The Change of Structural,Optical and Thermal Properties of a PVDF/PVC Blend Containing ZnO Nanoparticles

Nanocomposites consisting of a polyvinylidene fluoride (PVDF)/polyvinyl chloride (PVC) blend containing zinc oxide (ZnO) nanoparticles were prepared. The changes of the structural, optical and thermal properties of the PVDF/PVC blend before and after addition of ZnO were studied. The shift of intensity in IR bands suggested an interaction and compatibility between the blend and ZnO. The structural properties, crystallinity and grain size of the samples were studied using X-ray diffraction. The average grain size was approximately 16 nm confirmed by TEM observations. The X-ray peak positions of ZnO in doped samples were located in the same positions as those of pure ZnO indicating the crystal structure of ZnO was not altered by its incorporation into PVDF/PVC. The estimated values of the optical energy gap from UV/Vis spectra for indirect transition decrease with increasing ZnO due to charge transfer between PVDF/PVC and ZnO nanoparticles. The thermogravimetric analysis curves showed nearly identical behaviors for all samples. Samples that contained ZnO exhibited less weight loss compared to the pure blend attributed to crosslinking formation between the blend and ZnO. Transmission electron microscopy (TEM) images revealed that ZnO was uniformly distributed inside PVDF/PVC polymeric matrices and was superimposed on an amorphous background.     

Rheological and mechanical properties of PVC/CaCO3 nanocomposites prepared by in situ polymerization

Poly(vinyl chloride) (PVC)/calcium carbonate (CaCO₃) nanocomposites were synthesized by in situ polymerization of vinyl chloride (VC) in the presence of CaCO₃ nanoparticles. Their thermal, rheological and mechanical properties were evaluated by dynamic mechanical analysis (DMA), thermogravimetry analysis (TGA), capillary rheometry, tensile and impact fracture tests. The results showed that CaCO₃ nanoparticles were uniformly distributed in the PVC matrix during in situ polymerization of VC with 5.0 wt% or less nanoparticles. The glass transition and thermal decomposition temperatures of PVC phase in PVC/CaCO₃ nanocomposites are shifted toward higher temperatures by the restriction of CaCO₃ nanoparticles on the segmental and long-range chain mobility of the PVC phase. The nanocomposites showed shear thinning and power law behaviors. The ‘ball bearing’ effect of the spherical nanoparticles decreased the apparent viscosity of the PVC/CaCO₃ nanocomposite melts, and the viscosity sensitivity on shear rate of the PVC/CaCO₃ nanocomposite is higher than that of pristine PVC. Moreover, CaCO₃ nanoparticles stiffen and toughen PVC simultaneously, and optimal properties were achieved at 5 wt% of CaCO₃ nanoparticles in Young's modulus, tensile yield strength, elongation at break and Charpy notched impact energy. Detailed examinations of micro-failure micromechanisms of impact and tensile specimens showed that the CaCO₃ nanoparticles acted as stress raisers leading to debonding/voiding and deformation of the matrix material around the nanoparticles. These mechanisms also lead to impact toughening of the nanocomposites.     

An Efficient Preparation and Characterization of Nanocomposite Films Based on Poly(vinyl chloride) and Modified ZnO Quantum Dot with an Optically Active Diacid Containing Amino Acid as Coupling Agent

The nanocomposites were manufactured by the incorporation of modified ZnO into the poly(vinyl chloride). ZnO nanoparticles were modified with diacid containing alanine amino acid. Ultrasonic irradiation was used for all process. The PVC/ZnO@DA nanocomposites were investigated by field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, UV–visible spectroscopy, thermogravimetric, and mechanical analysis. Results showed the uniform dispersion of particles in the polymer matrix and ZnO@DA nanoparticles in quantum dot size. The optical properties of PVC were affected by the incorporation of modified quantum dot ZnO; also mechanical properties of PVC/ZnO@DA nanocomposites were improved.     

