Near infrared (NIR) studies of PVC film photodegradation

Near infrared (NIR) spectroscopy was used to develop predictive models of color development for PVC film formulations subjected to accelerated weathering. The high correlations between color and NIR spectra result from the common polyene sequences origin of both measurements. The methodology should be applicable to transparent and filled systems. It provides a probe for investigating polyene sequence formation with minimal saturation effect limitations. The NIR technique can provide a complementary approach to mid‐IR and Raman studies of polymer photodegradation. J. VINYL. ADDIT. TECHNOL., 11:39–46, 2005. © 2005 Society of Plastics Engineers     

Tween 20‐modified poly(vinyl chloride) exhibits enhanced blood‐compatibility

Poly(vinyl chloride) (PVC) resin was modified by grafting the non‐ionic surfactant poly(oxyethylene 20 sorbitan) monolaurate (Tween^® 20) using isocyanate chemistry. PVC was aminated using ethylenediamine and coupled with hexamethylene diisocyanate. Tween 20 was then reacted with the polymer, resulting in the grafting of the surfactant. The polymer modification was confirmed using infrared and X‐ray photo‐electron spectroscopy. Films of modified polymer were cast from a solution of tetrahydrofuran. The surface of films prepared from the modified polymer showed increased hydrophilicity as evidenced by contact‐angle measurements. The solid/water free energy of the modified polymer surface was nearly a quarter of the energy of the bare PVC surface. Static platelet adhesion studies using platelet‐rich plasma demonstrated significantly reduced adhesion onto a modified PVC surface compared with unmodified PVC. Data obtained demonstrate that modification of polymers with Tween 20 may be an interesting way of imparting protein‐ and cell‐repelling characteristics to them, thereby improving their blood‐compatibility. Copyright © 2005 Society of Chemical Industry     

Synergistic combination of metal stearates and β‐diketones with hydrotalcites in poly(vinyl chloride) stabilization

A synergistic effect of synthetic hydrotalcites as long term stabilizer with metal soaps (the mixture of calcium and zinc stearate) and metal acetylacetonates on dehydrochlorination of PVC has been studied. A proper balance between color stabilization and HCl scavenging capacity has been obtained. Hydrotalcite was prepared by hydrothermal treatment and characterized by EDX, XRD, FTIR, TGA, and SEM techniques. The material is reasonably crystalline and suggests a relatively well ordered sheet arrangement with crystallite size 24.87 nm. The interlayer water content was calculated from the TGA curves and the suggested formula is Mg_0.76 Al_0.24(OH)₂(CO₃)_0.12·0.5H₂O. Synergism in PVC stabilization has been studied by measuring the HCl evolution during the processing at 180°C. Oven aging method was used to study the color stabilization at higher temperature. PVC sheet with different formulation was prepared using Labcoater and subjected to oven for different time interval. The color development (polyene formation) on oven ageing was recorded using UV–visible spectroscopy. UV–visible studies shows that an average sized polyene gives pale yellow color, whereas red or brown color was developed due to long range polyene (n = 10–14) sequences. Hence, the HCl evolution depends on the rate of dehydrochlorination but color depends on the kind of polyene formed. Mechanism of stabilization suggests that adsorption and ion exchange, both phenomenon, are responsible for hydrotalcites as long term stabilizers. The acetylacetonate complex too substitute allylic chlorides and inhibit formation of long polyene responsible for darkening. A clear effect of synergism has been observed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of wood sawdust content on rheological and structural changes,and thermo‐mechanical properties of PVC/sawdust composites

