Effect of carbon nanotube‐supported β nucleating agent on the thermal properties,morphology, and mechanical properties of polyamide 6/isotactic polypropylene blends

A new kind of β nucleating agent, multi‐wall carbon nanotube (MWCNT)‐supported calcium pimelate was introduced into polyamide 6 (PA 6)/isotactic polypropylene (iPP; 10/90 by weight) blend and the thermal properties, morphology, and mechanical properties were investigated. The results showed that β‐iPP appeared at low content of MWCNT‐supported calcium pimelate which surmounted the α‐nucleating effect of PA 6 for iPP, and the content of β‐iPP increased with increasing content of MWCNT‐supported calcium pimelate. The impact strength, elongation at break, and flexural modulus were improved with increasing content of MWCNT‐supported calcium pimelate without significantly deteriorating the tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The toughening mechanism of polypropylene/calcium carbonate nanocomposites

The toughening mechanism of polypropylene (PP) filled with calcium carbonate (CaCO₃) nanoparticles is described. In a previous study (Macromolecule 2008;41:9204), we observed that intensive ligament-stretching following debonding of nanoparticles was responsible for the significant improvement in the impact toughness of the annealed PP/CaCO₃ nanocomposites. Furthermore, we hypothesized that strong ligaments, which have high fracture stresses, are needed to stabilize the crack-initiation process and to increase the energy dissipation in the crack-initiation stage. In this study, we used a high-molecular-weight PP to test this hypothesis because strong ligaments could be created from this high-molecular-weight PP. The notched Izod impact strength of the nanocomposites containing the high-molecular-weight PP and 20 wt% CaCO₃ nanoparticles with a monolayer coating of stearic acid was measured to be about 370 J/m, whereas the impact strength of the unfilled PP was 50 J/m. The size of the plastic deformation zone was found to be dependent on the molecular weight of the PP matrix because the strong ligaments of the high-molecular-weight PP enabled the expansion of the plastic deformation zone, leading to a considerable increase in the impact strength. The synergic effect of the high-molecular-weight PP and the monolayer-coated nanoparticles produced nanocomposites with high impact strength, which is much greater than the inherent impact strength of the unfilled polymer. In addition, the effect of the high-molecular-weight PP on the dispersion of the nanoparticles was investigated.     

Mechanical properties and morphologies of PP/mPE/filler composites

Because of the poor impact behavior of polypropylene (PP) at low temperatures, the blending of PP with metallocene‐polymerized polyethylene (mPE) elastomers was investigated in this study. However, a reduced modulus of the overall blend was inevitable because of the addition to elastomers. To obtain a balance of the properties, we introduced rigid inorganic fillers to PP/mPE blends. The performance of the composites was characterized with tensile and Charpy notched impact tests, and the fracture morphology was examined with scanning electron microscopy. The results showed that the effects of fillers in a brittle matrix and in a ductile matrix were quantitatively different. For PP/mPE/filler ternary composites, the dependence of Young's modulus and yield strength on CaCO₃ content was not significant compared with that of PP/filler binary composites, whereas the elongation at break and tensile toughness at room temperature for PP/mPE/filler systems were more improved. The impact strength of the PP/mPE blends filled with untreated glass beads and CaCO₃ at a low temperature was lowered because of the weak interfacial bond. However, the values of the impact strength of the PP/mPE/filler composites at a low temperature remained at a high level compared with that of pure PP. In particular, a PP/mPE blend filled with surface‐treated kaolin had a higher low‐temperature impact toughness than the unfilled blend. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3029–3035, 2002; DOI 10.1002/app.2333     

Influence of different β‐nucleating agent on crystallization behavior,morphology, and melting characteristic of multiwalled carbon nanotube‐filled isotactic polypropylene nanocomposites

