Exploring the effect of cooling rate on non-isothermal crystallization of copolymer polypropylene by fast scanning calorimetry

Polypropylene is commonly used as a binder for ceramic injection molding,and rapid cooling is often encountered during processing.However,the crystallization behavior of polypropylene shows a strong dependence on cooling rate due to its semi-crystalline characteristics.Therefore,the influence of cooling rate on the quality of final product cannot be ignored.In this study,the fast differential scanning calorimetry(FSC)test was performed to study the influence of cooling rate on the non-isothermal crystallization behavior and non-isothermal crystallization kinetics of a copolymer polypropylene(PP BC03B).The results show that the crystallization temperatures and crystallinity decrease as the cooling rate increases.In addition,two exothermic peaks occur when cooling rate ranges from 30 to 300 K·s^(-1),indicating the formation of another crystal phase.Avrami,Ozawa and Mo equations were used to explore the non-isothermal crystallization kinetics,and it can be concluded that the Mo method is suitable for this study.

Influence ofβ-nucleating Compound Agents on the Mechanical Properties and Crystallization Behavior of Polypropylene Random Copolymer

A novel polypropylene random(PPR)composite materials with optimized properties was developed by addingβ-nucleating compound agents(rare earth complex WBG-2 and aryl amide derivative TMB-5)and ternary compound modifier(TPE/WBG-2/CaCO_(3)).The effects of differentβ-nucleating agents and ternary compound modifier on the mechanical properties and crystallization behavior of PPR were analyzed.The results show that,compared with pure PPR materials,both WBG-2 and TMB-5 could significantly improve the impact strength of PPR.The crystallization temperature of PPR increased with the addition ofβ-nucleating agent.The modified PPR prepared with ternary compound modifier showed the most excellent comprehensive properties.

CRYSTALLIZATION CHARACTERISTICS OF β-PHASE CRYSTALS IN COPOLYMERS OF POLYPROPYLENE WITH LOW ETHYLENE CONTENT

Polypropylene copolymers (CPP) containing β-nucleating agent were investigated by differential scanningcalorimetry (DSC), wide-angle X-ray diffraction (WAXD) and polarizing light microscopy (PLM). The results show thathigh content of β-phase crystals can also be formed for CPPs. Like PP homopolymers, the CPPs also have a most favorabletemperature near 132℃ for β-phase crystal growth. The crystallization rate of CPPs containing β-nucleating agent (β-CPP) ismuch greater than that of PP homopolymer containing β-nucleating agent (β-PP homopolymer). The observation ofspherulite morphology of β-CPP and β-PP homopolymer shows that the spherulites of β-CPP are more imperfect than thoseof β-PP homopolymer.

Critical Role of Ethylene-Propylene Block Copolymer in Impact Polypropylene Copolymer

Ethylene-propylene block copolymer(EbP) is a vital component in impact polypropylene copolymer(IPC), yet its distribution in the multiphase composite material and how it influences the phase structure and the mechanical properties are not well understood. In this work,four IPCs were investigated by atomic force microscopy-infrared(AFM-IR) to assess the phase compositions in situ, based on which in conjunction with the chain microstructure information obtained ex situ the distributions of the copolymer components were derived for each alloy. For the IPCs whose EbP comprises long P and long E segments, the EbP fraction was found to phase separate from the rubber and the PP matrix to form the cores of the disperse particles with the E-P segmented copolymer(EsP). In contrast, in the IPC with EbP composed of long P and short E segments, the EbP fraction formed an outer shell for the rubber particles with the cores comprising the EsP alone, and this IPC, containing a lower E comonomer content than its counterpart, exhibited both better impact resistance and higher flexural modulus. These results clarify how the chain structure of EbP governs the phase morphology in IPC, which in turn impacts the properties of the composite material.