Crystallization and unusual rheological behavior in poly(ethylene oxide)-clay nanocomposites

We report a systematic study of the crystallization and rheological behavior of poly(ethylene oxide) (PEO)-clay nanocomposites. To that end a series of nanocomposites based on PEOs of different molecular weight (10³ < MW < 10⁵ g/mol) and clay surface modifier was synthesized and characterized. Incorporation of organoclays with polar (MMT-OH) or aromatic groups (MMT-Ar) suppresses the crystallization of polymer chains in low MW PEO, but does not significantly affect the crystallization of high MW matrices. In addition, the relative complex viscosity of the nanocomposites based on low MW PEO increases significantly, but the effect is less pronounced at higher MWs. The viscosity increases in the series MMT-Alk < MMT-OH < MMT-Ar. In contrast to the neat PEO which exhibits a monotonic decrease of viscosity with temperature, all nanocomposites show an increase after a certain temperature. This is the first report of such dramatic enhancements in the viscoelasticity of nanocomposites, which are reversible, are based on a simple polymer matrix and are true in a wide temperature range.     

PMMA接枝纳米ZnO复合粒子改性PVC塑料性能研究

通过原位聚合将甲基丙烯酸甲酯（MMA）接枝于纳米ZnO表面,制备了PMMA接枝纳米ZnO复合粒子,将其加入聚氯乙烯（PVC） 基体中进行改性。研究了纳米ZnO粒子在PVC基体中的分散性和PVC复合材料的力学性能,探讨了改性纳米ZnO粒子填充PVC材料的抗紫外线性能。结果表明,改性后的纳米ZnO粒子在PVC基体中分散均匀, 提高了纳米ZnO粒子与PVC基体之间的相容性,使改性PVC材料的拉伸强度达到78 MPa,比纯纳米ZnO粒子改性PVC提高了35 %;冲击强度提高了近1倍,达到13.6 kJ/m2;加入改性纳米ZnO粒子的PVC还具有明显的吸收紫外线功能。     

Nanocomposites of PVC/TiO2 nanorods: Surface tension and mechanical properties before and after UV exposure

In this study, nanocomposites of poly(vinyl chloride) (PVC), using the synthesized titanium dioxide (TiO₂) nanorods and commercial nanopowder of titanium dioxide (Degussa P25) were produced by melt blending. The presence of TiO₂ nanorods in PVC matrix led to an improvement in mechanical properties of PVC nanocomposites in comparison with unfilled PVC. The photocatalytic degradation behavior of PVC nanocomposites were investigated by measuring their structural change evaluations, surface tension, and mechanical properties before and after UV exposure for 500 h. It was found that mechanical and physical properties of PVC nanocomposites are not reduced significantly after UV exposure in the presence of TiO₂ nanorods in comparison with the presence of TiO₂ nanoparticles, which can be due to the amorphous structure of the synthesized nanorods. Therefore, it can be concluded that TiO₂ nanorods led to an improvement in photostability and mechanical properties of PVC nanocomposites. The interfacial adhesion between TiO₂ nanorods and PVC matrix was also investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of silver nanoparticles on thermal properties of DBSA-doped polyaniline/PVC blends

Dodecylbenzenesulfonic acid (DBSA)-doped polyaniline (PAND) has been synthesized by redoping (PANDR) and aqueous polymerization (PANDA) methods. Silver nanoparticles were incorporated into the PANDR/tetrahydrofuran solution (PANDS) and then mixed with poly (vinyl chloride) (PVC) solution to prepare PANDS/PVC nanocomposites. In the present study, effects of silver nanoparticles on thermal properties of PAND/PVC blends have been investigated by employing thermal gravimetric analysis and heat flow microcalorimetry techniques. From these results it has been observed that the thermal stability of blends have increased by increasing the concentration of PAND in blends and nanocomposites. Addition of silver nanoparticles has suppressed the dehydrochlorination process and evolution/degradation of DBSA in PANDS/PVC nanocomposites. Presence of silver nanoparticles in PAND/PVC nanocomposites has reduced the mobility of PANI chains which in turn inhibited the transfer of free radicals formed during degradation of PAND and PVC through inter-chain reactions; hence, degradation process has been slowed down and thermal stability has been improved. Embedment of silver nanoparticles has reduced thermal weight loss corresponding to polymer degradation step and attains lower heat flow level in inert atmosphere for nanocomposites in contrast to those with no nanoparticles, thereby further improving thermal stability of nanocomposites. The heats of oxidation measured for blends and nanocomposites were independent of PAND/PVC blends composition.     