To obtain isotactic polypropylene (iPP) nanocomposites with high β‐crystal content, TMB5, calcium pimelate and calcium pimelate supported on the surface of nano‐CaCO₃ were used as β‐nucleating agent and MWCNT filled β‐nucleated iPP nanocomposites were prepared. The effect of different β‐nucleating agent and MWCNT on the crystallization behavior and morphology, melting characteristic and β‐crystal content of β‐nucleated iPP nanocomposites were investigated by DSC, XRD and POM. The results indicated that addition of MWCNT increased the crystallization temperature of iPP and MWCNT filled iPP nanocomposites mainly formed α‐crystal. The β‐nucleating agent can induce the formation of β‐crystal in MWCNT filled iPP nanocomposites. The β‐nucleating ability and β‐crystal content in MWCNT filled β‐nucleated iPP nanocomposites decreased with increasing MWCNT content and increased with increasing β‐nucleating agent content due to the nucleation competition between MWCNT and β‐nucleating agents. It is found that the calcium pimelate supported on the surface of inorganic particles as β‐nucleating agent has stronger heterogeneous β‐nucleation than calcium pimelate and TMB5. The MWCNT filled iPP nanocomposites with high β‐crystal content can be obtained by supported β‐nucleating agent. POLYM. COMPOS., 36:635–643, 2015. © 2014 Society of Plastics Engineers     

Effect of single‐mineral filler and hybrid‐mineral filler additives on the properties of polypropylene composites

The present study was carried out to determine the filler characteristics and to investigate the effects of three types of mineral fillers (CaCO₃, silica, and mica) and filler loadings (10–40 wt%) on the properties of polypropylene (PP) composites. The characteristics of the particulate fillers, such as mean particle size, particle size distribution, aspect ratio, shape, and degree of crystallinity were identified. In terms of mechanical properties, for all of the filled PP composites, Young's modulus increased, whereas tensile strength and strain at break decreased as the filler loading increased. However, 10 wt% of mica in a PP composite showed a tensile strength comparable with that of unfilled PP. Greater tensile strength of mica/PP composites compared to that of the other composites was observed because of lower percentages of voids and a higher aspect ratio of the filler. Mica/PP also exhibited a lower coefficient of thermal expansion (CTE) compared to that of the other composites. This difference was due to a lower degree of crystallinity of the filler and the CTE value of the mica filler. Scanning electron microscopy was used to examine the structure of fracture surfaces, and there was a gradual change in tensile fracture behavior from ductile to brittle as the filler loading increased. The nucleating ability of the fillers was studied with differential scanning calorimetry, and a drop in crystallinity of the composites was observed with the addition of mineral filler. Studies on the hybridization effect of different (silica and mica) filler ratios on the properties of PP hybrid composites showed that the addition of mica to silica‐PP composites enhanced their tensile strength and modulus. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

β成核剂改性聚丙烯树脂的微观结构、结晶行为及力学性能研究

采用熔融共混法制备了取代芳酰胺类β晶成核剂TMB-4改性聚丙烯(PP),并利用XRD、DSC、POM及SEM对改性PP的力学性能、结晶行为及微观结构进行了研究。结果表明:添加TMB-4成核剂后,PP树脂的α晶型被诱导转变为β晶型,结晶峰温度提高了16.2℃,晶粒细化;改性PP的冲击强度提高了152%,从脆性断裂转变为韧性断裂。     

The morphology of fracture surfaces and mechanical properties of composites of polypropylene with glass fibers having different interface adhesion

For composites polypropylene–short glass fibers having different interface adhesion, correlation has been proved to exist between the morphology of fracture surfaces, the temperature dependence of impact strength, and the deformational and fracture behavior in tensile loading. The results are interpreted in terms of the mechanism of distortion plasticity for unfilled PP and for filled PP having weak interface adhesion, and on the basis of dilatation plasticity for filled polypropylene with a higher interface adhesion. The transition from the distortion to the dilatation mechanism can be seen in fracture surfaces after tensile destruction in composites possessing a higher interface adhesion.     

Effect of thermal conductivity and heat transfer on crystallization,structure, and morphology of polypropylene containing different fillers

The crystallization behavior, structure, and morphology developed was investigated for polypropylene containing different fillers such as silica, calcium carbonate, talc, mica, graphite, etc. by using compression‐molded samples prepared at several cooling rates. It was observed that the crystallinity obtained for any given composition depended on the thermal conductivity of the filler and the PP composite containing it as well as the cooling rate to which it was subjected. These composites exhibited skin‐core type of morphology and the skin layer thickness was found to depend not only on the cooling rate but also on the type of filler, its thermal conductivity, etc. These various experimental findings were discussed in light of the phenomenological model described in our earlier work, which correlates thermal conductivity and degree of crystallinity for various compositions of PP containing additives. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 615–623, 2004     

