Effects of additives on non-isothermal crystallization kinetics and morphology of isotactic polypropylene

In this study, effects of commercial additives such as antioxidant and stabilizer on the non-isothermal crystallization kinetics of isotactic polypropylene without nucleating agents were investigated by differential scanning calorimetry (DSC) method. Kinetic parameters by Osawa, Avrami and Liu-Mo models and apparent activation energy of the crystallization by Kissinger model were calculated. A polarized optical microscope was also used to observe crystalline morphology of the polypropylene samples crystallized at different cooling rates. On the contrary rate inducing effects of the nucleating agents on the crystallization kinetics of the polypropylene, interestingly, it was found that such types of commercial additives reduced the overall crystallization rate of the polypropylene. Based on the crystallization kinetics and morphology of the samples, it was observed that commercial additives inhibit the chain diffusion toward the growing crystal faces thus slow the crystal growth rate. Furthermore, calculated nucleation activity (ϕ) for the additives showed that they do not act as effective nucleating agents. It was found that the crystallization activation energy of additive-free sample was higher than that of the sample which has commercial additives. Activation energies were found to be 233.6 and 276.7 kJ mol⁻¹ for the PP-1 and PP-2, respectively. Kinetic results also show importance of using of nucleating agents to increase the crystallization rate of polypropylene by increasing the nucleation and thus overall crystallization rate during polypropylene processing operations (esp. for a fast processing cycle in injection molding).     

Foaming behavior of isotactic polypropylene in supercritical CO2 influenced by phase morphology via chain grafting

Polystyrene (PS) and poly(methyl methacrylate) (PMMA) grafted isotactic polypropylene copolymers (iPP-g-PS and iPP-g-PMMA) with well-defined chain structure were synthesized by atom transfer radical polymerization using a branched iPP (iPP-B) as polymerization precursor. The branched and grafted iPP were foamed by using supercritical CO₂ as the blowing agent with a batch method. Compared to linear iPP foam, the iPP-B foams had well-defined close cell structure and increased cell density resulted from increased melt strength. Further incorporating PS and PMMA graft chains into iPP-B decreased the crystal size and increased the crystal density of grafted copolymers. In iPP-g-PS foaming, the enhanced heterogeneous nucleation by crystalline/amorphous interface further decreased the cell size, increased the cell density, and uniformized the cell size distribution. In contrast to this, the iPP-g-PMMA foams exhibited the poor cell morphology, i.e., large amount of unfoamed regions and just a few cells distributed among those unfoamed regions, although the crystal size and crystal density of iPP-g-PMMA were similar to those of iPP-g-PS. It was found that the iPP-g-PMMA exhibited PMMA-rich dispersed phase, which had higher CO₂ solubility and lower nucleation energy barrier than copolymer matrix did. The preferential cell nucleation within the PMMA-rich phase or at its interface with the matrix accounted for the poor cell morphology. The different effect of phase morphology on the foaming behavior of PS and PMMA grafted copolymers is discussed with the classical nucleation theory.     

聚丙烯复合材料的非等温结晶动力学

采用差示扫描量热仪研究了β成核剂和水滑石(LDH)/β成核剂复配的成核剂对聚丙烯(PP)非等温结晶动力学及熔融行为的影响。结果表明:加入成核剂后,PP中晶体分布不均匀且分散度增大。莫志深方法采用F(θ)表征聚合物在单位时间内达到某一结晶度时所需的冷却(或加热)速率,结晶度达到40%时,纯PP的F(θ)为3.82,加入β成核剂的PP的F(θ)为3.30,加入LDH/β成核剂的PP的F(θ)为2.49。与纯β成核剂相比,LDH/β成核剂能更好地提高PP的结晶温度、结晶速率,增强PP的β晶熔融峰,减弱β晶和α晶共存熔融峰和α晶熔融峰。     

Some crystallization kinetics of isotactic polypropylene

Infra-red evidence is presented that the building of helices in the crystallization process from the glassy (or smectic) phase or from the melt are second order or zero-th order respectively. The observation coupled with data from density and X-ray diffraction measurements is interpreted in molecular structural terms.     

