Crystallization Behavior Of iPP Research Articles

A new insight into the formation of β-crystals of isotactic polypropylene induced by zinc dicarboxylic acids

Some zinc dicarboxylic acids can induce numerous β-crystals formation in isotactic polypropylene (iPP), thus improving the crystallization behavior and mechanical properties of iPP. However, the corresponding nucleation mechanism of β-crystals remains inadequate, leading to the absence of a theoretical basis for the design and preparation of new and high-efficiency β-nucleating agents (β-NAs). In this work, we demonstrate a new mechanism that β-crystals can be formed when the interfacial interaction between β-NAs and iPP is comparable to that between β-PP and iPP. The interfacial interaction occurs when iPP epitaxially crystallizes on the NA surface, which will affect the folding and arrangement of iPP chains, thereby leading to formation of different crystalline forms of iPP. The interaction energy of iPP chain with α-PP and β-PP is used as a judgment criterion, which is resolved by molecular dynamics (MD) simulation. We surprisingly found that when the interaction energy of NA/iPP was close to that of β-PP/iPP, the NA can be acted as β-NA; β-crystals were inclined to form when the interaction energy of NA/iPP was close to that of β-PP/iPP. Furthermore, the simulation results are well verified by the crystallization behavior of iPP in the presence of aromatic zinc dicarboxylic acids of zinc terephthalate (ZnCC1) and zinc 4-carboxybenzoate (ZnCC2), lending strong support to the proposed nucleation mechanism and method. This work proposes a new insight into the formation of β-crystals of iPP based on the interaction energy of NA and iPP, and demonstrates a method to rapidly predict and evaluate the β-nucleation effect of NAs, thus may serve as a theoretical guidance for the design of NAs that can induce iPP with specific crystalline forms.

The orientation of the dispersed phase and crystals in an injection-molded impact polypropylene copolymer

The orientation of the dispersed phase and crystals in the injection-molded bar of an impact polypropylene copolymer (IPC) containing isotactic polypropylene (iPP), ethylene-propylene rubber (EPR) and a β-nucleating agent (β-NA) were studied simultaneously. In the IPC, iPP and EPR act as the matrix and dispersed phase, respectively. The EPR is amorphous and the iPP is crystallizable in α- and β-crystalline forms in the presence of the β-NA. The orientation and orientation distribution for both of the EPR phase and the iPP crystals, as well as the crystallization behavior of iPP, were investigated by two-dimensional wide-angle X-ray diffraction (2D-WAXD), two-dimensional small-angle X-ray scattering (2D-SAXS), scanning electron microscope (SEM) and differential scanning calorimetry (DSC). The results of the experiment show that orientation exists for both the EPR phase and the iPP crystals. But their orientation distribution manifests an opposite tendency. The EPR phase was observed to be highly oriented in the core layer but the orientation of the iPP crystals was weakened gradually from skin to core. The difference in the orientation behavior between the EPR phase and the iPP crystals reflects the distinct response of the micrometer-scale EPR particles and nanometer-scale iPP chains upon the flow field and temperature gradient in the mold. The diffraction geometry of the β-crystals has also been discussed in detail. The observations in this study may shed light on the study in the structure and property relationship for the IPC injection-molded products.

Trap Level Characteristics and DC Breakdown Performance of Isotactic/Syndiotactic/Atactic Polypropylene Blend Insulation

Polypropylene (PP) material as a DC cable insulation material has great prospects as a recyclable alternative to cross-linked polyethylene. This paper aims at investigate the effect of PP blends crystallinity morphology and trap energy level distribution on DC breakdown strength. Five different ratios iPP/sPP/aPP blends samples are prepared by melt-blending method. Polarizing optical microscope (POM) experiments are conducted to characterize the crystallinity morphology of five iPP/sPP/aPP blends and isothermal surface potential decay (ISPD) methods are employed to measure the trap levels distribution in composite dielectric. The DC breakdown strength is tested by ball-plate electrodes equipment, and the result of DC breakdown experiment indicates that sPP30 exhibits the highest breakdown field strength, which is 29.2% higher than sPP0. The addition of sPP can act as a nucleus to help the crystallization behavior of iPP, and the distribution of spherulites in sPP30 is the most uniform and dense among the five iPP/sPP/aPP blends samples, which can improve the trap characteristics of polymers. The ISPD results show that the decay rate of the sPP30 sample is the slowest at 50 °C, 70 °C and 90 °C, indicating that sPP30 is more conducive to suppressing the dissipation process of carriers during the depolarization process. Moreover, sPP30 has higher deep trap density and lower shallow trap density and exhibits superior breakdown performance. It is deduced that the addition of sPP can effectively regulate the crystallinity morphology of iPP, and then effectively improve the trap energy level distribution of iPP/sPP/aPP blends, and it shows the improvement of DC breakdown performance macroscopically.