Study on mechanical properties of perlite‐filled gamma‐irradiated polypropylene

This study covers the preparation and characterization of perlite‐filled polypropylene (PP). The compositions of 15, 30, and 50 % by weight perlite–PP composites were prepared by melt‐mixing. The PP used in this study was either applied in the virgin form or γ‐irradiated in air at the doses of 10, 25, 50, and 100 kGy to determine the effect of oxidative degradation in composite properties. Furthermore, the active sites containing oxygen produced by γ‐irradiation in PP may provide a possible enhancement by the interfacial interaction between perlite and PP. An initial sharp drop in torque readings during the melt‐mixing of perlite–PP composite preparation indicated an extensive chain scission and degradation by γ‐irradiation. The thermal properties of the composites were characterized by DSC. The ultimate tensile strength and elongation and also impact strength decreased in all composites with γ‐irradiation. Yet, these changes appeared not to be faster than was the change in unfilled PP upon irradiation. Scanning electron microscopy revealed an interfacial adhesion between perlite and irradiated PP while virgin PP did not show any evidence of adhesion. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2670–2678, 2001     

Effect of the composition ratio of pimelic acid/calcium stearate bicomponent nucleator and crystallization temperature on the production of β crystal form in isotactic polypropylene

The influence of the composition ratio of pimelic acid/calcium stearate bicomponent nucleator on the β crystal form content of isotactic polypropylene (iPP) had been studied at the crystallization temperature of 120°C and duration of 30 min. It was found that the β crystal form content increased continuously with increasing amount of calcium stearate at the constant amount of 0.15% pimelic acid. High β crystal form content polypropylene could be produced when the amount of calcium stearate was greater than 0.30% (the mass composition ratio of pimelic acid/calcium stearate was less than 1/2, the mole ratio was less than 1.89/1). It was shown that pimelic acid and calcium stearate could react to produce a high effective β nucleator (calcium pimelate) “in situ” during the melt‐mixing of iPP and the bicomponent nucleator. The influence of crystallization temperatures (100–140°C) on the β crystal form content of iPP had also been studied at the constant composition ratio of 0.15% pimelic acid/0.5% calcium stearate (the calcium pimelate produced in situ was 0.16%, which was calculated from stoichiometry). It was found that the β crystal form content increased continuously with increasing crystallization temperature and it maximized at 130°C. β Crystal form content decreased sharply at the crystallization temperature of 140°C. It was shown that β → α modification transformed between 130 and 140°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

多层塑料复合板废料改性聚丙烯的研究

将用偶联剂和增容剂改性的多层塑料复合板固体废料粉末（GFRP）加入到聚丙烯（PP）基体中,制备复合材料。采用差示扫描量热仪（DSC）、扫描电子显微镜（SEM）研究了复合材料的微观结构和热性能,并测试了材料的力学性能。研究结果表明,当1 %硅烷偶联剂KH570处理的GFRP的含量为20份（质量份,下同）,增容剂马来酸酐接枝聚丙烯（PP-g-MAH）含量为2份时,复合材料的冲击强度显著提高,弯曲强度与弯曲模量也有一定程度的提高,拉伸强度下降不大。SEM观察结果表明,PP/改性GFRP/PP-g-MAH复合材料在断裂过程中发生塑性变形。DSC分析表明,GFRP的加入没有改变PP的晶型。     

Effect of crystallization and interface formation mechanism on mechanical properties of film‐insert injection‐molded poly(propylene) (PP) film/PP substrate

A previous study has shown that the adhesion between the film and substrate of film‐insert injection‐molded poly(propylene) (PP) film/PP substrate was evident with the increases in barrel temperature and injection holding pressure. In this second part of the research work, the crystallinity at the interfacial region (i.e., region between the film and the injected substrate) was extensively studied using FTIR imaging, polarized light microscopy, and DSC in an attempt to determine the level of influence that crystallinity has on the interface and bulk mechanical properties. Consequently, a more thorough and clearer picture of the influence of the inserted film on the interfacial crystallinity and subsequently the substrate mechanical properties, such as peel strength and impact strength, has been revealed. The initial proposition that crystallinity could enhance film–substrate interfacial bonding has been confirmed, judging from the higher peel strength with increasing crystallinity at the interfacial region. Nevertheless, the change in crystallinity was not only confined to the interfacial region. With the film acting as heat‐transfer inhibitor between the injected resin and the mold wall, the total crystal structure of the substrate was substantially altered, which subsequently affected the bulk mechanical properties. The lower impact strength of film‐insert injection‐molded samples compared to that of samples without film inserts provided evidence of how the film could impart inferior properties to the substrate. The difference in cooling rate between the substrate and film might also cause other defects such as warpage and/or residual stress build‐up within the product. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 294–301, 2005     

