Mechanical properties and fracture morphology of Al(OH)3/polypropylene composites modified by PP grafting with acrylic acid

Al(OH)₃/polypropylene (PP) composites modified by polypropylene grafted with acrylic acid (FPP) were prepared by melt extrusion. Effect of PP grafting with acrylic acid on mechanical properties and fracture morphology of Al(OH)₃/polypropylene composites were investigated. Although incorporation of Al(OH)₃ reduced the mechanical properties of PP, addition of FPP increased the mechanical properties of Al(OH)₃/PP composites. It is suggested that addition of FPP improve the dispersion of Al(OH)₃ and the interfacial interaction between filler and matrix. Mechanical properties of Al(OH)₃/FPP/PP composites depend on the grafting rate and the content of FPP. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2617–2623, 2001     

Synergistic flame retardant effect of BiFeO3 in intumescent flame‐retardant polypropylene composites

The BiFeO₃ was used to intumescent flame retardant (IFR) polypropylene (PP) composites as a synergist. The limiting oxygen index (LOI) and UL‐94 tests indicated that there is an optimum synergistic concentration of BiFeO₃ in the PP/IFR composites. Thermogravimetric analysis (TG) results of flame retardant PP showed that the moderate of BiFeO₃ can reduce the decomposition rate of sample at high temperatures. TG of APP/PER/BiFeO₃ showed that BiFeO₃ main affects the third mass loss stage of APP/PER. So the morphology and composition of the char residue of APP/PER/BiFeO₃ composites were characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and laser Raman spectroscopy (LRS). An appropriate amount of BiFeO₃ can react with APP/PER forming Bi O P and Fe O P bond, and so more P elements was involved in a crosslinking reaction to form more stable char residue, which can effectively increase the flame retardant properties of PP. POLYM. COMPOS., 38:2771–2778, 2017. © 2015 Society of Plastics Engineers     

聚磷酸铵粉体改性及对聚丙烯力学性能的影响

采用氯化铝和氨水溶液为原料,在液相体系中生成氢氧化铝,使其包覆在阻燃剂聚磷酸铵(APP)颗粒的表面,制备了表面包覆氢氧化铝的聚磷酸铵复合颗粒(N-APP)。通过调整合适的反应参数对工艺条件进行优化设计,确定了最佳反应条件。同时对最终产品的表面形貌、抗水性以及热稳定性等进行了表征,扫描电镜(SEM)结果表明,经包覆改性后,粉体的表面粗糙度明显增加,并且,改性后产品N-APP(6#)的接触角由未改性时的8.9°提高到118.9°,具有较好的疏水性能;热失重分析结果表明,包覆改性在一定程度上提高了产品的热稳定性。将经包覆改性后的产品在聚丙烯(PP)填充应用,与添加未改性APP的PP复合材料相比,添加包覆改性产品的PP复合材料的力学性能明显提升。     

氧等离子体对聚丙烯粉体的表面处理研究

用氧等离子体对聚丙烯（PP）粉体进行表面处理,采用水接触角（WCA）、红外光谱（IR）对处理前后PP粉体的水接触角、表面组分的变化进行了分析。实验结果表明,随着等离子体处理时间延长,水接触角减小。IR分析表明,在氧等离子体处理中,PP粉体表面有含氧极性官能团生成,导致粉体表面水接触角减小。     

Effects of nano calcium carbonate modified by a lanthanum compound on the properties of polypropylene

The surface modification of nano calcium carbonate (nCaCO₃) particles was carried out with a soluble compound of lanthanum via a coating process of chemical deposition, and nCaCO₃ particles covered with a compound of lanthanum (nCaCO₃? La) were prepared. The polypropylene (PP)/nCaCO₃ and PP/nCaCO₃? La composites were prepared with a two‐roll mill. The measurements of the mechanical properties showed that the impact strength of the composites increased at first and then decreased with the addition of fillers, and the tensile strength was reduced at the same time. The impact strength of PP/nCaCO₃? La was higher than that of PP/nCaCO₃, and the impact strength of PP/nCaCO₃? 5La was three times that of virgin PP. Transmission electron microscopy and scanning electron microscopy showed that nCaCO₃? La dispersed well in the PP matrix, the size distribution of the particles was uniform, and nCaCO₃? La adhered to the PP matrix very closely. The crystallization properties of virgin PP and its composites were studied with differential scanning calorimetry and wide‐angle X‐ray diffraction. The results showed that the β‐PP phase easily formed with the addition of the lanthanum compound. In comparison with virgin PP, the addition of nCaCO₃? La led to a higher crystallization temperature. The size of the crystallites increased with the addition of nCaCO₃? La, and the nucleation of PP crystalline was also improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1154–1160, 2005     

