The adhesion to hydrophilic surfaces of plasticized poly(vinyl chloride) containing novolac - hexamethylenetetramine

The addition of relatively small amounts of novolachexamethylenetetramine phenolic to poly(vinyl chloride) plastisols has been used to increase the adhesion of the fused plastisol to hydrophilic surfaces like those of glass and steel. The principal mechanism by which this occurs has been studied and found to be, first, the dissolution of the novolachexamethylenetetramine complex in the plasticizer; second, the interaction of the nearby phenolic groups with the hydrophilic surface; and, third, the chain extension and crosslinking of the phenolic to form perhaps a very open cell foam structure through the plasticized vinyl that is attached to the substrate. Additional adhesion may arise from the adsorption of particles of the undissolved novolac complex on the surface and from viscoelastic effects from the cured vinyl composition. The problem with the decreased adhesion of thin plastisol coatings was also studied. It was found to be unrelated to the thickness per se. Rather, it seems to arise from the loss of hexamethylenetetramine at the air interface. Though hexamethylenetetramine is lost also from thicker coatings, the concentration near the adherend interface is less affected.     

Structure and properties of poly(vinyl chloride)‐triallyl cyanurate plastisols

Triallyl cyanurate (TAC) has been used as a reactive plasticizer to promote the high‐temperature creep resistance of poly(vinyl chloride) (PVC) plastisols. The resultant crosslinked structure is characterized using gel content and swell ratio measurements as well as Fourier transform infrared spectroscopy. The crosslinking reaction was initiated using peroxide. The effect on the network structure of using a free radical scavenger in the formulation has also been studied. The gel yield and crosslink density in the gel increase with increasing TAC concentration in the plastisol, while the grafted PVC fraction and the residual unsaturation of TAC behave in the opposite way. Introduction of TAC into the plastisol promotes creep resistance at high temperatures, and the logarithmic creep rate was found to decrease linearly with increasing crosslink density.     

NOTE The Application of Surface Analysis Techniques in the Adhesive Bonding of Oily Automotive Steel

There are fewer papers on the adhesive bonding of steel for structural applications than for aluminum and titanium alloys. However, the approach to the adhesive bonding of all three adherends has been similar, that is, the surfaces are pretreated prior to bonding. Trawinski, et al.^1,2,3 reviewed several conversion coatings or etching processes used for steel. Haak and Smith⁴ selected two surface treatments among nineteen based on minimal cost, simplicity and good durability. Smith⁵ has reported work on stainless steel-epoxy bonds under hydrothermal stress. Bischof, et al.⁶ investigated the effect of surface pretreatment of steel on bonding strength obtained with polyvinyl chloride. Ziane, et al.⁷ identified four fracture zones resulting from shear loading of epoxy bonded galvanized steel following four different surface pretreatments. But in some cases, as in the automotive industry, there is a need to bond oily steel directly without surface pretreatment. Rosty, et al.⁸ have reported a study of the role of fillers and cure temperature on the shear strength of oily steel bonded with epoxy. None of the reported research utilizes both microscopic and spectroscopic techniques to analyze the fracture surfaces.     

Unique benzoate plasticizer for reducing viscosity and fusion temperature

Plastisol viscosity reduction and control is an important property specification in many vinyl plastisol formulations. A unique benzoate plasticizer is under development that functions as a viscosity reducer. It also is a highly solvating plasticizer in standard plastisol systems. Data are presented on the effects of the new benzoate plasticizer on the properties of phthalate‐ and benzoate‐containing plastisols and vinyl sheet.     

EIS study of organic coating on zinc surface pretreated with environmentally friendly products

The life time of many steel structure can be remarkably improved by protecting the steel with zinc layers. However, also the zinc coating can be involved by corrosion phenomena with the consequence that some steel surface is unprotected.

The reduction of the corrosion rate of zinc is therefore an important topic. These results can be obtained by introducing zinc alloys with lower corrosion rate (ZnNi, ZnFe, etc.) or by protecting the zinc surface with organic or inorganic layers able to reduce the corrosion rate.

In the past a very popular way to reduce the corrosion rate of zinc was the use of chemical conversion layers based on Cr⁶⁺, able to increase the passivation tendency of the zinc (chromating). This procedure is quite effective also for improving the adhesion of organic coatings deposited on the zinc surface, but there is the important problem that the use of chromium salts is now restricted because of environmental protection legislation.

It is therefore very important to develop new zinc surface treatments environmentally friendly to improve the corrosion resistance of zinc and the adhesion with the final organic protective layer.

In this paper a characterisation of environmentally friendly conversion treatments based on Cr³⁺ for zinc surface will be reported in comparison with traditional based Cr⁶⁺ pretreatments on different zinc layers protected by organic coatings.