Structure Development in Polymers during Fused Filament Fabrication (FFF): An in Situ Small- and Wide-Angle X-ray Scattering Study Using Synchrotron Radiation

Microstructure formation in individual layers during fused filament fabrication (FFF) of a Π-shaped multilayer single-walled polymer sample was studied by simultaneous measurement of small- and wide-angle X-ray scattering (SAXS and WAXS, respectively) methods employing synchrotron radiation. We investigated individual layers and the welding zone between individual layers. As a model material, we used isotactic polypropylene (iPP), which is a commodity semicrystalline polymer and has a strong potential as a feedstock material for additive manufacturing. The layers were deposited by an FFF three-dimensional (3D) printer that was custom-built to fit into the synchrotron beamline. WAXS data were utilized to determine the temperature of the irradiated volume. The polymer microstructure was characterized in terms of crystallinity and long-spacing. Avrami analysis indicates that the crystallization behavior of iPP in thin layers is rather similar to that observed in quiescent crystallization of bulk iPP, suggest...

Mechanistic insights into the shear effects on isotactic polypropylene crystallization containing β-nucleating agent

The crystalline structures and crystallization behaviors of iPP containing β nucleation agent TMB-5 (iPP/TMB-5) were investigated by synchrotron radiation wide angel X-ray diffraction (SR-WAXD), differential scanning calorimeter (DSC) and polarized light microscope (PLM). It was found that α-crystallization lagged behind β-crystallization at normal temperatures, but the discrepancy reduced with increasing temperature. TMB-5 could not induce β-iPP when the nucleation agent is wrapped up with α-crystal that crystallized at high temperatures. The polymorphic composition of iPP/TMB-5 was susceptible to the introductory moment of shear. New crystallization process of β-nucleated iPP was proposed to understand the experimental phenomena which could not be explained by those reported in the literature. It was supposed that polymer crystallization initiated from mesophase, and the formations of iPP crystals involved the organization of helical conformation ordering within mesophase. It was proposed that the iPP melt contained mesophases with stereocomplex-type ordering of right-handed and left-handed helical chains which could be disturbed by shear or TMB-5, leading to different polymorphic structures.

Mechanistic Insights into the Shear-Inducedβ-Form Crystal Formation of iPP

The conformation of a helical type polymer chain in the crystalline phase prefers the state with lower energy. The molecular simulation of the melting behaviors of α and β isotactic poly(propylene) (iPP) crystals with ultrafast heating shows that the ratio of right-handed and left-handed helix stays at 50% in α-iPP and changes from 100% to 50% in β-iPP before and after melting. Till date, the formation of β form crystal in iPP has not been understood well together with the mechanism of the crystallization process. One of the approaches to produce β-iPP is to shear the melt. The influence of shear flow on the crystallization behavior of iPP was investigated via ex situ and in situ X-ray measurements. It was found that preceding or simultaneously initiated formation of β-iPP together with α-iPP occurs under proper shear conditions. The β-rich iPP sample could no longer form β crystal at 135 °C after heating to the β-melting temperature with the melting of β-iPP and the retaining of oriented α-iPP, which is contrary to the accepted formation process of β-iPP. A mechanism was proposed to understand the shear-induced β crystal in iPP, considering the mesophase and stereocomplex type helical conformation of the polymer chains.

Effects of nucleating agent 1,3,5-benzenetricarboxylic acid tris(cyclohexylamide) on properties and crystallization behaviors of isotactic polypropylene

Amide derivatives of 1,3,5-benzenetricarboxylic acid are a type of novel nucleating agents for isotactic polypropylene (iPP). Effects of nucleating agent 1,3,5-benzenetricarboxylic acid tris(cyclohexylamide) (BTCA-TCHA) on properties and crystallization behaviors of iPP were investigated and the results were compared with those of iPP nucleated with a highly effective commercial nucleating agent Millad 3988. The results showed that BTCA-TCHA was highly effective and it improved greatly the mechanical and optical properties of iPP and increased crystallization peak temperature of iPP obviously. When the addition concentration of BTCA-TCHA was 0.2 wt.%, tensile strength and flexural modulus of iPP were increased by 9.7 and 12.4 %, respectively, and the haze value of iPP was decreased by 53.5 %. When the cooling rate was 20 °C/min, the crystallization peak temperature of iPP was increased from 114.6 °C of virgin iPP to 126.8 °C. In addition, it was found that the nucleation efficiency of BTCA-TCHA was comparable for that of Millad 3988.