Effect of Long Chain Branching on the Rheological Behavior,Crystallization and Mechanical Properties of Polypropylene Random Copolymer

Long chain branched polypropylene random copolymers （LCB-PPRs） were prepared via reactive extrusion with the addition of dicumyl peroxide （DCP） and various amounts of 1,6-hexanediol diacrylate （HDDA） into PPR. Fourier transform infrared spectrometer （FTIR） was applied to confirm the existence of branching and（ investigate the grafting degree for the modified PPRs. Melt flow index （MFI） and oscillatory shear rheological properties including complex viscosity, storage modulus, loss tangent and the Cole-Cole plots were studied to differentiate the LCB-PPRs from linear PPR. Differential scanning calorimetry （DSC） and polarized light microscopy （PLM） were used to study the melting and crystallization behavior and the spherulite morphology, respectively. Qualitative and quantitative analyses of rheological curves demonstrated the existence of LCB. The effect of the LCB on crystalline morphology, crystallization behavior and molecular mobility, and, thereby, the mechanical properties were studied and analyzed. Due to the entanglements between molecular chains and the nucleating effect of LCB, LCB-PPRs showed higher crystallization temperature and crystallinity, higher crystallization rate, more uniformly dispersed and much smaller crystallite compared with virgin PPR, thus giving rise to significantly improve impact strength. Moreover, the LCB-PPRs exhibited the improved yield strength. The mobility of the molecular chain segments, as demonstrated by dynamic mechanical analysis （DMA）, was improved for the modified PPRs, which also contributed to the improvement of their mechanical properties.

CHARACTERIZATION OF IMPACT POLYPROPYLENE COPOLYMERS BY SOLVENT FRACTIONATION

The compositional heterogeneity of two impact polypropylene copolymers（IPCs） was studied by a combinatory investigation of temperature rising elution fractionation（TREF） and solvent fractionation.The chain structures and composition of fractions obtained from solvent fractionation were examined in detail.The TREF results shows that there are much more E-P segmented copolymer and more uniform distribution of ethylene sequence in IPC-1,which is responsible for its better comprehensive mechanical performance.The fractions from hexane and heptane are ethylene-propylene rubber phase and E-P block copolymers respectively.The result of solvent fractionation method also shows that custom hexane or heptane extractions can not extract the E-P copolymer completely.

INFLUENCE OF SHEARING ON IMPACT POLYPROPYLENE COPOLYMER:PHASE MORPHOLOGY,THERMAL AND RHEOLOGICAL BEHAVIOR

The influences of shearing conducted by a Brabender behavior of a commercial impact polypropylene copolymer （IPC） rheometer on phase morphology, thermal and rheological were studied. The crystallization and melting traces show that short-time annealing at 210℃ is unable to completely erase the influence of shearing on the samples. When the samples which were treated at a rotation speed of 80 r/rnin crystallize at a cooling rate of 10 K/min, their Tcs and corresponding Tms obviously rise with the increase of shearing time. Furthermore, the POM results reveal that the shearing can lead to the formation of shish-kebab and the shish-kebab amount is proportional to shearing time. The rheological measurement results show that the treated samples exhibit different G＇-ω dependences. The ＇second plateau＇ appears when the sample is treated at a rotation speed of 60 r/min or 80 r/min for 10 min, and linear G＇-ω dependence is observed at other rotation speeds. In addition, it is found that the appearance of the ＇second plateau＇ depends on the shearing time when the rotation speed is fixed. According to SEM observations, it is proposed that the ＇second plateau＇ of IPC samples should be ascribed to the aggregation of dispersion particles.

PLASMA MODIFICATION OF POLYPROPYLENE SURFACES AND GRAFTING COPOLYMERIZATION OF STYRENE ONTO POLYPROPYLENE

The surface of polypropylene （iPP） is modified with glow discharge plasma of Ar, so that the modified surfaces of iPP films are obtained. The studies of scanning electron microscopy （SEM） show the surface etching pattern of iPP films. The chemical structures of iPP films are confirmed by X-ray photoelectron spectroscopy （XPS） and Fourier transform infrared （FTIR） spectroscopy. The wetting properties of modified surfaces of iPP films are characterized by contact angle, and the free energy of surfaces is calculated. The free radical of modification surfaces of iPP is measured by chemical method. The surfaces of iPP are achieved with Ar plasma treatment followed by grafting copolymerization with styrene （St） in St. The grafting polymer of St onto iPP is characterized by FTIR. The grafting rate is dependent on plasma exposure time and discharge voltage. The studies show that homopolymerization of St is undergone at the sane time during the graftingcopolymerization of St onto/PP.

