 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. Addition of PP-g-MA promotes the formation of β-PP in the β-nucleated PP/PA6 alloys. The increase in the PA6 content has a little influence on the of PP and the β-PP content in the compatibilized β-nucleated PP/PA6 alloys. The non-isothermal crystallization kinetics of PP in the alloys was evaluated by Mo’s method.     

Polymer blends based on the β-modification of polypropylene

iPP/sPP, iPP/rPP, iPP/PVDF and iPP/PA-6 blends, and their β-nucleated forms were prepared in the present study. The components of iPP/sPP and iPP/rPP blends are compatible in the molten state. The phase structure of the melt of iPP/PVDF and iPP/PA-6 blends is heterogeneous. The melting and crystallisation characteristics as well as the structure and polymorphic composition of these blends were studied by polarised light microscopy (PLM) and differential scanning calorimetry (DSC). When semicrystalline polymers are added to iPP, the most important factor of the formation a blend with β-crystalline phase is the α-nucleation effect of the second polymer. In the case of polymers with an α-nucleating effect, the temperature range of their crystallisation should be lower than that of β-iPP. β-nucleated iPP/PVDF and iPP/PA-6 blends are extreme examples showing that completely β-iPP matrix can not form even in the presence of a highly effective β-nucleant, because of the strong α-nucleating ability and higher crystallisation temperature range of PVDF and PA-6. We found that the β-crystallisation tendency of random propylene copolymers can be enhanced by adding an iPP homopolymer.     

Study of nucleation induced structure modification in isotactic polypropylene by DMTA and solid state NMR

Isotactic polypropylene (iPP) modified by heterogeneous nucleation and molten state drawing was investigated using the DMTA and NMR methods. The nucleation was realized by specific α and β nucleating agents, 1,3,2,4-bis(3,4-dimetylobenzylideno) sorbitol (Millad 3988, Miliken) leading to the creation of the α phase, and N,N′-dicyklohexylo-2,6-naftaleno dikarboxy amid (NJ100) as the β phase promoter. The processing induced modification was performed by molten state drawing during an extrusion in the range between the die exit and the calibration unit. An increase of the glass transition temperature of iPP was found to be drawing independent for the β-nucleated samples, and dependent in the case of the α-iPP. Changes in the macromolecular mobility, depending on the α/β iPP structure and molten state drawing, was found by NMR lineshape and second moment measurements.     

Study on photodegradation of injection-moulded β-polypropylenes

The effects of UV irradiation on β-nucleated injection-moulded polypropylenes (β-iPP) have been studied at several structural levels. Commercially available isotactic polypropylene was modified by 0.03 wt.% β-nucleating agent based on N,N′-dicyclohexylnaphthalene-2,6-dicarboxamide. β-iPP specimens were injection-moulded using a processing set-up in which only mould temperature was varied. It was found that specimens consisted of a skin-core structure, which was strongly influenced by varying mould temperatures. The structural development consequently affected the specimen degradability as shown by wide-angle X-ray scattering, light microscopy and micro-infrared microscopy.     

Blends of the β-modification of polypropylene

Preparation, crystallization and melting characteristics of blends of β-nucleated isotactic polypropylene with different elastomers and polyethylenes were studied. Blends of β-polypropylene can be prepared if the polymer additive is amorphous or has negligible α-nucleating effect during the crystallization of polypropylene.     

The effect of compatibilizers on the crystallisation, melting and polymorphic composition of β-nucleated isotactic polypropylene and polyamide 6 blends

Non-compatibilized and compatibilized blends of isotactic polypropylene (iPP) and polyamide 6 (iPP/PA6) as well as their β-nucleated versions were prepared using maleic anhydride functionalized iPP (MAPP) with different anhydride contents as compatibilizer. Ca-suberate, a highly efficient and selective β-nucleating agent was added to the blends in order to promote the formation of the β-modification of iPP. The melting and crystallisation characteristics, as well as the polymorphic composition of the blends were studied by differential scanning calorimetry (DSC). The supermolecular and phase structure of the blends were studied by polarised light microscopy (PLM). iPP and PA6 form blends with heterogeneous phase structure; the PA6 component is dispersed in the iPP matrix in the concentration range studied. The compatibilizer promotes the dispersion of PA6 resulting in smaller particles than without MAPP. In the non-compatibilized β-nucleated blends, an iPP matrix consisting mainly of the α-modification was formed already at low PA6 content. On the contrary, predominantly β-iPP matrix developed in the presence of MAPP compatibilizers. The formation of α-iPP matrix in the absence of compatibilizer is related to the selective encapsulation of the nucleating agent in the polar PA6 phase. The influence of the blending technique on the polymorphic composition of the matrix supports the hypothesis of selective encapsulation. Compatibilizers, besides their traditional benefits assist the distribution of the β-nucleating agent between both phases of the blends and promote the formation of a matrix rich in β-iPP. In the presence of β-nucleating agent MAPP with low anhydride content and blends of iPP containing maleated polypropylene crystallise predominantly in the β-form.     