Influence of a novel β-nucleating agent on the structure, mechanical properties, and crystallization behavior of isotactic polypropylene

A novel β-nucleating agent of isotactic polypropylene (iPP), the potassium salt of 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (CA-19), was found and its effects on the mechanical properties, content of β-crystal, and crystallization behavior of iPP were investigated. The results showed the content of β-crystals of nucleated iPP ( kβ value) can reach 46.3% with 0.25 wt% CA-19. The impact strength and crystallization peak temperature of nucleated iPP greatly increased. Compared with pure iPP, the impact strength of nucleated iPP shows two times increase, and the crystallization peak temperature ( Tp) of nucleated iPP increased by 7°C. The spherulite size of the nucleated iPP dramatically decreased compared with that of pure iPP. The Caze et al. method was used to investigate the nonisothermal crystallization kinetics of nucleated iPP and the crystallization activation energy was obtained by the Kissinger method.

Temperature‐dependent selective crystallization behavior of isotactic polypropylene with a β‐nucleating agent

AbstractThe crystallization behavior of isotactic polypropylene (iPP) induced with various concentrations of the β‐form nucleating agent aryl amide derivative (TMB‐5) at different temperatures was investigated with synchrotron small‐angle X‐ray scattering and wide‐angle X‐ray scattering (WAXS) and polarized optical microscopy. The WAXS results indicate that TMB‐5 is a temperature‐dependent selective nucleating agent for iPP crystallization. This means that only β crystals or α crystals form at low or high crystallization temperatures, respectively; both β and α crystals can be found at a suitable crystallization temperature. A mechanism was proposed to understand this phenomenon and the crystallization behavior of iPP with the nucleating agent. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Effect of Hyperbranched Polymer on Crystallization Kinetics of Isotactic Polypropylene

In this paper, the isothermal crystallization kinetics of isotactic polypropylene (iPP) and iPP with 5% hyperbranched polymer (HBP) added had been investigated by differential scanning calorimetry (DSC). The results show that a small addition of HBP affects the crystallization behavior of iPP. During isothermal crystallization, the crystallization rate of the blend is higher than those of iPP remarkably. An increase in the Avrami exponent may be attributed to the fractal structure of hyperbranched polymer. The crystallization activation energy is estimated by the Friedman equation, the results show that the activation energy decreases remarkably by addition of HBP and the crystallization rate of the blend is more sensitive to temperature than that of iPP.

Effects of α/β Compound Nucleating Agents on Mechanical Properties and Crystallization Behaviors of Isotactic Polypropylene

Sodium 2,2’-methylene-bis (4,6-di-tert-butylphenyl) phosphate (commercial name: Irgastab NA-11) and N,N’-dicyclohexylnaphthalene-2,6-dicarboxamide (commercial name: NU-100) are highly effective nucleating agents for α-isotactic polypropylene (iPP) and β-isotactic polypropylene (iPP) respectively. Effects of a total concentration of 0.2 wt% NA-11/NU-100 compound nucleating agents with different ratios of NU-100 on mechanical properties and crystallization behaviors of iPP were studied in this paper. The results showed that good balance between decreased stiffness and increased toughness of iPP was realized when the ratio of NU-100 was 50 wt%. Compared with those of virgin iPP, tensile strength, tensile modulus, flexural strength, and flexural modulus of iPP nucleated by the compound nucleating agent with 50 wt% NU-100 decreased by only 2.9%, 4.8%, 3.8% and 6.1% respectively, while the notched Izod impact strength of the nucleated iPP was increased by 212.8%. In addition, differential scanning calorimetry analysis results showed that addition of the NA-11/NU-100 compound nucleating agent increased the peak crystallization temperature of iPP significantly, but the crystallization rate of the nucleated iPP decreased with increasing ratio of NU-100 in compound nucleating agents.