各种羧酸二盐对嵌段共聚聚丙烯的β成核研究

合成了6种己二酸盐、庚二酸盐作为嵌段共聚聚丙烯(PP-B)的成核剂,研究其对PP-B的β成核影响。结果表明,庚二酸钙、庚二酸钡、庚二酸镁均具有明显β成核PP-B的效果,且成核效应由大到小次序为:庚二酸钙、庚二酸钡、庚二酸镁;庚二酸钠是低活性的β成核剂;己二酸盐类中己二酸钠和己二酸钡对PP-B是高效的β-成核剂,二者的成核效果相当。通过差示扫描量热分析(DSC)和力学性能测试表明,当己二酸钠的用量为0.2%(质量分数)时,经β成核改性产物的缺口冲击性能最佳,且KDSC(β晶型相对含量)最大。     

Morphology and mechanical properties of PP/POE/nano‐CaCO3 composites

The mechanical properties including tensile, flexural, and impact of the nanometer on calcium carbonate (nano‐CaCO₃) filled polypropylene (PP)/poly (ethylene‐co‐octene) (POE) composites were measured at room temperature to identify the effects of the POE content on the mechanical properties. It was found that the Young's modulus, tensile strength, and tensile elongation at break decreased nonlinearly while the tensile fracture strength varied slightly with increasing the POE weight fraction; the V‐notched and unnotched Izod impact fracture strength increased nonlinearly with an increase of the POE weight fraction; the flexural modulus and strength decreased roughly linearly with increasing the POE weight fraction. Furthermore, the impact fracture surface of the specimens was observed by means of a scanning electronic microscope to discuss the toughening mechanisms. POLYM. COMPOS., 37:539–546, 2016. © 2014 Society of Plastics Engineers     

Mechanical properties and morphologies of polypropylene with different sizes of calcium carbonate particles

Three polypropylene (PP) matrixes with different intrinsic toughness were used to study the morphologies and mechanical properties of PP filled with four sizes of calcium carbonate particles. PP1 was a homopolymer, PP2 was a propylene‐ethylene copolymer, and PP3 was a mixture of PP1 and PP2 (PP1:PP2 = 1:1, weight ratio). Calcium carbonate (CC25, CC4, CC1.8, and CC0.07) with an average particle size of 25, 4, 1.8, and 0.07 μm, respectively, was used. It was clear that the PP matrix and filler size had key effects on improvement of mechanical properties of PP matrix. For all three PP matrixes, the yield strength, the flexural strength and modulus of the composites filled with CC25, CC4, and CC1.8 could be regarded as the same. But the yield strength, the flexural strength and modulus of composites filled with CC0.07 were obviously lower than those of composites filled with other sizes of particles. Among four sizes of calcium carbonate particles, CC0.07 had the best toughening effect to improve the impact strength of PP matrix, and the toughening effect of CC0.07 was influenced by PP matrix. For all PP matrixes, only in the case of moderate matrix toughness (PP3 matrix), the composite could receive the highest extent of toughness increase (4.3 times that of matrix). With regard to all PP composites, the best combination of properties was PP2 nanocomposite filled with 20 wt% CC0.07. POLYM. COMPOS., 27:443–450, 2006. © 2006 Society of Plastics Engineers     

Single screw extrusion compounding of particulate filled thermoplastics: State of dispersion and its influence on impact properties

The compounding of calcium carbonate filled polypropylene (PP) is discussed with reference to a single-screw extruder and variants of mixing sections. The mixing section on the screw is exchangeable, and two dispersive mixing elements, namely the Zorro and the Maddock elements, were used. The calcium carbonate was surface treated with a liquid titanate coupling agent (LICA12). The impact strength was measured by a notched Izod impact tester with specimens having a U-shaped sharp notch. The fracture toughness for the PP homopolymer and the filled composites was determined using fracture mechanics principles. The results were correlated with the state of dispersion of the calcium carbonate filler. The effects of filler concentration and surface treatment were examined as well. Correlation between state of dispersion and impact properties for calcium carbonate filled PP was obtained. We also investigated the effect of various mixing elements on the state of dispersion. The experimental results indicate that good dispersion would improve the impact properties of the polymer matrix, but only at moderate filler loading. © 1996 John Wiley & Sons, Inc.     