成核剂含量对β晶相聚丙烯结晶与熔融行为的影响

用DSC研究了β成核剂含量对β聚丙烯在等温与非等温结晶条件下的结晶与熔融行为的影响,发现当成核剂含量为0.005％时,结晶焓△H_c、β晶的熔融焓△H_(mβ)及熔点T_(mβ)均为最大,而α晶的相对含量最小.广角X-衍射数据表明,成核剂含量高的试样的(301)衍射峰的相对强度下降,反映分子链排列的纵向有序性降低.根据聚丙烯分子在β成核剂上附生结晶的成核机理解释了上述结果.     

Tensile behaviour of isotactic polypropylene modified by specific nucleation and active fillers

Commercial-grade 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% (by weight) of different calcium carbonate fillers. These fillers differed in particle size and surface treatment. The β-phase content, morphology and tensile mechanical properties were investigated. A distinct β-nucleation activity was found with surface-treated fillers; nevertheless, to obtain stiff and reasonably ductile composite materials, a matrix containing a critical nucleant concentration (0.03 wt%) was necessary.     

The role of specific nucleation in polypropylene photodegradation

The paper focuses on the effects of polymorphism on photodegradation of isotactic polypropylene. The starting polymer was modified by a specific α-nucleating agent, 1,3;2,4-bis(3,4-dimethylbenzylidene)sorbitol, by a specific β-nucleating agent, N,N′-dicyclohexylnaphthalene-2,6-dicarboxamide, or their combination. Samples prepared by compression moulding were then exposed to UV-irradiation in the interval from 0 to 240 h. The differences in morphology were reflected in different photooxidative behaviour. Infrared spectroscopy showed that neat polypropylene was the most sensitive to photooxidation and the sample modified solely by the β-nucleating agent was the least sensitive. The remaining two samples exhibited an intermediate sensitivity. Differential scanning calorimetry revealed that the UV-exposure led to gradual changes in crystallization mechanism specifically asserting in individual materials. This behaviour was ascribed to homogeneous nucleation of partly degraded macromolecules. Possible changes of the nucleating agent itself during UV-exposure were also discussed.     

Injection-moulded α- and β-polypropylenes: II. Tensile properties vs. processing parameters

Resuming our comprehensive study, present Part II directs attention towards the effects of mould temperature and holding pressure on the tensile properties of neat and β-nucleated isotactic polypropylenes. A commercial-grade of isotactic polypropylene was modified with a β-specific nucleator. From both the original material (α-iPP) and the β-nucleated material (β-iPP), tensile test specimens were injection-moulded. Stress-strain measurements performed at room temperature revealed a positive influence of higher mould temperatures but negligible effect of holding pressure on the elastic modulus of injection-moulded specimens. It was suggested that at optimum processing conditions the elastic modulus of both α- and β-iPP may be comparable. The softening effect of β-form manifested itself in systematically lower yield stress values of β-iPP as compared to α-iPP. The yield strain of both α- and β-iPP decreased with the increase of mould temperature and the decrease of holding pressure. Prolonged solidification times at higher mould temperatures negatively influenced the strain at break of the specimens; the values of β-iPP exceeded by several folds those of α-iPP. The stress at break of β-iPP decreased correspondingly to strain at break. On the contrary, the increase of strain at break in α-iPP was followed by a decrease of stress at break.     

Crystallization behavior of sorbitol derivative nucleated polypropylene block copolymer under high pressure

The preparation of γ-phase in polypropylene is still an interesting issue in a long-term. In this work, we introduced a highly effective α-phase nucleating agent 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol derivatives (DMDBS) into polypropylene block copolymer (PPB) and investigated the crystallization behaviors of nucleated PPB sample under high pressure. The crystallization and melting behaviors of samples were characterized by differential scanning calorimetry, and the crystalline structure as well as the relative fraction of γ-phase in the sample was characterized by wide-angle X-ray diffraction (WAXD) and two-dimensional WAXD. Scanning electron microscope was used to characterize the supermolecular structure of samples. The results show that the effects of DMDBS and high pressure on crystallization behavior of PPB were dependent on the content of DMDBS. When the content of DMDBS is smaller than the critical value, there is a synergistic effect between DMDBS and high pressure to promote the formation of γ-phase. Specifically, the critical pressure under which γ-phase dominates completely is also decreased dramatically. When the content of DMDBS is higher than the critical value, there is a competition between the effect of DMDBS, which promotes the formation of α-phase and the effect of high pressure which promotes the formation of γ-phase.     