Effect of polycyclopentene on crystallization of isotactic polypropylene

The application of some polymers as nucleating agents for polypropylene has been examined. Among various polymeric nucleating agents, polycyclopentene was found to be a superior nucleating agent to typical organic nucleating agents. When polycyclopentene was added to polypropylene, the crystallization temperature and the degree of crystallinity of polypropylene increased. In addition, the crystallization rate and the number of spherulites increased whereas the size of spherulites decreased remarkably. As a result of polycyclopentene addition, the transparency of polypropylene film could be improved considerably. © 1994 John Wiley & Sons, Inc.     

Substrate effect on the crystallization of isotactic polypropylene

The evolution of storage modulus measured by a rotational rheometer shows that the isothermal crystallization of isotactic polypropylene (iPP) melts in contact with aluminum plates (PP-Al) are considerably faster than that with stainless-steel plates (PP-SS). The difference is bigger at higher temperatures, and this behavior is opposite to that expected by our numerical simulation considering uniform bulk phase transition and substrate's ability to remove the latent heat. Polarized optical observations and surface energy evaluations via contact angle measurement indicate that surface energy of the substrates, including the effects of submicrometer morphology and roughness, should be the key factor to affect the crystallization of iPP. Transcrystallization zones, in which the nucleation density is controlled by the surface energy of substrates, were observed to grow toward the bulk with the thickness of about 0.2 mm for iPP to affect the global crystallization behavior. The critical value of surface energy of substrate to promote the interfacial crystallization of a polymer melt is derived, in terms of which the aluminum and stainless steel as well as optical glass, promote the surface nucleation with respect to the bulk nucleation of iPP. As a consequence, the conventional differential scanning calorimetry measurement mainly gives the heat fluxes of interfacial crystallization rather than the bulk crystallization due to the large surface-to-volume ratio of the specimen and the aluminum pan used which is a high surface energy substrate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PP非等温结晶动力学处理方法的研究

采用Jeziorny法和Ozawa法研究了聚丙烯(PP)的非等温结晶动力学,确立了PP结晶动力学的适合范围及处理方法,揭示了PP结晶速率和结晶形式随结晶条件的变化规律。结果表明,在相对结晶度为0.04~0.80的快速结晶段,在结晶峰温度(Tp)的两侧,以Jeziorny法处理PP结晶动力学是合适的,Tp两侧的结晶速率和结晶形式存在较大差异;在相近的结晶速率范围内,用Ozawa法处理PP结晶动力学是合适的,PP主要在(125.0±5.0)℃结晶,温度影响PP的结晶形式。     

Quiescent and shear-induced non-isothermal crystallization of isotactic polypropylene-based nanocomposites

The paper reports a study of the effect of the addition of clay nanoparticles on melt rheology, phase structure, and non-isothermal crystallization process of isotactic polypropylene/hydrogenated oligocyclopentadiene (iPP/HOCP) system in quiescent conditions by DSC and under shear applied at different temperatures by SAXS. For both crystallization conditions, the addition of clay and/or HOCP shifts always the crystallization onset to lower values with respect to iPP. These results can be attributed to the diluent effect of HOCP that causes a decrease in the rate of nucleation and grow of the crystals, to the presence of segregated non-crystallizable phases/particles which hinder the transport of macromolecules chains toward the growing nuclei, and to the formation of beta iPP crystals and in the case of shear-induced crystallization to the presence of HPS which seems to reduce, mainly at low T _s, the amount of oriented polymer crystals, which are nuclei for the crystallization. At a given composition, the crystallization temperatures related at the crystallization under shear are always higher that those obtained by quiescent crystallization supporting the idea that the presence of extended chains in these samples act as nucleating agents favoring the crystallization process of iPP.     