The use of untreated sawdust as a filler in poly(vinyl chloride) (PVC) was examined—the effects of sawdust content on structural and thermal changes, and rheological and mechanical properties being of main interest. The results revealed that the torque and die entrance pressure drop values during mixing were independent of sawdust particles up to 23.1 wt%. The extrudate swell monotonically decreased up to 33.3 wt% sawdust content. Smooth wood‐like texture with controllable size of the extrudate could be obtained at a sawdust content greater than 33.3 wt%. Tensile, impact, flexural and hardness properties of the PVC/sawdust composites considerably decreased with up to 16.7 wt% sawdust content before leveling off for higher sawdust loadings. The composites having sawdust higher than 16.7 wt% showed a benefit of cost savings. The decreases in the mechanical properties of PVC with sawdust are explained in association with the presence of moisture, interfacial defects between fibre and polymer, and fibre dispersions in the PVC matrix. Thermal degradations of PVC in PVC/sawdust composites were evidenced by a decrease in decomposition temperature and an increase in polyene sequences, which were caused by Cl cleavage due to strong hydrogen bonds of fibre–PVC molecules. The maximum of tanδ transition and the glass transition temperature were found to improve with sawdust content as a result of re‐formation of hydrogen bonds between the macromolecules of the fibre and the polymer. The overall results in this work suggest that the properties of PVC/sawdust composites were strongly influenced by sawdust content up to 16.7 wt%. Beyond this value the effect of sawdust content on the properties was comparatively small. Copyright © 2003 Society of Chemical Industry     

Acceleration and Inhibition Effect of Tertiary Amines on Thermal Degradation of Poly(Vinyl Chloride)

Poly(vinyl chloride) (PVC) is occasionally discolored yellow or red by the formation of polyene chains in the polymer backbone. It has been noted that the formation of such polyene structures is caused by dehydrochlorination of the PVC, accelerated by tertiary amines. Thus, in the present study, we investigated the influence of amines on the formation of polyene structures in PVC, using resonance Raman spectroscopy. The amount of polyene produced by thermal treatment with amine vapor exposure was determined based on the resonance Raman intensity ratio of the polyene band to the PVC band. The results showed that the discoloration of PVC, indicating the formation of polyene structures, was most prominently caused by 1,4‐diazabicyclo[2.2.2.]octane (DABCO), bis(2‐dimethylaminoethyl)ether (BDMEE), or N,N,N′,N′‐tetramethyl‐1,6‐diaminohexane (TMDAH), because of their high basicity and nucleophilicity. In addition, the formation of polyene structures was inhibited by the co‐presence of amine and protic solvent (water, ethanol, and 2‐propanol) or additives containing hydroxyl groups (glycerin, poly[vinyl alcohol]), suggesting that amine nucleophilicity toward PVC is reduced by the protonation of amine to lone pairs of tertiary amines. J. VINYL ADDIT. TECHNOL., 26:253–258, 2020. © 2019 Society of Plastics Engineers     

Nachweis von Polyensequenzen in thermisch gealtertem Polyvinylchlorid durch Resonanz-Ramanspektroskopie

A Raman spectroscopical method allowing the evaluation of polyene sequences in heat-treated polyvinylchloride (PVC) samples is described. The enormous increase of Raman scattering with increasing number of conjugated double bonds, utilizing the Raman resonance phenomenon, renders the laser Raman spectroscopy an extremely sensitive analytical method. A polyene sequence length of n ～ 20 could be deduced from the frequency of the resonance line. This frequency was independent of the amount of HCl split off within the limits of 1·10^?4 to 0,1 wt.-% HCl. The activation energy of HCl-elimination for a graft copolymer of vinyl chloride onto poly(ethylene-vinylacetate) was found to be E_A = 32,7 kcal/mole by both Raman spectroscopy and conventional detection from the elimination reaction. A commercial suspension PVC showed evidence of polyene sequence formation already at 60°C.     