Structure and properties of polypropylene alloy in situ blends

A series of polypropylene (PP) alloys containing different ethylene contents have been prepared by the in situ sequential polymerization technique, using Ziegler–Natta catalyst (MgCl₂/TiCl₄/BMF; BMF is 9,9‐bis(methoxymethyl)fluorine, as an internal donor) without any external donor. The structure and properties of PP alloys obtained have been investigated by nuclear magnetic resonance, Fourier transform infrared spectroscopy, dynamic mechanical analysis, differential scanning calorimetry, and scanning electron microscopy (SEM). The results have suggested that PP alloys are the complex mixtures containing PP, the copolymer with long sequence ethylene chain, ethylene‐propylene rubber (EPR), and block copolymer etc. In the alloys, PP, EPR, and the copolymer with long sequence ethylene chain are partially compatible. The investigation of the mechanical properties indicates that notched Izod impact strength of PP alloy greatly increases at 16°C/?20°C in comparison with that of pure PP. The noticeable plastic deformation is observed in SEM photograph. The increase in the toughness, the mechanical strength of PP alloy decreases to a certain extent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4804–4810, 2006     

Flammability and mechanical properties of Al(OH)3 and BaSO4 filled polypropylene

The flammability and mechanical properties of Al(OH)₃/BaSO₄/polypropylene (PP) composites were investigated. The flow, morphological, and thermal properties were also analyzed by melt flow index (MFI), Scanning electron microscopy (SEM), and Differential scanning calorimeter (DSC) studies, respectively. Total filler amount was fixed at 30 wt % to optimize physical characteristics of the composites. In addition to the flame retardant filler Al(OH)₃, BaSO₄ was used to balance the reduction in impact strength at high filler loadings. Substantial improvement in mechanical properties was achieved for 20 wt % Al(OH)₃ (i.e., 10 wt % BaSO₄) composition while maximum flammability resistance was obtained for 30 wt % Al(OH)₃ composite. SEM studies showed that the presence of aggregated Al(OH)₃ particles led to low interfacial adhesion between them and PP matrix ending up with decreased mechanical strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reinforcement of Si3N4 nanoparticles in polypropylene single fibers through melt extrusion process and their properties

We have successfully aligned/dispersed the rod and spherical‐shaped Si₃N₄ nanoparticles in the polypropylene (PP) fibers through melt extrusion process to fabricate polymer nanocomposite (PNC) single fibers. The alignment/dispersion of Si₃N₄ nanoparticles in PP/Si₃N₄ PNC fibers has been carried out in a systematic manner to produce uniform single fibers. The PNC fibers were first uniformly stretched and stabilized using a two‐set Godet machine. The as‐extruded single PNC fibers were tested for their thermal and tensile properties. The test results of PNC fibers were compared to neat PP polymer single fibers fabricated using the same procedure as PNC fibers. These results show that the PNC fibers are much (307%) higher in tensile strength and modulus (>1000%) when compared with the neat PP polymer single fibers. The field emission scanning electron microscope results clearly show the alignment of rod‐Si₃N₄ nanoparticles in polymer matrix. The differential scanning calorimetry results show ～ 12% increase in crystallinity for rod‐Si₃N₄ PNCs when compared with the neat PP single fibers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical properties and morphologies of polypropylene composites synergistically filled by styrene‐butadiene rubber and silica nanoparticles