Effects of clay on polymorphism of polypropylene in polypropylene/clay nanocomposites

The effects of clay on polymorphism of polypropylene (PP) in PP/clay nanocomposites (PPCNs) under various thermomechanical conditions were studied. In extruded PP and PPCN pellet samples, only α-phase crystallites existed, as they were prepared by rapidly cooling the melt extrudates to room temperature. Under compression, β-phase crystallites can develop in neat PP under various thermal conditions, of which isothermal crystallizing at 120 °C gave the highest content of β-phase crystallites. In contrast, no β-phase crystallite was detected in the PPCN samples prepared under the same conditions. This indicated that clay significantly inhibits the formation of β-phase crystallites. The likely reason is that the presence of clay in PPCNs greatly sped up the crystallization process of the α phase, whereas it had an insignificant effect on the crystallization rates of the β phase. The results also showed that clay may slightly promote the formation of γ-phase PP crystallites in PPCNs. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1810–1816, 2004     

MULTIPLE MELTING BEHAVIOR OF β-CRYSTALLINE PHASE POLYPROPYLENE

Differential scanning calorimetry and X-ray diffraction experiments on β-nucleated polypropylene were made on the samples crystallized at different temperatures and processed by injection molding. The crystal perfection was shown to vary with crystallization temperature. The observed multiple peaks could be related to a ill-phase with defective inclination of the chains, a recrystallized or original β_2-phase of more perfect inclination, and the α-phase. Injection molded samples could be analyzed from the established DSC interpretation.     

Spectroscopic study of α- and β-phase isotactic polypropylene and of atactic polypropylene in solution

Raman spectroscopy is used to investigate the conformation and packing of isotactic crystalline α-phase polypropylene compared with lower-order β-phase isotactic polypropylene and to study the solution behavior of atactic polypropylene. The high-frequency region of the spectrum is analyzed in light of a normal-mode calculation that takes into account the methyl-group vibrations. This region is sensitive to both chain conformation and packing, and because of the high intensity of the methyl and methylene high-frequency stretching modes, it can be used to probe small changes in intermolecular or intramolecular order. Differences in the thermal behavior between the two solid isotactic polypropylene samples are explained interms of packing defects which exist in the β-phase form. In the solution study, we demonstrate that, for molecules in which bands sensitive to intermolecular interactions exist, as is the case of the methyl and methylene vibrations of polypropylene, spectroscopic techniques can be used to estimate the minimum overlap concentration.     

Non-isothermal crystallization, melting behavior and polymorphism of polypropylene in β-nucleated polypropylene/recycled poly(ethylene terephthalate) blends

β-Nucleated polypropylene (PP), non-compatibilized and compatibilized β-nucleated PP/recycled poly(ethylene terephthalate) (r-PET) blends were prepared on a twin-screw extruder. The compatibilizers were maleic anhydride grafted PP (PP-g-MA), glycidyl methacrylate grafted PP (PP-g-GMA), maleic anhydride grafted polyethylene-octene (POE-g-MA) and polyethylene-vinyl acetate (EVA-g-MA) elastomers. Effects of r-PET content, compatibilizer type and content, pre-melting temperature and time on the non-isothermal crystallization and melting behavior, and polymorphism of PP in the blends were investigated by differential scanning calorimeter (DSC). DSC results show that the crystallization temperature of PP crystallized predominantly in β-modification was higher than that of neat PP. In the non-compatibilized blend, PP matrix crystallized mainly in α-modification even if r-PET content was only 10 wt%. However, PP-g-MA compatibilization made PP matrix crystallize mainly in β-modification, but PP-g-GMA, POE-g-MA and EVA-g-MA did not improve the β-modification content distinctly. The α-crystal melting peak temperature of PP decreased with increasing pre-melting temperature, but r-PET content, compatibilizer type and content as well as pre-melting time had no obvious effect on the melting temperature of PP. The increase in PP-g-MA content, pre-melting temperature and time was benefit for the formation of β-modification. It is suggested that the β-nucleating agent is encapsulated or dissolved in polar r-PET in β-nucleated PP/r-PET blend, addition of PP-g-MA to the non-compatibilized blend resulted in transferring β-nucleating agent from r-PET phase into PP phase, the increase in PP-g-MA content, melting temperature and time was benefit for transferring β-nucleating agent from r-PET phase into PP phase. The non-isothermal crystallization kinetics of PP in the blends were evaluated by Mo’s method.     

DSC and morphological studies on the crystallization behavior of β-nucleated isotactic polypropylene composites filled with Kevlar fibers

The crystallization behavior of β-nucleated isotactic polypropylene (PP) composites filled with Kevlar fibers (KFs), as well as that of non-nucleated PP/KF composites for comparison, was investigated using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The morphological observations revealed that the KF addition could induce thick α-transcrystalline layer around their surfaces in PP/KF composites, while no obvious transcrystalline layer could be detected in β-nucleated PP/KF composites. Detailed DSC investigations suggested that for the PP/KF composites, the dominant modification was α-form, and the crystallization process of matrix was promoted by KF addition, as illustrated by faster isothermal crystallization rate, shorter induction time, and higher crystallization temperature. However, for β-nucleated PP/KF composites, the main modification was β-form, and their crystallization characteristics were independent of KF addition, indicating that the α-nucleating effect of KFs was absent in this system. The DSC results were confirmed by further rheological and wide angle X-ray diffraction (WAXD) studies. The mechanism of the formation of transcrystalline layer was also discussed.