Cavitation during isothermal crystallization of isotactic polypropylene

Cavitation during isothermal crystallization of thin films of isotactic polypropylene was investigated systematically by light microscopy. Cavitation results from the negative pressure buildup due to density change during crystallization in the pockets of melts occluded by impinging spherulites. The morphology of such areas was also studied by SEM. The value of the negative pressure at the moment of cavitation was calculated from the drop of the spherulite growth rate. It was shown that the process of cavitation and the value of the negative pressure causing cavitation depend on the crystallization temperature. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2439–2448, 2001     

Character of crystallization nuclei in isotactic polypropylene

Examination of the isothermal crystallization and the effect of melting conditions on samples of isotactic polypropylene and its composite with talc, combined with electron-microscopic observation, has shown two types of heterogeneous nuclei effective in the crystallization process: (1) metastable nuclei, representing the unmelted crystalline phase of polypropylene, stabilized by solid heterogeneities, and operating after melting at relative low melting temperature and/or short melting time; and (2) stable crystallization nuclei, associated with solid heterogeneities, being probably catalyst residues. On the surface of these nuclei isotactic polypropylene tends to crystallize in an ordered fashion.     

Quantification of non-isothermal,multi-phase crystallization of isotactic polypropylene: The influence of cooling rate and pressure

The structure of semi-crystalline polymers is strongly influenced by the conditions applied during processing and is of major importance for the final properties of the product. A method is presented to quantify the effect of thermal and pressure history on the isotropic and quiescent crystallization kinetics of four important structures of polypropylene, i.e. the α-, β-, γ- and mesomorphic phase. The approach is based on nucleation and growth of spherulites during non-isothermal solidification, described by the Schneider rate equations combined with the Komogoroff-Avrami expression for space filling. Using an optimization routine the time-resolved multi-phase structure development is accurately described using crystal phase dependent growth rates and an overall nucleation density, all as function of temperature and pressure. It is shown that the maximum growth rate of the α-, and γ-phase increases with applied pressure, while it decreases for the mesomorphic phase. Addition of β-nucleation agent is interpreted as a secondary nucleation density with a coupled β-phase growth. This complete crystallization kinetics characterization of isotactic polypropylene allows prediction of the multi-phase structure development for a wide range of quiescent processing conditions.     

Improving crystallization behaviors of isotactic polypropylene via a new POSS‐sorbitol compound

A new compound was synthesized by chemical combination of (3‐mercapto)propyl‐heptaisobutyl polyhedral oligomeric silsesquioxane (POSS‐SH) and 1,3:2,4‐bis(3,4‐dimethylbenzylidene) sorbitol (DMDBS) via epichlorohydrin while hydroxyl groups were still retained in the product POSS‐DMDBS. The prepared POSS‐DMDBS was introduced into isotactic polypropylene (iPP) to improve crystallization behaviors of iPP and obtain nanocomposites with suitable mechanical properties. Crystallization and mechanical properties of iPP/POSS‐DMDBS were systematically investigated by wide‐angle X‐ray diffraction, polarization microscopy, atomic force microscopy, differential scanning calorimetry, and tensile tests. The spherulite size of the modified iPP was obviously decreased with the addition of POSS‐DMDBS, while the crystallization temperature was increased by 5°C to 9°C depending on the content of POSS‐DMDBS incorporated. POSS‐DMDBS exhibited relatively higher nucleating efficiency on iPP which is similar to that of DMDBS, confirmed by the increased crystallization temperature. It was also found that the tensile modulus of iPP after adding POSS‐DMDBS increased significantly with respect to pristine iPP, but the elongation values decreased. Introduction of POSS‐DMDBS in content less than 1 wt% could bring about effective influence on the crystallization behaviors of iPP, demonstrating its potential applications . POLYM. ENG. SCI., 57:357–364, 2017. © 2016 Society of Plastics Engineers     

Kinetics of non-isothermal crystallization of polyethylene and polypropylene

Differential scanning calorimetry (d.s.c.) data on non-isothermal crystallization of isotactic polypropylene and high-density polyethylene from the melt at different cooling rates were treated in terms of the Ozawa equation. It was found that the crystallization of polypropylene follows the Ozawa equation but in the case of polyethylene the Ozawa theory is not valid.     