Reconstruction of Core-Shell Dispersed Particles in Impact Polypropylene Copolymer during Extrusion

We reported an approach to reconstruct the complex phase morphology of impact polypropylene copolymer （IPC） with core-shell dispersed particles and to optimize its toughness in approximate shear condition. The molten-state annealing results indicate that the phase structure with core-shell dispersed particles is unstable and could be completely destroyed by static annealing, resulting in the degradation of impact strength. By using a co-rotating twin screw extruder, we found that the dispersed particle with core-shell structure could be rebuilt in appropriate condition with the recovery of excellent impact strength due to both the huge interfacial tension during solidification and the great difference in viscosity of components. Results reveal that almost all the extruded IPCs show the impact strength 60%-90% higher than that of annealed IPCs at room temperature. And the twice-extruded IPC shows the highest impact strength, 446% higher than that of IPC annealed for 30 min. As for low temperature tests, the impact strength of extruded IPCs also increases by 33%-58%. According to adjusting the processing conditions including extrusion speed, extrusion frequency and temperature, an optimization of toughness was well established.

Microstructure, morphology, crystallization and rheological behavior of impact polypropylene copolymer

Impact polypropylene copolymer (IPC), named polypropylene catalloy, not only possesses excellent impact property, but also presents good rigidity. Its superior performances result from the complicated composition and microstructure. In the present article, recent progress in the studies on microstructure, morphology, crystallization and rheological behavior of IPC is summarized, and findings of the authors and their collaborators are reported. In general, IPC is divided into three components, i.e., ethylene-propylene random copolymer (EPR), a series of different segment lengths ethylene-propylene copolymer (EbP) and propylene homopolymer. The reasonable macromolecular structures of EbP and a multilayered core-shell model of dispersed phase structure in IPC were proposed, in which the dispersed phase consists of an outer EbP shell, an inner EPR layer and an EbP core. It is found that the annealing at melt-state may lead to an abnormal phase inversion, and the phase inversion disappears when temperature cools down to room temperature. The cause of phase inversion is ascribed to the existence of EbP component, which results in the stronger activity of the dispersed phase. The crystalline structure and morphologic results confirm the formation of β-iPP in IPC. Furthermore, it is found that the ethylene content in IPC and cooling rate of the samples have an important influence on the formation of β-iPP. Based on the crystallization kinetics analyzed by Lauritzen-Hoffman theory, crystallization behavior of different IPC samples is discussed and it is proposed that the dilution effect of ethylene propylene copolymer has a more remarkable influence on surface nucleation than on crystal growth. In addition, annealing at high temperature can result in the changes of chain structure for IPC, and this instability is ascribed to the oxidative degradation and crosslink reaction mainly in iPP component.

COMBINED EFFECT OF MODIFIED ZEOLITE 13X AND β-NUCLEATING AGENT ON IMPROVING β-CRYSTAL CONTENT AND TOUGHENING POLYPROPYLENE RANDOM COPOLYMER

Although addition of β-nucleating agent directly into homo-polypropylene （PPH） is a useful method to improve ,β-crystal content and toughen PPH, polypropylene random copolymer （PPR） makes this method powerless due to its random structure and low crystallinity. In this study, the β-nucleated PPR with high β-crystal content was prepared by a novel high effective β-nucleating system which consists of β-nucleation agent （TMB-5） and modified zeolite 13X （M13X）. It was found that M13X and TMB-5 had a synergistic influence on improving β-crystal content and toughening PPR. The content of β-crystal in PPR/M13X/TMB-5 was significantly larger than the sum of that in PPR/M13X and PPR/TMB-5. Besides, fracture behavior, phase morphology and relaxation of matrix chain segments were also investigated. The results showed that M13X and TMB-5 improved the mobility of amorphous chain segments at low temperature and contributed to much energy dissipation. This work provides a powerful method to modify PPR.