The mechanical properties and morphologies of PP/SBR/SiO₂ nanocomposites have been studied using mechanical testing, wide‐angle X‐ray diffraction (WAXD), polarizing optical microscopy (POM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The mechanical properties of neat polypropylene can be considerably improved by synergistically filling with SiO₂ and SBR nanoparticles, especially for the notched Izod impact strength. The results from the WAXD, POM, SEM, DSC, and TGA measurements reveal that: (i) the β‐phase crystal structure of PP is formed when SiO₂ and SBR nanoparticles are synergistically filled with polypropylene and its formation plays a role for the enhancement of the impact strength for PP/SBR/SiO₂ nanocomposites; (ii) the dispersion of SiO₂ and SBR nanoparticles in PP/SBR/SiO₂ composites is homogeneous, indicating that synergistic incorporating method decreases the aggregation of nanoparticles and thus increases the sites for dissipation of shock for impact energy in PP/SBR/SiO₂ nanocomposites; (iii) the thermal analysis shows high thermal stability for the PP/SBR/SiO₂ nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Statically non-wetting electrospun perfluorocyclobutyl (PFCB) aryl ether polymer doped with room temperature ionic liquid (RTIL)

A statically non-wetting, electrospun surface of non volatile room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium hexafluorophosphate, (BMIM-PF₆), hosted in a solution-processable, semi-fluorinated perfluorocyclobutyl (BP-PFCB) aryl ether polymer was successfully prepared by electrospinning and compared with a surface prepared by spin casting. The surface properties of undoped and BMIM-PF₆ doped systems were analyzed by water contact angle (WCA) and atomic force microscopy (AFM). BMIM-PF₆ doped BP-PFCB surfaces prepared by spin casting showed a WCA of 90° while non-woven electrospun surfaces with the same BMIM-PF₆ concentration showed high degree of hydrophobicity with a WCA greater than 150°. Morphologies of the electrospun surfaces were characterized by scanning electron microscopy (SEM). The surface composition was analyzed by energy-dispersive X-ray spectroscopy (EDXS) and attenuated total reflectance infrared spectroscopy (ATR-IR). Thermal analysis of the electrospun, non-woven surfaces of the doped and the undoped system of BP-PFCB were done by TGA.     

Tuning of polypropylene wettability by plasma and polyhedral oligomeric silsesquioxane modifications

In this work, we have exposed polypropylene (PP) to plasma treatment and then reactively coated with polyhedral oligomeric silsesquioxane-isothiocyanate (POSS-NCS) in order to modify both of its surface characteristics: chemical composition and roughness. The results of scanning electron microscopy (SEM), atomic force microscopy (AFM), and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) showed a strong relation between plasma exposure time and PP roughness, as expected. On the other hand, the POSS-coating promoted the reduction of surface roughness, but induced a substantial increase in the water contact angle (WCA), probably due to the modification of the surface chemical nature. Besides, the surface tuning method discussed here is a fast, industrial-suitable procedure which can be applied to different polymers.     

Physical and mechanical properties of Al(OH)3/polypropylene composites modified by in situ‐functionalized polypropylene

Al(OH)₃/polypropylene (PP) composites modified by in situ‐functionalized polypropylene (FPP) were prepared by a one‐step melt‐extrusion process. The effect of in situ FPP on the crystallization and melting behavior, melt‐flow index, limiting oxygen index, thermal degradation, mechanical properties, and fracture morphology of Al(OH)₃/PP composites was studied. Formation of in situ FPP resulted in a decreased crystallization temperature and melting point of PP in the composites, an increased melt‐flow index, and improved tensile and flexural strengths of Al(OH)₃/PP composites, whereas the thermal degradation behavior and limiting oxygen index was not been influenced. The impact strength of the Al(OH)₃/PP composites modified by in situ FPP depended upon the content of the initiator, dicumyl peroxide, and the monomer, acrylic acid. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2850–2857, 2002; DOI 10.1002/app.10269     

Polypropylene Graft Poly(methyl methacrylate) Graft Poly(N-vinylimidazole) as a Smart Material for pH-Controlled Drug Delivery

Surface modification of polypropylene (PP) films was achieved using gamma-irradiation-induced grafting to provide an adequate surface capable of carrying glycopeptide antibiotics. The copolymer was obtained following a versatile two-step route; pristine PP was exposed to gamma rays and grafted with methyl methacrylate (MMA), and afterward, the film was grafted with N-vinylimidazole (NVI) by simultaneous irradiation. Characterization included Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and physicochemical analysis of swelling and contact angle. The new material (PP-g-MMA)-g-NVI was loaded with vancomycin to quantify the release by UV-vis spectrophotometry at different pH. The surface of (PP-g-MMA)-g-NVI exhibited pH-responsiveness and moderate hydrophilicity, which are suitable properties for controlled drug release.     