Effects of CO2 on crystallization kinetics of polypropylene

When CO₂ dissolves into a polypropylene (PP), its crystallization kinetics changes These changes were studied, in the expectation that the information would reflect on the behavior of other semicrystalline polyolefins. The isothermal crystallizatior rate of the PP‐CO₂ solutions was measured using a high‐pressure differential scanning calorimeter (DSC), which performed calorlmetric measurements while keeping the polymer in contact with pressurized CO₂. Although the measured crystallizatior rate followed the Avrami equation, the value of the crystallization kinetic constant was different from that measured for PP crystallized in air under atmospheric pressure. The dissolved CO₂ decreased the overall crystallization rate of PP within the nucleation dominated temperature region. This suggests that the dissolved CO₂ decreases the melting and the glass transition temperatures and prevents formation of critical size nuclei.     

Isothermal and non-isothermal crystallization kinetics of hydroxyl-functionalized polypropylene

Hydroxyl-modified polypropylenes (PPOH) with side chains containing OH groups were synthesized by copolymerization of the propylene and undecenyloxytrimethylsilane monomers. The isothermal and non-isothermal crystallization behavior of the modified polypropylenes (PPOH) with side chains containing up to 6.8 mol% OH groups were compared with that of polypropylene (PP). The introduction of the OH-comonomer decreased the overall rate of isothermal crystallization compared with PP due to steric effects of the hydroxyl-containing side-chains that hindered packing of the PP backbone chains into a lamellar structure. However, a maximum reduction in the rate of crystallization occurred at an intermediate hydroxyl concentration as a consequence of a competition between the effects of the comonomer on the nuclei density and the thermodynamic barrier to crystallization. Steric hindrance by the comonomer side-chains also reduced the radial growth rate of the crystals in PPOH and produced a coarser crystal morphology than that for PP. PP and PPOH exhibited an identical α-monoclinic crystal structure, but the introduction of only ∼6.8 mol% comonomer reduced the fold-surface free energy of the crystals by 42%. For non-isothermal crystallization, the crystallization peak temperature (T_p) decreased for low concentrations of OH, but above a critical OH concentration, T_p increased, a result similar to the isothermal crystallization rate.     

Crystallization morphologies and non-isothermal crystallization kinetics of isotactic polypropylene modified by α/β compounded nucleating agents

采用偏光显微镜(POM)及示差扫描量热(DSC)法考察了3种α/β复合成核剂NA40/NABW、NA40/HHPA-Ba、NA40/PA-03对成核等规聚丙烯(iPP)的结晶形态及非等温结晶动力学的影响。对成核iPP结晶形态的研究结果表明：α/β复合成核剂的加入能够减小iPP的球晶尺寸。影响α/β复合成核剂成核iPP结晶形态的主要因素是ΔT_Cp（ΔT_Cp为成核iPP结晶峰值温度与iPP结晶峰值温度的差值）,即复合体系中ΔT_Cp较大的成核剂在iPP结晶过程中起主导作用,最终的结晶形态与单独添加这一成核剂时iPP的结晶形态相类似;当两种成核剂的ΔT_Cp接近相同时,两者竞争成核,成核iPP的结晶形态表现为两种成核剂共同作用的结果。因此,通过改变α/β复合成核剂的复合比例即改变两种成核剂的添加浓度,进而改变其ΔT_Cp,可以得到结晶形态完全不同的iPP。采用Caze法对非等温动力学进行了研究,结果表明：添加α/β复合成核剂能够提高iPP的结晶温度,缩短半结晶时间。复合成核剂成核iPP的结晶行为也同样受成核剂ΔT_Cp的影响,复合成核iPP的Avrami指数接近于复合体系中ΔT_Cp较大的成核剂单独添加时iPP的Avrami指数。     