PMMA‐grafted‐silica/PVC nanocomposites: Mechanical performance and barrier properties

Poly(vinyl chloride) (PVC)/SiO₂ nanocomposites were prepared via melt mixture using a twin‐screw mixing method. To improve the dispersion degree of the nanoparticles and endow the compatibility between polymeric matrix and nanosilica, SiO₂ surface was grafted with polymethyl methacrylate (PMMA). The interfacial adhesion was enhanced with filling the resulting PMMA‐grafted‐SiO₂ hybrid nanoparticles characterized by scanning electron microscopy. Both storage modulus and glass transition temperature of prepared nanocomposites measured by dynamic mechanical thermal analysis were increased compared with untreated nanosilica‐treated PVC composite. A much more efficient transfer of stresses was permitted from the polymer matrix to the hybrid silica nanoparticles. The filling of the hybrid nanoparticles caused the improved mechanical properties (tensile strength, notched impact strength, and rigidity) when the filler content was not more than 3 wt %. Permeability rates of O₂ and H₂O through films of PMMA‐grafted‐SiO₂/PVC were also measured. Lower rates were observed when compared with that of neat PVC. This was attributed to the more tortuous path which must be covered by the gas molecules, since SiO₂ nanoparticles are considered impenetrable by gas molecules. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrical properties and thermal degradation of poly(vinyl chloride)/polyvinylidene fluoride/ZnO polymer nanocomposites

In this work, polymer nanocomposites consisting of a poly(vinyl chloride) (PVC) and polyvinylidene fluoride (PVDF) polymer network with ZnO nanoparticles as a dopant were prepared by solution casting. An XRD study of the PVC/PVDF/ZnO polymer nanocomposites shows predominantly sharp and high intensity peaks. However, the intensity and sharpness of the XRD peaks decreases with further increment in loading of ZnO (wt%), which reveals a proper intercalation of ZnO nanoparticles within the PVC/PVDF polymer system. Fourier transform infrared spectroscopy has been used to verify the chemical compositional change as a function of ZnO nanoparticle loading. TGA analysis clearly describes the thermal degradation of the pure polymer and polymer nanocomposites. The complex dielectric function, AC electrical conductivity and impedance spectra of these nanocomposites were investigated over the frequency range from 10 Hz to 35 MHz. These spectra were studied with respect to the Wagner ? Maxwell ? Sillars phenomenon in the low frequency region. Nyquist plots of the PVC/PVDF/ZnO nanocomposites were established from impedance measurements. The temperature‐dependent DC ionic conductivity obtained from the Nyquist plots follows Arrhenius behaviour. © 2016 Society of Chemical Industry     

Morphology,mechanical property,and processing thermal stability of PVC/La‐OMMTs nanocomposites prepared via in situ intercalative polymerization

Poly(vinyl chloride) (PVC) nanocomposites were prepared via an in situ intercalative suspension polymerization of vinyl chloride with four organic carboxylic acid salts (montmorillonite [MMT] units) containing thermally stable lanthanum ions. The effects of different lanthanum organic montmorillonites (La‐OMMTs) on the particle features and molecular weight were investigated. The transmission electron microscopy data indicated the formation of partially exfoliated or intercalated PVC/La‐OMMTs nanocomposites. The effect of different functional groups on the mechanical properties and processing thermal stability of PVC/La‐OMMT nanocomposites were investigated. Tensile testing and two‐roll mill processing results showed that La‐OMMTs could enhance the dynamic thermal stability and mechanical properties versus PVC pure resin and PVC/I.30P nanocomposites (composed of PVC and I.30P). This suggested that the double bond and amidogen group in La‐OMMTs could promote the dispersion of La‐OMMTs in the PVC matrix and also improve the adhesion between the La‐OMMTs and PVC matrix. The results have potential value in the industrial development of PVC/La‐OMMTs nanocomposites. J. VINYL ADDIT. TECHNOL., 26:97–108, 2020. © 2019 Society of Plastics Engineers     