The samples were studied using EIS measurements, and the data analysis was mainly based on the discussion of the mathematical combination (ratio, product, etc.) of different parameters of the equivalent electrical circuit model.

This approach was found more useful, in order to compare the performance of different materials, in comparison to the simple discussion of the numerical values of the parameters, being these values generally influenced by random defects present in the samples, affecting the measured impedance.

The results showed that the performance (adhesion and corrosion protection) of good formulated Cr³⁺ based pretreatments are not far from the results, which it is possible to obtain with industrial Cr⁶⁺ pretreatments and therefore Cr³⁺ conversion layers can be considered an interesting alternative to the traditional ones.     

无卤塑溶胶的开发及应用

采用无卤型丙烯酸树脂和环保型增塑剂及分散剂制备低温速固化的无卤塑溶胶。考查了增塑剂和分散剂用量对塑溶胶黏度、固化物强度的影响,不同固化温度和时间对强度的影响。结果表明,增塑剂含量越多,体系的黏度越小,固化物越软。适量的分散剂可以降低塑溶胶体系的黏度而不影响固化物强度。硅烷偶联剂的使用可以提高塑溶胶对基材的附着力。     

低温塑化型PVC塑溶胶用封端聚氨酯的研制

以异佛尔酮二异氰酸酯(IPDI)、聚己二酸丁二醇酯(PBA)和丙酮肟(DMKO)等为原料合成了封端聚氨酯(BPU),并以BPU作为附着力促进剂,加入到聚氯乙烯(PVC)增塑糊中,制备出一种低温塑化型车用PVC塑溶胶。研究了BPU对车用PVC塑溶胶的附着力、拉伸强度、断裂伸长率、剪切强度和耐过烘烤性能的影响。结果表明:加入适量的BPU后,可以明显提高车用PVC塑溶胶在电泳漆板上的附着力,使塑溶胶的塑化温度降低至120℃左右;经170℃烘烤后,塑溶胶仍保持较好的附着力且不黄变,其拉伸强度、断裂伸长率和剪切强度分别提高了62%、41%和57%。     

Fusion behavior of plastisols of PVC studied by ATR-FTIR

The behavior of PVC plastisols during gelation and fusion was studied by the ATR-FTIR technique (Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy). DBP, DOP, and DIDP, three common phthalate plasticizers for PVC, were used in plastisols formulations. Three heating rates—5, 10 and 15°C/min—and formulations with different plasticizer concentrations were studied. The IR spectra of a plastisol coincides with the IR spectra of the plasticizer except for the bands at 1435 and 613 cm^?1 from the PVC (CH₂ wagging and C—Cl stretching, respectively). When the plastisol is heated, a progressive decrease of the plasticizer bands areas can be observed, while bands from PVC increase their intensity, probably because of the adsorption of the plasticizer by the resin. On cooling, the area of all bands follows the same path as when heating, but the paths separate at a certain temperature, showing the irreversible nature of this process. The analysis of the band at 1280 cm^?1 (C(O)—O from plasticizer) during heating and cooling, shows that the temperature of separation areas (T_s) takes place at temperatures coherent with plasticizer compatibility. Studies at different heating rates and different plasticizer content are in good agreement with results using other techniques, available in the literature.     

Bonding of Natural Rubber to Steel: Surface Roughness and Interlayer Structure

This paper is concerned with two aspects of the adhesion produced by the vulcanisation bonding of a simple natural rubber (N.R.) compound to mild steel. Adhesion was measured using a 45° peel test.

When the N.R. was bonded, using a proprietary bonding agent (Chemlok 205/220), to 'smooth' steel (acid etched) or to 'rough' steel (phosphated) high values of peel energy (≥ 4.5 kJm^-2), and good environmental resistance to water were obtained, with failure cohesive largely within the rubber. The highest values of peel energy (≈ 7.5 kJm^-2) were associated with a phosphated surface which consisted of plate-like crystals which directed the stresses away from the substrate in a way which produced a failure surface within the rubber which showed extensive tearing and cracking.

The nature of the layer formed in the interfacial region by interaction between bonding system and rubber was investigated using a chlorinated rubber as a 'model compound' representing the adhesive and uncompounded N.R. to represent the rubber. When a blend of the two was heated in air at 150°C, evidence was found of a solid state chemical reaction in which carbonyl groups were incorporated into the blend which became visually homogeneous. Further evidence points to the relevance of this change to adhesion in rubber-to-metal bonding.     