Polypropylene/polypropylene‐grafted acrylic acid copolymer/ethylene–Acrylic acid copolymer ternary blends for hydrophilic polypropylene

Ternary blends of polypropylene (PP), a polypropylene‐grafted acrylic acid copolymer (PP‐g‐AA), and an ethylene–acrylic acid copolymer (EAA) were prepared by melt blending. The surfaces of films with different contents of these three components were characterized with contact‐angle measurements. Scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis were used to characterize the microstructure, melting and crystalline behavior, and thermal stability of the blends. The contact angles of the PP/PP‐g‐AA blends decreased monotonically with increasing PP‐g‐AA content. With the incorporation of EAA, the contact angles of the PP/PP‐g‐AA/EAA ternary blends decreased with increasing EAA content. When the concentration of EAA was higher than 15 wt %, the contact angles of the ternary blends began to increase. Scanning electron microscopy observations confirmed that PP‐g‐AA acted as a compatibilizer and improved the compatibility between PP and EAA in the ternary blends. Differential scanning calorimetry analysis suggested that acrylic acid moieties could act as nucleating agents for PP in the polymer blends. Thermogravimetric analysis and differential thermogravimetry confirmed the optimal blend ratio for the PP/PP‐g‐AA/EAA ternary blends was 70/15/15. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 436–442, 2006     

Plasma treatment of polymethyl methacrylate to improve surface hydrophilicity and antifouling performance

Surface modification of polymethyl methacrylate (PMMA) by O₂/CF₄ plasma is investigated to improve hydrophilicity and antifouling performance of PMMA. The PMMA surface before and after treatment is characterized by atomic force microscopy, contact angle measurement, and X-ray photoelectron spectroscopy. Antifouling properties are evaluated by protein adsorption and bacterial adhesion experiments using Staphylococcus aureus in vitro. Higher O₂ content in the mixture gas promotes hydrophilicity of the plasma-treated PMMA, while a hydrophobic surface forms at higher CF₄ content. Modifying PMMA improves antifouling performance regardless of the O₂/CF₄ volume ratio, and this improvement increases with rising CF₄ content in O₂/CF₄ plasma working gas. Functional groups C O and C F are detected in O₂/CF₄ plasma-treated PMMA surface and the ratio of C O to C F can be controlled by the O₂/CF₄ volume ratio in the plasma working gas.     

Glass fiber reinforced and β‐nucleating agents regulated polypropylene: A complementary approach and a case study

A two‐step process for preparing glass fibers (GFs) reinforced β‐nucleated PP composites was designed and developed. The complementary approach combined GFs reinforcement and β‐nucleating agents regulation using N,N′‐dicyclohexyl‐2,6‐napthalene‐dicarboxamide (TMB‐5) in the presence of maleic anhydride grafted polypropylene (PP‐g‐MA) through extrusion blending. The influence of TMB‐5 and GFs on the mechanical properties and crystallization behavior of PP was studied by mechanical test, wide‐angle X‐ray diffraction, differential scanning calorimetry, and scanning electron microscopy. A distinct complementary effect of GFs and β‐nucleating agent TMB‐5 on mechanical properties and crystallization behavior of PP was observed. Results showed that addition of 20 wt % GFs and 0.1 wt % TMB‐5 into PP matrix with the two‐step process could lead to significant increase to its mechanical properties: specifically 64.8% improvement in tensile strength, 107.1% enhancement in flexural modulus, and 167.7% increasement in notched impact strength compared to that of neat PP. Furthermore, with the combination of TMB‐5 and GFs, not only led to promoted interfacial adhesion, but also significantly improved overall comprehensive mechanical properties. The complementary process provided an alternative approach for the development of PP with balanced toughnesss and stiffness. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45768.     