An investigation on the mechanical and dynamic rheological properties of single and hybrid filler/polypropylene composites based on talc and calcium carbonate

Some results of experiments on the mechanical and rheological properties of mineral filled polypropylene were presented. Single filler and hybrid filler composites of talc and calcium carbonate (CaCO₃) were prepared in a co‐rotating twin‐screw extruder. The effect of filler type, filler content, and coupling agent on the mechanical and rheological properties of the polypropylene were studied. The coupling agent was maleic anhydride‐grafted polypropylene (PP‐g‐MA). It was found that the mechanical properties are affected by filler type, filler concentration, and the interaction between filler and matrix. The tensile strength of the composite is more affected by the talc while the impact strength is influenced mostly by CaCO₃ content. The elongation at break of PP/CaCO₃ composites was higher than that of PP/talc composites. The incorporation of coupling agent into PP/mineral filler composites increased the mechanical properties. Rheological properties indicated that the complex viscosity and storage modulus of talc filled samples were higher than those of calcium carbonate filled samples while the tan δ was lower. The rheological properties of hybrid‐filler filled sample were more affected by the talc than calcium carbonate. The PP‐g‐MA increased the complex viscosity and storage modulus of both single and hybrid composites. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Competing effect between filled glass bead and induced β crystal on the tensile properties of polypropylene/glass bead blends

The blends of the polypropylene (PP‐1) with various glass bead contents were prepared via melt blending. Differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) results indicated that the β crystal existed in PP‐1 and increased with increasing glass bead content up to 6 wt %. It was generally known that the stiffness of a polymer increased with introducing rigid particles, and the stiffness of the β crystal was less than that of the α crystal. This competing effect thus leads to the tensile modulus of PP‐1/glass bead blend decreasing with increasing glass bead content up to 6 wt %; thereafter, it increased with increasing glass bead content. For the purpose of comparison, the polypropylene (PP‐2) without the β crystal was employed to blend with glass bead. The tensile tests showed that the modulus of the PP‐2/glass bead blend increased continuously with increasing glass bead content. This result further supported that the tensile modulus behavior of PP‐1/glass bead blends resulted from the competing between the filled glass bead and the induced β crystal. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1729–1733, 2005     

轻质碳酸镁对PP结晶行为的影响

用熔融共混法制备了聚丙烯(PP)/轻质碳酸镁复合材料。利用差示扫描量热法(DSC)、X射线衍射(XRD)、冲击试验机和原子力显微镜(AFM)等对复合材料进行了测试与表征。结果表明:少量轻质碳酸镁能够诱导PP中β晶的产生,从而增强其韧性;随着轻质碳酸镁用量的增加,PP的结晶度降低,从而使其冲击强度降低;经硬脂酸改性的轻质碳酸镁较未改性的可进一步提高复合材料的结晶度和结晶速率,其在复合体系中的分散性较未改性的也有很大提高。     

Mechanical properties and morphology of polypropylene‐calcium carbonate nanocomposites prepared by dynamic packing injection molding

In this article, dynamic packing injection molding (DPIM) technology was used to prepare injection samples of Polypropylene‐Calcium Carbonate (PP/CaCO₃) nanocomposites. Through DPIM, the mechanical properties of PP/nano‐CaCO₃ samples were improved significantly. Compared with conventional injection molding (CIM), the enhancement of the tensile strength and impact strength of the samples molded by DPIM was 39 and 144%, respectively. In addition, the tensile strength and impact strength of the PP/nano‐CaCO₃ composites molded by DPIM increase by 21 and 514%, respectively compared with those of pure PP through CIM. According to the SEM, WAXD, DSC measurement, it could be found that a much better dispersion of nano‐CaCO₃ in samples was achieved by DPIM. Moreover, γcrystal is found in the shear layer of the DPIM samples. The crystallinity of PP matrix in DPIM sample increases by 22.76% compared with that of conventional sample. The improvement of mechanical properties of PP/nano‐CaCO₃ composites prepared by DPIM attributes to the even distribution of nano‐CaCO₃ particles and the morphology change of PP matrix under the influence of dynamic shear stress. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012