Morphology, mechanical, and crystallization behaviors of micro- and nano-ZnO filled polypropylene composites

The aim of this study was to study the effect of ZnO concentration on the morphology, mechanical, and crystallization behaviors of iPP. Three compositions of iPP/mZnO and iPP/nZnO composites were prepared in a co-rotational twin-screw extruder machine with ZnO content of 2 wt%, 5 wt%, and 8 wt%. Tensile tests showed that the tensile strength at yield and tensile modulus of the composites tended to increase with increasing contents of mZnO/nZnO particles. This improvement in the tensile properties was attributed to good interfacial adhesion between the fillers and the matrix, as evidenced by TEM examination. The tensile strength at yield and tensile modulus values of iPP/nZnO composite with the addition of 2–8 wt% nZnO are higher than those of virgin iPP, and even higher than those of iPP/mZnO composite with the addition of 2–8 wt% mZnO. The non-isothermal crystallization behavior of iPP/mZnO and iPP/nZnO composites was investigated using DSC. The results indicated that the interfacial interaction between iPP and mZnO/nZnO increased the crystallization temperature when the content of ZnO is 5 wt%.

Enthalpy Relaxation during Non-Isothermal Crystallization from the Melt of Polymer: For <i>I</i>PP as Example

The enthalpy relaxation rate (rh) is defined by enthalpy change in unit time to describe non-isothermal crystallization behavior of iPP from its melt. Dates of rhare transformed from those of heat flow rate which are collected by means of DSC directly. The curve by plotting with rhto time indicates that the process of non-isothermal crystallization can be separated into two stages by the time point of inflection at rhcurve. The two stages are called stage Ⅰand stage Ⅱ. The curve of rhis differentiated and the curve of Ahproduced. There are two time inflection point in curve of Ah. Combined different trends of rhand Ahduring the whole process, the non-isothermal crystallization are further separated into four sub-stages, which are called stage Ⅰ1, stage Ⅰ2, stage Ⅱ1and stage Ⅱ2. The critical values of time and relative crystallization degree which divide the process of non-isothermal crystallization of iPP are present. It provides one new method to uncover the details of non-isothermal crystallization process.

Effect of –COOH Functionalized Carbon Nanotubes on Mechanical, Dynamic Mechanical and Thermal Properties of Polypropylene Nanocomposites

Multi-walled carbon nanotubes (CNTs) were functionalized on treatment with nitric acid and the surface-modified CNT was characterized using Fourier transform infrared spectroscopy (FTIR). Isotactic polypropylene (iPP)/CNT composites at different CNT loadings (i.e., 0.1, 0.25, 1.00, and 5.00 wt%) were prepared by melt blending in a mini blender. The differential scanning calorimetric (DSC) studies showed the nucleating effect of CNTs on the crystallization behavior of iPP. Results of X-ray diffraction studies are in conformity with the results of DSC studies. Results of stress–strain measurements reveal that Young's modulus increases, while elongation at break decreases with increase in CNT loading and the ductility of the composites is adversely affected at high loading of CNTs (>1.0 wt%). Functionalization of CNTs causes an improvement in Young's modulus, at all loadings studied, but elongation at break increases only up to 0.25%. At higher loading, the elongation at break drops down. Storage modulus increases with increase in CNT loading and the effect is greater in the case of functionalized CNTs. Tan δ shows a decrease with increase in CNT loading, but the effect is less pronounced at high CNT loading (>0.1 wt%).

A novel highly efficient β‐nucleating agent for isotactic polypropylene

AbstractA 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 (kβ 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

The crystallization of polypropylene in multiwall carbon nanotube‐based composites

AbstractThe crystallization process of isotactic polypropylene (iPP) was studied under both dynamic and isothermal conditions for a series of multiwall carbon nanotube (MWCNT) composites with nanotube concentrations between 0.1 and 1.0% by weight. The nucleation activity of the nanofillers was confirmed for both dynamic and isothermal crystallization, and was shown to be composition dependent. The effect of the nanofiller on the crystallization of iPP was discussed using the temperature coefficients obtained to determine the interfacial free energy and free energy of nucleation. The basal interfacial free energy decreased with respect to that of neat iPP by up to 15% for as little as 0.1% MWCNT, subsequently decreasing linearly with increasing nanotube concentration. This behavior is in line with the crystallization behavior of iPP with conventional nucleating agents. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers

Non-Isothermal Crystallization Behaviors of Isotactic Polypropylene with and without 1,3:2,4-Bis(3,4-Dimethylbenzylidene) Sorbitol as a Nucleating Agent