Structure and isothermal crystallization behavior of polypropylene prepared at high polymerization temperature

The structure, morphology, and isothermal crystallization behaviors of polypropylene (PP) prepared with heterogeneous Ziegler‐Natta catalyst at high temperature (100°C) were investigated with differential scanning calorimetry, wide‐angle X‐ray diffraction, temperature‐rising elution fractionation, gel permeation chromatography, and ¹³C NMR. The results reveal that the crystalline structure changes with variation of the composition of the PP. The isotactic PP (iPP)1 prepared with Et₃Al and “TMA‐depleted” methylaluminoxane crystallizes from the melt in the mixtures of the α and β forms, whereas each fraction obtained from pure PP1 does not show β‐PP crystal at the same crystallization condition. In addition, the γ‐PP crystal is appeared for the fractions of low mmmm%‐[mmmm] (mmmm pentad content) values and molecular weight. Moreover, it was found that the iPP2 or iPP3 prepared with Hex₃Al crystallizes from the melt in mixtures of the α and γ forms, even at atmospheric pressure and for high molecular weight. The microstructure showed in the PP samples obtained at high temperature could be well explained with the shift in the alkylaluminium‐donor equilibrium reactions at high polymerization temperature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

On the physical behavior of isotactic polypropylene fibers extruded at different draw‐down ratios: II. Structure and properties

Microinterferometry (MIF), wide‐angle X‐ray scattering (WAXS), differential scanning calorimetry (DSC), and an Instron tensile tester (ITT) were used to determine the correlation between optical and structural properties of polypropylene (PP) fibers. For the purpose of the study a set of as‐spun isotactic PP fibers were extruded by melt spinning at different draw‐down ratios (DDR). The birefringence (Δn), degrees of orientation, degree of crystallinity (χ), Young's modulus (E_e), and tenacity (τ) were determined for PP fibers at the different DDR. An equiangular orientation of PP fibers at particular DDR was predicted experimentally, and the transverse modulus (E_t) was estimated for the tested fibers. Empirical formulae were developed for correlating the fiber birefringence with some of the studied structural properties of PP fibers. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Improving the adhesion properties of polypropylene using a liquid-phase sulfonation treatment

This work describes the effects of a stable, short-reaction time, liquid-phase sulfonation technique aimed at improving the adhesion properties of polypropylene. The relationships among SO₃ concentration (0.15, 0.2, and 0.3 N), treatment time, surface chemistry, and adhesion debond strength have been investigated for polypropylene (PP) sheets sulfonated with SO₃ dissolved in 1,1,2-trichloro 1,2,2-trifluoroethane and neutralized using ammonium hydroxide (NH₄OH) or polyethyleneimine (PEI). It was confirmed that PEI neutralized specimens, compared to untreated PP, exhibited a larger increase in debond strength (~269% increase) than similarly treated specimens neutralized with NH₄OH (~210% increase). ATR-FTIR spectroscopy indicates the formation of sulfonic acid, ethylenic, ketone and alcoholic hydroxyl groups. These results are supported by X-ray photoelectron spectroscopy (XPS) that show the O : C ratios increasing from 0.03 to 0.25 for both the NH₄OH and PEI, and the S : C atomic ratios increasing from 0.0 to 0.05 and 0.06 for the NH₄OH and PEI, respectively. Furthermore, XPS examination of PEI neutralized specimens revealed a nitrogenated surface (~6%), providing evidence that PEI had grafted onto the sulfonated surface. The observed increases in adhesion are attributed to formation of polar functionalities and increased wettability (as measured by water contact angle measurements). The neutralizing agent also affects degree of adhesion improvement: the PEI causes larger increases in adhesion compared to the NH₄OH. The physical effects of sulfonation were examined using environmental scanning electron microscopy (ESEM), which showed crack formation after 2 min of treatment. Sulfonation times beyond 5 min degraded the polymer surface (severe microcracking and sloughing of the surface layer) decreasing the adhesion debond strength.     

Hydrophilic modification of polypropylene microporous membranes by grafting TiO2 nanoparticles with acrylic acid groups on the surface

Hydrophilic microporous membranes were prepared based on polypropylene (PP) cast films blended with a commercial acrylic acid grafted polypropylene (PP-g-AA) via melt extrusion followed by grafting titanium dioxide (TiO₂) nanoparticles on its surface, annealing and stretching. ATR-FTIR, XPS and EDS analyses showed that the hydrophilic segments of an amphiphilic modifier (PP-g-AA) acted as surface functional groups on the film surface. The results indicated that the presence of the modifier was very important for grafting TiO₂ nanoparticles on the film surface. Compared to PP and PP/PP-g-AA blend films, the water contact angle decreased by a factor of 2.5 after grafting TiO₂ on the surface of the films, meanwhile the water vapor permeability of the microporous membranes prepared from those films increased by a factor of 1.5. All these results indicated that the hydrophilicity of the modified PP membranes was improved.