Morphology,mechanical properties,and thermal stability of rigid PVC/clay nanocomposites

PVC/Poly(ε‐caprolactone) (PCL)/organophilic‐montmorillonite (OMMT) and PVC/Polylactide (PLA)/OMMT nanocomposites were prepared by a two‐step process. PCL/OMMT and PLA/OMMT master batches were prepared by melt blending using a two‐roller mill first, and then they were blended with PVC via extrusion. PVC/OMMT nanocomposites were also prepared using a two‐roller mill. Morphology, mechanical properties, and thermal stability were investigated. The formation of exfoliated or intercalated nanocomposites was confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Only the PVC/PCL/OMMT nanocomposite showed both higher tensile strength and stiffness than unfilled PVC. Atomic force microscopy (AFM) indicated dependency of this behavior not only on the clay dispersion, but also on the adhesion between the OMMT and the polymer matrix. Furthermore, scanning electron microscopy (SEM) showed that the large plastic deformation of the PVC/PCL matrix also contributed to the strength increase of the PVC nanocomposites. The effect of PCL/OMMT on the improvement of the thermal stability of PVC was remarkable while the effect of PLA/OMMT was moderate. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Quasi‐brittle to ductile transition in impact‐modified PVC

The toughness of impact‐modified poly(vinyl chloride) (PVC) compounds was examined by using a modified Charpy test. Increasing impact speed resulted in a quasi‐brittle to ductile transition in all PVC compounds. In the quasi‐brittle region, a PVC of 56,000 M_w fractured through a craze‐like damage zone that could be described by a modified Dugdale model. Furthermore, the same molecular‐weight PVC modified with either 10 pph (parts per hundred parts by weight) of chlorinated polyethylene (CPE) or 10 pph of methylmethacrylate‐butadiene‐styrene (MBS) impact modifier also conformed to the Dugdale model with the craze‐like damage zone. The CPE effectively improved the impact performance of PVC by shifting the quasi‐brittle to ductile transition to a higher loading rate. Compared to CPE, MBS was a better impact modifier, and its use resulted in a higher quasi‐brittle to ductile transition loading rate in the same PVC matrix. Fracture initiation toughness of all the materials was described by the Hayes‐Williams modification of the Dugdale model. The intrinsic brittle fracture energy obtained by extrapolation to zero craze length was determined only by the PVC matrix and was independent of the impact modifier. However, the kinetics of craze growth, and hence the response to rapid loading, depended on the impact modifier. Increasing the molecular weight of the PVC resin resulted in a more complex damage zone that was not amendable to the Dugdale analysis. J. Vinyl Addit. Technol. 10:11–16, 2004. © 2004 Society of Plastics Engineers.     

Nanoparticules Mass Effect of ZnO on the Properties of Poly(4-Chloroaniline)/Zinc Oxide Nanocomposites

4-Chloroaniline (4ClAni) in the presence of zinc oxide (ZnO) nanoparticles were prepared by chemical oxidative polymerization in hydrochloric acid solution using Ammonium persulfate as oxidant. The effects of amount of ZnO nanoparticles (1, 1.5, 2, 2.5 and 3 g, respectively) on the properties of products were investigated. The obtained nanocomposites was characterized using XRD, IR, UV–visible, and XPS which confirmed the incorporation of the nanoparticle ZnO in the P(4ClAni) matrix and the maximum interaction occurs for 2 g ZnO loading. The TGA analysis was used to confirm the thermal stability and number of water molecules in each nanocomposites chain unit. Although the incorporation of ZnO nanoparticles reduces the electric conductivity of the P(4ClAni), the resulting nanocomposites still keep high conductivities, ranging between 2.19 × 10^?2 and 5.92 × 10^?4 S cm^?1. Good electrochemical response has been observed for samples of amounts ZnO less than 2 g; the observed redox processes indicate that the polymerization on ZnO nanoparticles produces electroactive polymers. The P(4ClAni) layer adhered well to the ZnO nanoparticles and can be used as practical applications.     