The effect of talc on the crystallization of isotactic polypropylene

Isotactic polypropylene (iPP) has been crystallized in the presence of talc under the quiescent state and shear flow of injection molding. The resulting morphology has been investigated by means of polarizing microscopy, transmission electron microscopy, and wide angle X‐ray diffraction. In the quiescent state, the iPP lamellae grew from the surface of talc and the transcrystalline region was formed at the interface between iPP melt and the talc. The nucleation of iPP was very frequent on the cleavage plane of talc. The X‐ray diffraction pattern of the transcrystal showed a*‐axis orientation to the crystal growing direction. In injection‐molded samples of the talc‐filled iPP, the morphology of lamella growing from talc appeared as same as that of the transcrystal. However, the crystalline orientation of injection‐molded talc‐filled iPP, in which the b axis was oriented to the thickness direction and the a* and the c axis was oriented to the flow direction, was quite different from that of the transcrystal. This b‐axis orientation results from the orientation of the plate plane of talc, which induces the nucleation and the crystallization under shear flow. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1693–1703, 2001     

Effect of nucleating agent addition on crystallization of isotactic polypropylene

The isothermal and nonisothermal crystallization kinetics of nonnucleated and nucleated isotactic polypropylene (iPP) were investigated by DSC and a polarized light microscope with a hot stage. Dibenzylidene sorbitol (DBS) was used as a nucleating agent. It was found that the crystallization rate increased with the addition of DBS. The influence of DBS on fold surface energy, σ_e, was examined by the Hoffman and Lauritzen nucleation theory. It showed that σ_e decreased with the addition of DBS, suggesting that DBS is an effective nucleating agent for iPP. Ozawa's theory was used to study the nonisothermal crystallization. It was found that the crystallization temperature for the nucleated iPP was higher than that for nonnucleated iPP. The addition of DBS reduced the Ozawa exponent, suggesting a change in spherulite morphology. The cooling crystallization function has a negative exponent on the crystallization temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2089–2095, 1998     

Hydrogenated petroleum resin effect on the crystallization of isotactic polypropylene

The influence of the hydrogenated petroleum resin P125 on the crystallization behavior, crystallization kinetics, and optical properties of polypropylene (PP) were investigated. The results of differential scanning calorimetry, successive self‐nucleation, and annealing fractionation demonstrated that P125 reduced the interaction between the PP molecules, decreased the crystallization, prevented PP from forming thick lamellae, and encouraged the formation of thin lamellae. The isothermal crystallization kinetics, self‐nucleation isothermal crystallization kinetics, and polarized optical microscopy observations showed that P125 slightly decreased the nucleation rate, significantly decreased the crystal growth rate, generally reduced the overall crystallization rate, and effectively deceased the crystallite sizes of PP. The optical properties studies showed that P125 effectively decreased the haze and increased the surface glossiness and yellowness index of PP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Formation of β-modification of isotactic polypropylene in its late stage of crystallization

In the late stage of the crystallization of isotactic polypropylene (IPP), melt inclusions are encapsulated by the crystallized phase. The contraction caused by the proceeding crystallization within the inclusion leads to a reduced pressure accompanied by the appearance of vacuum bubbles. In the surface layer of the melt surrounding the vacuum bubbles, the polymer chains are subjected to extension during the development of bubbles, which leads to the formation of -row nuclei. As has been observed during the shear-induced crystallization of IPP, the row-nuclei formed in situ can also induce the growth of the β-phase in this case. It was demonstrated that a possible reason for the — β transition on the surface of growing -spherulites is the local mechanical stress caused by the contraction. Based on experimental results, suggestions are made for the origin of the strongly birefringent phase observed by Duval et al. during the crystallization of blends of IPP and IPP grafted with maleic anhydride.