Bio‐based Mg(OH)2@M‐Phyt: improving the flame‐retardant and mechanical properties of flexible poly(vinyl chloride)

Two novelty bio‐based multifunctional metallic phytate coated (M‐Phyt, M ≡ Cu, Zn) Mg(OH)₂ (MH@M‐Phyt) were designed and incorporated into flexible poly(vinyl chloride) (PVC). MH@M‐Phyt was incorporated into PVC materials in a powder form. The morphology of the interface between MH and M‐Phyt and their binding states were characterized by TEM and X‐ray photoelectron spectroscopy (XPS), respectively. The TEM images of MH@M‐Phyt indicated that M‐Phyt was successfully coated on the MH surface. Additionally, from the XPS spectra M‐Phyt and MH were connected by Mg–O–P bonds. The flame retardancy and mechanical properties of the PVC composites were investigated through the limiting oxygen index, cone calorimetry and mechanical tests. The char residues were analyzed by SEM. The results revealed that the MH@M‐Phyt powder functioned well in PVC, with a flame retardancy, smoke density, tensile strength and elongation at break better than those of PVC/MH. With 10 phr loading, the peak heat release rate of PVC/MH@Zn‐Phyt and PVC/MH@Cu‐Phyt decreased by 33.5% and 24.6%, respectively, benefitting from the formation of firmer and denser char layers on the char residues. © 2019 Society of Chemical Industry     

Enhanced Solid‐Phase Photocatalytic Degradation Activity of a Poly(vinyl chloride)‐TiO2 Nanocomposite Film with Bismuth Oxyiodide

A new type of photodegradable poly(vinyl chloride)‐bismuth oxyiodide/TiO₂ (PVC‐BiOI/TiO₂) nanocomposite film was prepared by embedding a nano‐TiO₂ photocatalyst modified by BiOI into the commercial PVC plastic. The solid‐phase photocatalytic degradation behavior of the as‐prepared film was investigated in ambient air at room temperature under UV light irradiation, with the aid of UV‐Vis spectroscopy, weight loss monitoring, scanning electron microscopy, and FT‐IR spectroscopy. Compared to the PVC‐TiO₂ nanocomposite film, the PVC‐BiOI nanocomposite film and the pure PVC film, the PVC‐BiOI/TiO₂ nanocomposite film exhibited a higher photocatalytic degradation activity. The optimal mass ratio of BiOI to TiO₂ was found to be 0.75 %. The weight loss rate of the PVC‐BiOI/TiO₂ nanocomposite film reached 30.8 % after 336 h of irradiation, which is 1.5 times higher than that of the PVC‐TiO₂ nanocomposite film under identical conditions. The solid‐phase photocatalytic degradation mechanism of the nanocomposite films was briefly discussed.     

Improvement of the photostabilization of PVC films in the presence of 2N‐salicylidene‐5‐(substituted)‐1,3, 4‐thiadiazole

The photostabilization of poly(vinyl chloride) (PVC) films by 2N‐salicylidene‐5‐(substituted)‐1,3,4‐thiadiazole compounds was investigated. The PVC films containing concentration of complexes 0.5% by weight were produced by the casting method from tetrahydrofuran (THF) solvent. The photostabilization activities of these compounds were determined by monitoring the carbonyl, polyene, and hydroxyl indices with irradiation time. The changes in viscosity average molecular weight of PVC with irradiation time were also tracked (using THF as a solvent). The quantum yield of the chain scission (ϕ_cs) of these complexes in PVC films was evaluated and found to range between 4.72 × 10⁻⁸ and 8.99 × 10⁻⁸. Results obtained showed that the rate of photostabilization of PVC in the presence of the additive followed the trend: According to the experimental results obtained, several mechanisms were suggested depending on the structure of the additive. Among them, UV absorption, peroxide decomposer, and radical scavenger for photostabilizer mechanisms were suggested. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adhesion of microwave‐plasma‐treated fluoropolymers to thermoset vinylester

Poly(tetrafluoroethylene) and a fluoroethylene copolymer were surface treated with a 2.45‐GHz microwave plasma to enhance their adhesion to a vinylester thermoset. The plasmas were generated with an inert gas (Ar) and with reactive gases (H₂, O₂, and N₂). The lap‐joint shear stress was measured on fluoropolymer samples glued with the vinylester. In general, the stress at failure increased with increasing plasma‐energy dose. The H₂ plasma yielded the best adhesion, and X‐ray photoelectron spectroscopy revealed that it yielded the highest degree of defluorination of the fluoropolymer surface. The defluorination efficiency declined in the order H₂, Ar, O₂, and N₂. Contact angle measurements and scanning electron microscopy revealed that the surface roughness of the fluoropolymer depended on the rate of achieving the target energy dose. High power led to a smoother surface, probably because of a greater increase in temperature and partial melting. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 838–842, 2005     

碳钢表面钛酸酯和PVC复合修饰膜的耐蚀性

<正>金属表面修饰,是一种有效的提高耐蚀性的手段。化学修饰同电化学修饰相比,操作简便,节能,而且实用性强,具有实际推广的意义。 钛酸酯是由美国Kenrich石油化学公司开发的一类以Ti为中心元素的新型偶联剂。它有比较独特的分子结构,一端能与无机物表面的羟基反应,生成牢固的化学键,另一端能与有机物发生交联。由于钛酸酯的这一特点,其应用范围正在不断扩大,在涂料、粘合剂、塑料和橡胶等方面都得到了广泛应用。Sugerman和SalVatore研究了钛酸酯在水基和高固涂料中的耐蚀性能,探讨了烷基钛酸酯与金属表面清漆耐蚀性的关系。Yoshitaka等研究了α-Fe_2O_3经钛酸酯修饰后表面性质的变化,并初步探讨了钛酸酯与金属的成键方式。总之,钛酸酯的作用愈来愈受到重视。     

Quantifying adsorption of heparin on a PVC substrate using ATR‐FTIR

The surface modification of poly(vinyl chloride) (PVC) tubing by heparin was performed to increase its blood compatibility. A solution of benzalkonium heparinate was used in the treatment of two types of plasticized PVC. The modification of the PVC surface was monitored after various treatment conditions, and quantitative results were obtained by using ATR‐FTIR spectroscopy. The treatment times and the PVC type have a strong influence on the observed amount of heparin. A partial removal (20–30 %) of heparin was observed after rinsing the PVC surface with a 0.9 wt% NaCl aqueous solution. The more flexible PVC tubing, having a lower T_g, had a higher concentration of heparin. Final heparin concentrations on the PVC surfaces were found to be in the range 1–17 µg cm^?2. Copyright © 2004 Society of Chemical Industry     

Small‐angle X‐ray scattering study of modified porous suspension–poly(vinyl chloride) particles

Small‐angle X‐ray scattering (SAXS) was applied to investigate the microstructure of unmodified and modified porous commercial suspension‐type poly(vinyl chloride) (PVC) particles. The modified PVC particles were prepared by an in situ stabilizer‐free polymerization/crosslinking of particles absorbed with a monomer/crosslinker/peroxide solution. The modifying polymers include styrene with or without divinyl benzene (DVB) as a crosslinker and methyl methacrylate (MMA) with or without ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The SAXS method was used to highlight the effect of polystyrene (PS) on the microstructure of PVC particles and to evaluate the characteristic lengths, both in the PVC/PS and the PVC/XPS (PS crosslinked with 0 and 5% DVB, respectively) systems. A model is suggested, where during the synthesis modification process, swelling of PVC by styrene and styrene polymerization occur simultaneously. PVC swelling by styrene causes destruction of the PVC subprimary particles, whereas styrene polymerization leads to phase separation resulting from incompatibility of the polymers. It was further suggested that because of PVC swelling by styrene, structure of the subprimary particles is lost. Therefore the characteristic lengths of PVC/PS and PVC/XPS, as calculated from the SAXS measurements, were attributed to the size of the phase‐separated PS and XPS inclusions, respectively. The SAXS method also shows that PMMA and XPMMA do not influence the PVC microstructure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1024–1031, 2005     

Poly(vinyl chloride) films plasticized with novel poly‐nadic‐anhydride polyester plasticizers

In this work, several novel poly‐nadic‐anhydride polyester plasticizers were developed to be used in poly(vinyl chloride) (PVC) film fabrication for the first time. Mechanical properties of the films, the compatibility of plasticizers in PVC resin, as well as testing of migration of the plasticizers, were performed in order to evaluate the efficiency of plasticization. Scanning electron microscopy, Fourier‐transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry were used to characterize the unplasticized and plasticized polymer. The results demonstrated that the as‐prepared poly‐nadic‐anhydride plasticized PVC film significantly improved the plasticization efficiency of PVC film based on the increase in the break in elongation of the films. According to scanning electron microscopy analysis, the poly‐nadic‐anhydride polyester plasticizers presented good compatibility with PVC resin. In volatility and extraction tests, PVC films plasticized with the poly‐nadic‐anhydrides showed enhanced migration resistance. The plasticizing effects induced by the poly‐nadic‐anhydride polyester plasticizers were also confirmed by a glass transition temperature shift toward lower temperatures in the plasticized films. J. VINYL ADDIT. TECHNOL., 23:321–328, 2017. © 2015 Society of Plastics Engineers     

Cold plasma surface modification of conventionally and nonconventionally plasticized poly(vinyl chloride)‐based flexible films: Global and specific migration of additives into isooctane

The effect of plasma‐induced surface crosslinking of poly(vinyl chloride) (PVC)‐based flexible films was investigated to limit its migration from packaging into fatty foodstuffs. The global migration was monitored by immersion into isooctane and the specific migrations of di‐2‐ethylhexyladipate (DEHA) and epoxidized soybean oil (ESO) were monitored by supercritical fluid chromatography analysis of the resulting isooctane solution. The plasma induced modifications were monitored with respect to the surface energy, weight loss, and surface crosslinking. The global migration from conventionally plasticized film, whose composition corresponds to an ordinarily used formulation for the manufacture of PVC wrap films, was controlled by different plasma treatments and the best results were obtained with Ar plasma. Further decreases in global migration were obtained by treating permanently plasticized films containing an elastomeric ethylene‐based terpolymer (EE) in complete or partial replacement of DEHA. Before treatment, the replacement of DEHA with EE increased the DEHA and ESO specific migrations. Argon plasma treatment of permanently plasticized films led to samples that did not exhibit any migration. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1384–1393, 2001     

One simple and stable coating of mixed‐charge copolymers on poly(vinyl chloride) films to improve antifouling efficiency

An antifouling surface is highly desirable for many biomedical applications. In this study, poly(vinyl chloride) (PVC) films were endowed with the improved properties of resisting nonspecific protein adsorption and platelet adhesion simply through being coated with a kind of mixed‐charge zwitterionic polymer, poly(3‐sulfopropyl methacrylate–methacrylatoethyl trimethyl ammonium chloride–glycidyl methacrylate) (PSTG), with random moieties of negatively charged 3‐sulfopropyl methacrylate potassium, positively charged [2‐(methacryloyloxy)‐ethyl] trimethylammonium chloride, and glycidyl methacrylate. The PSTG‐grafted PVC films were formed by the simple immersion of an amino‐functionalized PVC film into a PSTG solution. A grafting density of 220.84 µg/cm² of PSTG4‐grafted PVC film was successfully obtained. The PSTG4‐grafted PVC film showed a lower contact angle (37.5 °) than the ungrafted PVC film (98.3 °). The in vitro protein adsorption results show that the bovine serum albumin adsorption amount decreased 6.72 µg/cm² in the case of the PSTG4‐grafted PVC film, whereas that on the ungrafted PVC film was 28.54 µg/cm². So, PSTG‐grafted PVC films could be promising materials for medical devices. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44632.     