Annealing Induced Microstructure and Mechanical Property Changes of Impact Resistant Polypropylene Copolymer

The effects of annealing on microstructure and mechanical properties of an impact resistant polypropylene copolymer （IPC） were investigated. Different annealing temperatures ranging from 80 ℃ to 160 ℃ were selected. The phase reorganization of IPC during annealing process was studied through morphological characterization technologies, including scanning electron microscopy （SEM） and transmission electron microscopy （TEM）. The crystalline structure changes in the IPC sample, including the iPP matrix and PE component, were investigated using wide angle X-ray diffraction （WAXD） and differential scanning calorimetry （DSC）. Dynamic mechanical analysis （DMA） was used to analyze the relaxation extent of 1PC before and after annealing. The results showed that annealing induced phase reorganization in IPC and the degree of phase reorganization depended on annealing temperature. The annealed IPC samples exhibited largely increased crystallinity compared with the unannealed one. Intensified damping peak with increased molecular chain mobility was achieved for the annealed IPC samples. At an appropriate annealing tem. perature （140 ℃）, largely enhanced impact strength was achieved for the annealed IPC sample. The toughening mechanisms were analyzed based on the phase reorganization and relaxation behavior.

Enhanced Ultraviolet Resistance of Polypropylene Random Copolymer Filled by ZnO-supported Mesoporous Zeolite

To enhance the ultraviolet resistance of ZnO based polymer materials, ZnO-supported mesoporous zeolite（M-ZnO） was prepared and characterized by atomic absorption spectroscopy and scanning electron microscopy. The ultraviolet resistance, crystallization behavior and melting characteristics of ZnO and M-ZnO filled PPR composites were compared by FTIR spectra and differential scanning calorimetry. The ultraviolet resistance of M-ZnO filled PPR composites is higher than that of ZnO filled PPR composites, indicating higher ultraviolet resistance of M-ZnO than that of ZnO. The crystallization temperatures of mesoporous zeolite filled PPR were higher than those of M-ZnO and decreased with increasing UV-irradiation time. But the crystallization temperatures of M-ZnO filled PPR composites were not influenced by UV-irradiation time. The ZnO supported on the surface of zeolite is effective in enhancing the ultraviolet resistance of ZnO based polymer materials.

Enhanced Mechanics in Injection Molded Isotactic Polypropylene/Polypropylene Random Copolymer Blends via Introducing Network-like Crystal Structure

The crystallization behavior, rheological behavior, mechanical properties and microstructures of injection molded isotactic polypropylene （iPP）, polypropylene random copolymer （co-PP） and iPP/co-PP blends were investigated. Differential scanning calorimetry （DSC） and dynamic rheological analysis illustrated that iPP and co-PP were compatible in the blends and co-PP uniformly dispersed in the/PP phase. Polarizing optical microscope （POM） was adopted to observe the crystal size and morphology evolution. The results of mechanical properties and scanning electron microscopy （SEM） indicated that the crystal size of iPP in iPP/co-PP blends （10 wt% co-PP ＋ 90 wt% iPP and 30 wt% co-PP ＋ 70 wt% iPP） radically decreased after the incorporation of co-PP. During crystallization, the molecular chain segments of co-PP could penetrate iPP spherulites and form a network-like crystalline structure. The network-like crystal structure could effectively transmit stress and consume more energy to overcome intermolecular forces to resist stretching. In this way, the strength would improve to a certain degree. The impact fracture mechanism of iPP/co-PP blends is quasi ductile fracture by multiple crazes. Our work discovered that the blends containing 10 wt% and 30 wt% ofco-PP exhibited prominent toughness and reinforcement.