Role of copper alumina nanoparticles on the performance of polyvinylchloride nanocomposites

Poly(vinyl chloride) (PVC) nanocomposites with different contents of copper alumina (Cu-Al₂O₃) nanoparticles were prepared by the solution casting method. The effects of the nanoparticles on structural, thermal, electrical, contact angle and mechanical properties were thoroughly examined. The presence of Cu-Al₂O₃ in the macromolecular chain was confirmed through Fourier transform infrared (FTIR) spectroscopy. The X-ray diffraction (XRD) analysis of PVC nanocomposites showed the systematic arrangement of Cu-Al₂O₃ nanoparticles within the polymer, which indicated the higher crystallinity of the nanocomposites. The surface morphology of PVC was changed into hemispherical shaped particles by the inclusion of nanofiller was analyzed from SEM images. The glass transition temperature of the nanocomposites obtained from differential scanning calorimetry (DSC) was found to be increased with an increase in loading of nanoparticles in the polymer. The AC conductivity and dielectric studies revealed that the inclusion of nanofiller increases the electrical properties of the material and the composite with 7 wt.% sample showed the maximum conductivity and dielectric constant. The mechanical properties such as modulus, tensile strength, hardness, and impact properties of the PVC nanocomposites were significantly enhanced by the reinforcement of nanoparticles into the PVC matrix. The reinforcing mechanism behind the increase in tensile strength with the addition of nanoparticles was correlated with different theoretical models. The highest mechanical and electrical properties were observed for 7 wt.% Cu-Al₂O₃ loaded nanocomposite. Contact angle measurements of PVC with various loadings of Cu-Al₂O₃ nanofillers demonstrated that the nanoparticle attachment increased the hydrophobicity of the polymer matrix.     

Investigation of the thermal,mechanical and morphological properties of poly(vinyl chloride)/polyhedral oligomeric silsesquioxane nanocomposites

Research into organic–inorganic nanocomposites has recently become popular, particularly the development of new polymer nanocomposites. Compared to pristine polymers or conventional composites, these nanocomposites exhibit improved properties. The storage modulus of a poly(vinyl chloride) (PVC)/polyhedral oligomeric silsesquioxane (POSS) nanocomposite slightly decreased with POSS content, but had a higher modulus from 50 to 100 °C. Some of the material appeared to be aggregated with 1 wt% POSS in the polymeric matrix. Conversely, with a POSS content of 5 wt%, a better dispersion of the nanoparticles was observed. The presence of POSS in the plasticised PVC compound had little influence on the final properties of the nanocomposites, showing weaker interactions between the POSS and the plasticised PVC compound. Copyright © 2010 Society of Chemical Industry     

Antibacterial Nanocomposite of Poly(Lactic Acid) and ZnO Nanoparticles Stabilized with Poly(Vinyl Alcohol): Thermal and Morphological Characterization

The effect of polyvinyl alcohol (PVA) as a surface coating agent on the antibacterial and thermal properties of polylactic acid (PLA)/ZnO nanocomposites prepared by melt blending was investigated. The ZnO nanoparticles were coated and stabilized with PVA using a solvothermal method. Nanocomposites were prepared with different ZnO nanoparticle content: 1, 3 and 5 wt.%. Electron transmission microscopy and Fourier transform infrared spectroscopy showed the presence of a layer around the nanoparticles and the interaction between nanoparticles and PVA, respectively. DSC analysis revealed that the thermal properties of the nanocomposites were not affected by the coating of ZnO nanoparticles with PVA. The PLA/ZnO nanocomposites with coated nanoparticles presented better antibacterial activity than those containing uncoated nanoparticles.     