In‐line monitoring and analysis of polymer melting behavior in an intermeshing counter‐rotating twin‐screw extruder by ultrasound waves

An ultrasound in‐line monitoring system that includes a homemade probe and a fast data acquisition system was used to investigate the melting behavior of linear low density polyethylene (LLDPE) in pellet form and four polyvinyl chloride (PVC) compounds in powder form in an intermeshing counter‐rotating twin‐screw extruder. Ultrasound signal patterns obtained from experiments revealed various melting phenomena in C‐chambers, depending on materials, processing conditions, and screw configurations. The experimental results suggest that PVC particles were suspended in the polymer melt in the melting process of most PVC compounds, while melted film was still observed in the melting process of the PVC/dimethyl phthalate (DMP) system and the PVC/polybutylene adipate (PBA) system. Based on the analysis of wave attenuation, the normalized amplitude ratio K was used to characterize the melting level and uniformity across screw channels at screw speeds of 40 and 50 rpm, respectively. POLYM. ENG. SCI., 45:998–1010, 2005. © 2005 Society of Plastics Engineers     

Low‐temperature UV irradiation induced the color change kinetics and the corresponding structure development of PVC film

The low‐temperature ultraviolet (UV) irradiation equipment, developed in our Lab, was used to study the photo‐aging of poly (vinyl chloride) (PVC) films at low temperature. The color change kinetics and corresponding structure development of PVC film during low‐temperature UV aging were studied through L*a*b* coordinates Commission International d' Eclau‐age (CIE 1976 color space) and Ultraviolet spectrophotometer (UV–vis) and Fourier transform infrared spectroscopy (FTIR). It was found that the yellowness difference (?b*) and color difference (?E*) of the PVC film increased almost linearly with the aging time. Their values had a slower change at lower temperature. The kinetic study showed that the relationship between the velocity of coloration of the PVC film and the temperature agreed well with Arrhenius equation at low temperature. The activation energy of coloration of the PVC film was calculated. The FTIR spectra indicated that photo‐dehydrochloration, resulting in the generation of conjugated carbon–carbon double bonds, was the main reaction for PVC during photo‐aging at low temperature. Meanwhile, the photo‐oxidation was also obvious and could not be neglected. It clearly confirmed that the absorption peaks of conjugated carbon–carbon double bond increased and shifted to longer wavelength during photo‐aging in the UV‐abs analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Effects of polyvinyl chloride and aluminum trichloride on structure and property of polyaniline composite films by electron beam deposition

Polyaniline (PANI) composite films were prepared on silicon and quartz glass substrates by electron beam deposition (EBD), using polyvinyl chloride (PVC), aluminum trichloride (AlCl₃), and mixture of PVC and AlCl₃ as dopants. Molecular structure, morphology, optical, and electrical properties of PANI composite films were investigated by Fourier transform infrared spectroscopy, UV–vis spectroscopy, four‐probe method, and atomic force microscope. The results show that PANI film prepared by EBD has a similar molecular structure with initial powder. PVC is dehydrochlorinated under electron beam irradiation, but HCl fails to protonate the quinoid site of PANI during films deposition. AlCl₃ doped in PANI films induces the decrease of surface resistance and the formation of a two‐layered morphological structure in composite film. In addition, AlCl₃ enhances the decomposition of PVC and increases the surface resistance of (AlCl₃, PVC)‐doped PANI composite film. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Surface‐enhanced infrared absorption (SEIRA) and its use in analysis of plasma‐modified surface

A thin film (<10 nm) of fine metal clusters (silver or gold) with an island form was deposited on a CaF₂ salt plate by slow vacuum thermal evaporation. Molecular layers of stearic acid, p‐nitrobenzoic acid, and m‐nitrobenzoic acid (p‐ and m‐NBA) were prepared on the thin metal film. The system was then examined by infrared spectroscopy attenuated total reflection (IR–ATR). It was found that through the interaction between the metal islands film and the electric field of the incident IR beam the infrared absorption of the molecule layers adsorbed on the islands was enhanced by a factor of 17. The surface‐enhanced IR absorption (SEIRA) also presents a selection rule. This method was then used to study the surface modification with O₂ and NH₃ plasma and the plasma polymerization of allylamine. This is the first time that SEIRA has been used in plasma investigations. A model is provided to explain the interactions between the metal islands film and the electric field of the incident IR beam in the SEIRA. The in‐plasma‐built functional groups can be further used to graft biofunctional molecules for the biomedical industry. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1231–1237, 1999