1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol (DMDBS) is the third-generation sorbitol-based nucleating agent for isotactic polypropylene (iPP). In this study, the non-isothermal crystallization behaviors of iPP with and without DMDBS as a nucleating agent were investigated by means of a differential scanning calorimeter (DSC), and the Caze method was used to analyze the non-isothermal crystallization kinetics. The results show that the addition of DMDBS can increase the crystallization peak temperature (Tp) of iPP greatly under the same cooling rate. When concentration of DMDBS is 0.2 wt.% and the cooling rate is 10°C/min, Tp of iPP nucleated with DMDBS can be increased from 118.7°C of virgin iPP to 130.1°C. Under non-isothermal conditions, the addition of DMDBS changes the spherulite growth pattern of iPP. In addition, nucleation activity of DMDBS was calculated by using the method proposed by Dobreva and Gutzow, and the results showed that DMDBS had high nucleation activity.

Comparison of Nucleation Effects of Organic Phosphorous and Sorbitol Derivative Nucleating Agents in Isotactic Polypropylene

Organic phosphorous and sorbitol derivatives are two types of very effective nucleating agents for isotactic polypropylene (iPP). The effects of two kinds of organic phosphorous nucleating agents, Irgastab NA-11 and ADK NA-21, and two kinds of sorbitol derivatives, Irgaclear DM and Millad 3988, on mechanical properties and crystallization behaviors of iPP are compared in this paper. The organic phosphorous nucleating agents had better effects on mechanical properties of iPP than sorbitol derivatives, whereas the latter had better effects on transparency of iPP than the former. At the same time, the organic phosphorous nucleating agents and sorbitol derivatives had similar effects on the crystallization peak temperature (Tc) of iPP. When the concentration of nucleating agents was 0.2 wt%, compared to those of virgin iPP, the tensile strength and flexural modulus of iPP nucleated with Irgastab NA-11 and ADK NA-21 were increased by 19.35% and 17.67%, and 29.48% and 24.84%, and the haze value was decreased by 43.58% and 44.01%, respectively. On the other hand, the tensile strength and flexural modulus of iPP nucleated with Irgaclear DM and Millad 3988 were increased by 7.03% and 7.46%, and 7.20% and 11.96%, and the haze value was decreased by 51.03% and 52.23%, respectively. When the cooling rate was 10°C /min, the Tc of iPP nucleated with these four nucleating agents was increased from 118.74°C of virgin iPP to about 130°C. Meanwhile, the morphology study showed that addition of both organic phosphorous and sorbitol derivative type nucleating agents could decrease the spherulite size of iPP significantly and that sorbitol derivatives have greater effects.

A highly active novel β-nucleating agent for isotactic polypropylene

A highly active novel β-nucleating agent for isotactic polypropylene (iPP), cadmium bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (BCHE30), was found and its effects on the mechanical properties, the content of β-crystal, and crystallization behavior of iPP were investigated, respectively. The results show that the impact strength and crystallization peak temperature of nucleated iPP are greatly increased, while the spherulite size of nucleated iPP is dramatically decreased than that of pure iPP. The content of β-form of nucleated iPP (kβ value) can reach 87% with 0.1wt% BCHE30. The Caze method was used to study the non-isothermal crystallization kinetics of nucleated iPP and the crystallization active energy was achieved by Kissinger method.

Experimental study of flow-induced crystallization in the blends of isotactic polypropylene and poly(ethylene -co-octene)

The crystallization behavior of the blends of isotactic polypropylene ( iPP) and poly(ethylene -co-octene) (PEOc) under quiescent condition and shear flow were studied by differential scanning calorimetry (DSC) and rheology, respectively. The DSC curves of the iPP phase in the blends showed similar crystallization exothermic peaks to that of pure iPP itself, indicating that the addition of PEOc up to a percentage of 30 in weight almost had no influence on the crystallization behavior of iPP at quiescent condition. The rheological results of isothermal flow-induced crystallization (FIC) of iPP in the blends showed that the crystallization kinetics of iPP was enhanced with the increase of shear rate, similar to that of pure iPP, but the presence of PEOc enhanced the effect of shear on the crystallization kinetics of iPP significantly in the cases of shear rates larger than 0.2 s −1, which was due to that PEOc played an important role to promote the nucleation of iPP. The rheological results also implied that the characteristic relaxation times of blends were longer than that of pure iPP during the FIC process, indicating a different relaxation mechanism which might be related to the occurrence of interface relaxation and chain relaxation of the PEOc phase in the blends.