Rigid PVC/(layered silicate) nanocomposites produced through a novel melt‐blending approach

On the basis of the fusion behavior of poly(vinyl chloride) (PVC), the influence of compounding route on the properties of PVC/(layered silicate) nanocomposites was studied. Four different compounding addition sequences were examined during the melt compounding of PVC with montmorillonite (MMT) clay, including (a) a direct dry mixing of PVC and nanoclay, (b) an addition of nanoclay at compaction, (c) an addition of nanoclay at the onset of fusion, and (d) an addition of nanoclay at equilibrium torque. Both unmodified sodium montmorillonite (Na⁺‐MMT) and organically modified montmorillonite (Org.‐MMT) clays were used, and the effect of the addition sequence of the clay during compounding on its dispersion in the matrix was evaluated by X‐ray diffraction and transmission electron miscroscopy. The surface color change, dynamic mechanical analysis, and flexural and tensile properties of PVC/clay nanocomposites were also studied. The experimental results indicated that both the extent of property improvement and the dispersion of nanoparticles in PVC/(layered silicate) nanocomposites are strongly influenced by the degree of gelation achieved in PVC compounds during processing. The addition of nanoclay to PVC must be accomplished at the onset of fusion, when PVC particles are reduced in size, in order to produce nanocomposites with better nanodispersion and enhanced mechanical properties. Overall, rigid PVC nanocomposites with unmodified clay (Na⁺‐MMT) were more thermally stable and exhibited better mechanical properties than their counterparts with organically modified clay (Org.‐MMT). J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

PVC塑料复合材料的热性能和电导率的研究

实验测定了聚氯乙烯-多壁碳纳米管(PVC/MWNT)复合材料在直流、交流条件下的热性能和电导率。采用热压缩法制备了PVC/MWNT复合材料,实验结果显示:材料存在超低渗透阈值(φc)0.045%。电导率对温度的依赖关系表明,在PVC/MWNT复合材料中,离子电导率低于φc,而复合材料中沿MWNT相的电荷输运的电子类型高于(φc)。热力学分析表明,在聚合物基体的体积内形成了一个刚性的填充网络,限制了聚合物向塑性状态的转变。     

纳米二氧化硅颗粒表面设计及其填充聚氯乙烯复合材料的性能

利用表面原位接枝聚合在纳米二氧化硅颗粒表面引入聚甲基丙烯酸甲酯(PMMA)高分子链段,用共混法制备了nano-SiO2/PVC复合材料,研究了不同界面特性时SiO2/PVC复合材料的力学性能.研究结果表明通过表面原位接枝聚合反应可以在纳米二氧化硅颗粒表面接枝聚甲基丙烯酸甲酯;表面接枝PMMA的nano-SiO2/PVC复合材料在力学和加工性能等方面都优于偶联剂处理和表面未处理样品.在纳米二氧化硅颗粒填充量为0%～8%(wt)时,复合材料的拉伸强度和冲击强度随着填充量的提高先上升后下降,并在4%～6%(wt)达到最大值.经PMMA表面接枝后SiO2/PVC具有更强的界面作用,偶联剂KH570处理的次之,表面未处理样品的最差.     

PVC nanocomposites—Nanoclay chemistry and performance

Nanoclay applications in poly(vinyl chloride) (PVC) have been limited, as the organic modifier of conventional nanoclays can promote PVC degradation. Novel nanoclays designed for enhanced PVC compatibility were compounded with PVC. Hectorite and bentonite clays were studied as nanoclay fillers. Two incorporation methods were evaluated to determine the effect on nanoclay dispersion and composite performance. A two‐stage method, in which the nanoclay was predispersed in plasticizer, resulted in good nanoclay dispersion at both the micrometer and nanometer scales. The nanocomposites were characterized by using a wide range of analytical tools. They exhibited significantly improved heat stability, an increase of up to 200% in storage modulus, and a decrease of up to 77% in oxygen permeation, as compared to unfilled PVC. Bentonite nanoclays provided a greater increase in barrier and mechanical properties. No change was seen in the PVC glass transition temperature. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers