Surface Modification of Poly Vinyl Chloride (PVC) Using Low Pressure Argon and Oxygen Plasma

In this study, commercial poly vinyl chloride （PVC） films were treated by oxygen and argon plasmas in a cylindrical glass tube which was surrounded by a DC variable magnetic field, with different sample positions in the plasma reactor and also different exposure durations. Effects of the plasma treatment on the hydrophilic properties of the films were studied by mea- suring the water drop contact angle on the surface of the samples. The surface topography of the untreated and plasma treated films was analyzed and compared by atomic force microscopy （AFM）. The optical characteristic changes in treated samples were investigated using reflective spectrophotometry. Also, the chemical changes which appeared on the surface of the samples were investigated using Fourier transform infrared spectroscopy （FTIR）. The results show that the plasma treated PVC becomes more hydrophilic with an enhanced wettability. A sharp de- crease in the water contact angle may also be a consequence of the surface texturization. The aging effect on wettability of the samples was also investigated. The results show that the effect of oxygen plasma on the surface properties of the samples is more pronounced compared with that of argon plasma.

Development of a Poly(vinyl chloride)-based Nitrate Ion-selective Electrode

The authors developed a nitrate ion-selective electrode（ISE） based on poly（vinyl chloride）（PVC） membrane with methyltrioctylammonium nitrate as a carrier and 1-decanol as a plasticizer.The performance of the nitrate-sensitive membranes was optimized by tuning the composition of components.The electrode exhibits a linear response with a Nernstian slope of（52±1.0） mV per decade for the nitrate ion concentration ranging from 5.8×10-5 mol/L to 1.0 mol/L.The electrode can be used to detect a low concentration of nitrate ions down to 3×10-5 mol/L in a pH range of 2.1―11.5 without any compensation.The advantage of the electrode includes simple preparation,short response time and good repeatability.The detection performance of the novel electrode on nitrate ions has been tested for water samples.

Rare Earth Stearates as Thermal Stabilizers for Rigid Poly(vinyl chloride)

A series of stearates with different rare-earth ion were investigated as thermal stabilizers for rigid PVC at 180 ℃ in air. Their stabilizing efficiency was based on measuring the rate of dehydrochlorination. The resulted revealed the higher stabilizing efficiency of the investigated rare-earth stearates as thermal stabilizers for rigid PVC compared with the thermal stabilizers for industry: calcium stearate, zinc stearate, butyl stannum mercaptide, phosphite esters, β-diketone and epoxidized sunflower oil. This was well illustrated by longer incubation period (T_S) values and lower rate of dehydrochlorination. The stable efficiency was affected by the nature of rare-earth element's individual electronic shell. The mechanism for the stabilizing effect of rare-earth stearates was proposed. The result was experimentally proved based on IR spectrum.

Creep Behaviour of Wood Flour/Poly(vinyl chloride) Composites

The experimental creep data were focused on wood-flour （WF）/poly vinyl chloride （PVC） composites with the variations in additive concentrations of wood flour, silane coupling agent, organomodified montmorillonite （OMMT） and nano-cacium carbonate （nano-CaCO3）. Their effects were analyzed using the Four-element Burger Model incorporating microscopic mechanisms. Total creep strain was low with increasing WF while elastic strain was high and plastic flow strain was low in modeling. Modification of WF with silane was beneficial to creep resistance, so did adding low ratio of OMMT （1.5 wt%） and nano-CaCO3 in composites. Thus, it was effective in reducing creep either by stiffening the PVC matrix using rigid nano-particles or by improving their adhesion with resin. However, superfluous quantity of any additament did not benefit the improvement owing to either earlier destruction of their agglomerates or stress-concentrated cracks in the over-incrassated interface.

Antiplasticizing Effect of MOCA on Poly(vinyl chloride)

An obvious antiplasticizing effect has been observed in PVC with small amount of MOCA, 3,3’-dichloro-4,4’-diamino-diphenylmethane. PVC-MOCA interaction and crystallization behavior of PVC/MOCA blends were investigated in detail to explain the mechanism of antiplasticization on the basis of a series of techniques including DMA, FTIR, and DSC. The results of mechanical properties tests show that the tensile strength of PVC with 5 phr of MOCA reaches a maximum value, 69.5 Mpa, which is about 23 % higher than that of pure PVC. The rise in tensile strength was attributed to an antiplasticizing effect of MOCA on PVC as confirmed by DMA measurements. The evidences from FTIR reveal that a strong hydrogen-bonding interaction takes place between the nitrogen atom of –NH2 groups in MOCA and the methine proton of PVC repeat units. The results of DSC analysis indicate that crystallization behavior of MOCA is suppressed completely and the crystallinity of PVC decreases with the increase of MOCA amount.

Influence of Annealing and Additives on the Crystallization Behavior and Properties of Poly(vinyl chloride)

Acetanilide （AC）, adipic acid （AA） and potassium hydrogen phthalate （PHP） were chosen as additives to accelerate PVC crystallization and improve its mechanical properties. The influences of the additives and annealing on the crystallization behavior, micromorphology and the tensile properties were investigated by the thermal analysis, scanning electron microscopy （SEM） and the tensile test. Based on the analysis results, it was concluded that the melting peaks ranging from 110 to 200 ℃ and 200 to 240 ℃ were caused by the fusion of the fringed micelle crystals and chain-folded crystals respectively. AC advanced the fringed micelle crystal to develop, while AA and PHP promoted obviously the chain-folded crystal to grow. The addition of the foreign additives did not change the growth pattern ofPVC crystallites, the growth of the micelle crystal was favorable at 110 ℃, and the chain-folded crystal was developed at higher temperature. For PVC/ AA and PVC/PHP, when annealed at 110 ℃, a regular nest like network was formed, the crystallinity and the crystallite size were increased as well, and as a result, the tensile strength, Young＇s modulus and the elongation at break point were improved simultaneously and greatly.

Structures of LDHs Intercalated with Ammonia and the Thermal Stability for Poly(vinyl chloride)

MgAl-NH3 LDHs (layered double hydroxides), ZnAl-LDHs and ZnAl-NH3 LDHs with different molar ratio of Al/ammonia were synthesized by co-precipitation method. The synthetic LDHs samples were characterized by XRD, FT-IR, TGA-DTG and SEM techniques and tested by Congo red method. In addition, after PVC (Poly vinyl chloride) and DOP (Dioctylphthalate) were added to LDHs, the thermal stability for PVC was characterized by TGA-DTG. The results indicated that LDHs intercalated with ammonia improved thermal stability for PVC significantly, MgAl-NH3 LDHs (Mg2+:Al3+: NH3·H2O = 3:1:0.5) and ZnAl-NH3 LDHs (Zn2+:Al3+:NH3·H2O=2:1:1.5) showed the best thermal stability for PVC, interlayered space of LDHs became larger by intercalating ammonia.

Synthesis of Bio-Plasticizer from Soybean Oil and Its Application in Poly(Vinyl Chloride) Films

Herein,epoxidized soybean oil methyl ester(ESOM)plasticizer was synthesized for the preparation of plasticized poly(vinyl chloride)(PVC)films by the alcoholysis and epoxidation.The chemical structure of ESOM was investigated by infrared spectrum and 1 H nuclear magnetic resonance.The effect of content of ESOM and petroleum based plasticizer di-2-ethylhexyl phthalate(DEHP)on the performance of plasticized PVC films was studied.The result showed that substituting DEHP with ESOM can improve the thermal stability of plasticized PVC films.When the weight ratio of ESOM and PVC is fixed at 1:2,plasticized PVC film presents higher elongation at break(350.8%vs.345.1%)and lower tensile strength(14.21 MPa vs.15.8 MPa)compared with PVC plasticized with DEHP.ESOM showed less weight loss than DEHP in all solvents.The excellent migration resistance of ESOM is helpful to improve stability of plasticized PVC films.In all,the obtained bio-based plasticizer will be potential to replace petroleum based plasticizer DEHP in flexible PVC materials.

Preparation of MgAl LDHs Intercalated with Amines and Effect on Thermal Behavior for Poly(vinyl chloride)

MgAl LDHs intercalated with CO(NH2)2, NH4Cl and NH3·H2O were prepared by co-precipitation and XRD, FT-IR, TGA-DTA and SEM techniques were employed for characterization. The results indicated that the layer-layer spacing of LDHs was enlarged by 0.169, 0.285 and 0.227 Åwith the intercalation of CO(NH2)2, NH+4 and NH3, separately. The effects on thermal stability and degradation behavior of synthesized LDHs where mole ratios of Mg/Al/urea = 3:1:1, Mg/Al/NH4Cl = 3:1:1.5 and Mg/Al/NH3·H2O = 3:1:0.5 were investigated by Congo Red Method and thermogravimetric analysis (TGA) from 25°C - 800°C under N2. The TGA and DTA results showed, by incorporating 5% MgAl-CO(NH2)2 LDH, the dehydrochlorination temperature of PVC composites is 12°C higher than MgAl-NH+4 and MgAl-NH3 LDHs. MgAl-NH3 LDH enhances the ending temperature of the first degradation stage of PVC composites by 8°C compared with MgAl LDH. The LDH intercalated with CO(NH2)2 is proved to be an effective thermal stabilizer for PVC processing.

PHASE EQUILIBRIUM FOR THE TERNARY SYSTEM VINYL CHLORIDE-CHLORINATED POLYETHYLENE-POLY(VINYL CHLORIDE)

Swelling capacity of vinyl chloride (VC) in chlorinated polyethylene (CPE) with 25—40 wt% Cl at temperature 30—57℃ was studied and their relationships were correlated with Langmuir and Freundlich adsorption equations. A ternary phase diagram for VC-CPE-PVC was also established. In-situ polymerization conditions of CPE-g-VC were proposed and CPE content control was analyzed for the manufacturing process of CPE-g-VC graft product based on results of phase equilibrium study.

Microstructure and Mechanical Properties of Poly (Vinyl Chloride) Modified by Silica Fume /Acrylic Core-Shell Impact Modifier Blends

This research explored replacing acrylic core-shell impact modifier （AIM） by silica fume to toughen PVC. 100%, 75%, 50% and 25% of AIM （8 phr） were substituted by silica fume in PVC respectively, and then processed by dry blending and twin-screw extrusion. Severe silica fume agglomeration was observed by scanning electron microscope （SEM） in the PVC matrix when 8 phr pure silica fume was used and processed by screw speed of 20 rpm. Its tensile strength was thereby reduced by 38% comparing to unmodified PVC. The silica fume was successfully dispersed while the screw speed was slowed down to 10 rpm to give a stronger screw torque and a longer melt residential time in the extruder. The tensile strength was ’recovered’ to a level comparable to unmodified PVC. Impact test were performed on all formulations extruded at 10 rpm screw speed and synergetic toughening effect was found with 50% substitution and it had the impact strength that was comparable to 8 phr pure AIM toughened PVC.

Microwave Synthesis of Inulin Acetate as Potential Bio- Based Additive for Poly(Vinyl Chloride)

The paper presents the findings of an experimental study on the microwave synthesis (MW) of inulin acetateand its possible application as bio-additive in poly(vinyl chloride) (PVC). The obtained inulin acetate has beenidentified and characterized by spectroscopic methods. Advantages of the MW compared with the conventionalsynthesis were defined. In order to evaluate possible application of the product as bio-based additive forpolymers, effect of the inulin ester on PVC behavior and characteristics has been investigated by differentialscanning calorimetry (DSC) and deformation upon extension. Experimental results show that in concentrationrange up to 30.0 wt. % the inulin ester influences positively the properties of PVC causing effect similar toplasticizing one. At concentration over 30 wt.% the ester shows more specific behavior, which will be furtherinvestigated. Conclusions about potential application of MW synthesized inulin acetate as bio-based additive forPVC have been drawn.

Kinetics of Vinyl Chloride Polymerization with Mixture of Initiators

Kinetic models for the rate constants of vinyl chloride polymerization in the presence of initiator mixtures were proposed. They may be used to design the initiator recipes for the vinyl chloride polymerization with uniform rate at different temperatures at which various grades of poly(vinyl chloride) will be prepared.

Evaluation of Lignin-Calcium Complex as Thermal Stabilizer for Poly Vinyl Chloride

Chemical modification of lignin was carried out by reacted it with HI acid, then the modified lignin treated with calcium hydroxide to prepare calcium-lignin chelating complex, this derivative was examined as thermal stabilizer for PVC, thermal degradation of PVC neat as blank and containing three weight percents (1, 2, and 4) into polymer was accelerated by heat treatment at 190°C for 2 hr. then PVC films were casting from THF solvent with thickness 0.03 mm. Thermal stabilization activity of this derivative was investigated by using infrared spectroscopy, according to the results obtained calcium-lignin complex have suitable activity to increased PVC stability at low concentration depending on it’s ability to reaction with HCl as well as the chemical structure of lignin that contain phenolic properties.

十二烷基硫酸钠表面改性水滑石对PVC热稳定性能的影响

采用十二烷基硫酸钠(SDS)对镁铝镧碳酸根型水滑石(LDHs)表面进行湿法改性,讨论了不同改性条件对聚氯乙烯(PVC)静态热稳定性能的影响,通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)和红外光谱仪(FTIR)进行表征。采用刚果红试纸法、烘箱变色法、转矩流变法、热重分析法等测定了SDS改性前后PVC/LDHs样品的热稳定性能。结果表明,恒定pH=7,SDS为LDHs质量的10%,水浴80℃下搅拌3 h,改性效果最佳;SDS并未破坏LDHs的晶体结构,仅吸附在表面,增强了与PVC的相容性;改性后的PVC/LDHs样品静态及动态热稳定时间达65、28.5 min,改善了后期着色,更易塑化成型;最大质量损失速率对应温度为346℃,较未添加前增加55℃,能较好地抑制PVC的热降解。

PVC树脂产品质量提升总结

针对PVC树脂“鱼眼”数超标问题,进行了系统排查分析。通过采取增大注水速率,调整助剂配方和用量等措施,减少了PVC树脂中的“鱼眼”,提高了产品的优等品率。

PVC/TPU共混材料静动态力学性能及本构模型研究

利用万能材料试验机和高速拉伸试验机对2种成型方式和6种共混比的聚氯乙烯/热塑性聚氨酯(PVC/TPU)共混材料开展静动态拉伸力学性能测试,并基于断裂伸长率和邵氏硬度进行成型方式和共混比优选。进一步获取了共混材料在较宽应变率范围(0.001~700 s-1)的应力⁃应变数据,并进行了拉伸断面的微观表征。结果表明,模压成型材料断裂伸长率更高,共混比为90/10时材料具有最高的断裂伸长率,邵氏硬度符合试验假人软组织材料的硬度范围(邵尔40~70 A)。共混比为90/10(PVC/TPU)材料在静动态载荷下均具有显著的应变率效应。选取朱⁃王⁃唐(ZWT)方程和Sherwood⁃Frost方程构建了材料的本构模型,对比发现Sherwood⁃Frost方程拟合效果更好。形貌分析发现,静动态加载下,材料均为典型的脆性断裂,未出现明显的相分离现象。随着应变率的增加,断面逐渐变粗糙,并产生空穴及微小裂纹。