Pressure Sensitive Adhesives Based on VectorR SIS Polymers I. Rheological Model and Adhesive Design Pathways

Dexco Polymers (a Dow/Exxon partnership) has been manufacturing Vector^R SIS polymers since 1990.¹ This paper describes experiments carried out to study Vector SIS polymers and model pressure sensitive adhesive (PSA) formulations based on Exxon Chemical's Escorez^R 1310LC tackifier. The adhesive behavior of tackified polymers was quantitatively analyzed by applying the rheological principle of time-temperature superposition² and the mapping approach,^3,4 and the pressure sensitive rheological model⁵ developed earlier. This model⁵ was developed by expanding and modifying an equation [adhesive fracture strength = (intrinsic adhesion) × (bulk energy dissipation)] proposed by Gent et al.^6,7 and Andrews et al.^8,9 This study delivers two key results. The first is that the fracture strength of the PSA/steel bond is the multiplication of three terms: the intrinsic (or interfacial) adhesion, the bonding and the debonding terms (Fig. 1). The debonding term is correlated with the logarithm of the loss modulus at the PSA debonding frequency or with the logarithm of the monomeric friction coefficient of the block copolymer/tackifier system. Both the loss modulus and the monomeric friction coefficient measure the energy dissipation in the bulk adhesive. The second is that PSA design pathways can be established by a mapping approach in the rheological space of the plateau modulus versus the loss modulus peak position in the frequency scale (Fig. 2). Plateau modulus is the bonding parameter because it measures the wetting capability of the adhesive with the substrate surface. The loss modulus peak position is the debonding parameter because it corresponds approximately to the time scale (or the frequency scale) in which one deforms the adhesive to maximize energy dissipation. Therefore, the tackifier and oil combination lowers the plateau modulus, but increases the T_g of the polyisoprene phase of the SIS polymer. This increase in T_g is equivalent to the lowering of the rate of local rearrangement (frequency of segment jumps) of the polyisoprene chains of the block copolymer. An optimal “tackification pathway” in this rheological space is achieved by tailoring the tackifier type and T_g, and the amount of oil used in the PSA.

In brief, the PSA rheological model and mapping approach described in this work for Vector SIS polymers give a comprehensive understanding and adhesive design pathways. This concept and approach not only allow raw material suppliers to improve and design better tackifier and polymer products, but also provide PSA formulators a quantitative tool to achieve PSA end property results.     

铝合金表面钒酸铈改性环氧涂层的制备与性能研究

通过水热合成法制备钒酸铈(CeVO4)纳米填料,将CeVO4分散到环氧树脂中获得改性涂层.分别涂覆在打磨后碱洗处理铝合金和直接喷砂处理铝合金上.采用XRD、FT-IR和SEM对CeVO4粉体进行表征,并通过附着力测试、电化学阻抗和长期浸泡实验对改性前后的涂层进行研究.结果表明:利用水热合成法可成功制备CeVO4纳米填料...     

Biomimetic Preparation and Characterization of Bioactive Coatings on Alumina and Zirconia Ceramics

For the preparation of bioactive coatings on alumina and zirconia ceramic surfaces a fast biomimetic method using a supersaturated solution containing Na⁺, Ca²⁺, Cl⁻, HCO₃⁻, and PO₄³⁻ ions was used. The coatings were analysed with the use of an X-ray diffraction spectrometer and a transmission electron microscope equipped with an energy-dispersive spectroscopy detector. After the precipitation both coatings were composed of poorly crystallized, nanosized, plate-like particles with the octacalcium phosphate (OCP) crystal structure. The adhesion of the coatings was improved by a heat treatment at 1050°C for 1 h. During this heat treatment the calcium phosphate layer, deposited from a supersaturated solution onto the surface of the substrates, was sintered to form a dense coating. At the same time the OCP crystal structure was transformed into that of hydroxyl apatite, the coating's crystallinity was increased, and the particles grew isotropically up to 300 nm in size. The bioactivity of the coated ceramic was confirmed before and after the heat treatment using a simple simulated body fluid test.     

Brass Powder in Rubber Vulcanizates. The Effect on Adhesion

Brass plating is presently used for promoting the adhesion of rubber to steel cords used in tires. It is generally accepted that the adhesion is due to chemical bonds that are formed between the rubber and brass,¹ although evidence has been obtained indicating that the adhesion is the result of a physical phenomenon.² In addition, a catalytic oxidation theory also has been advanced.¹

Natural rubber vulcanizates loaded with brass powder showed an increase in crosslinking (by swelling measurements), indicating an interaction or bonding between the rubber and brass. Techniques previously employed with reinforcing fillers such as carbon black were used to evaluate the effect of brass on adhesion. The addition of brass powder decreased the scorch time and optimum cure time indicating that the rubber immediately surrounding the brass was being cured at a faster rate. Copper powder, on the other hand, inhibited the cure completely. When exposed to air or oxygen, even small amounts of brass catalyzed oxidation of the rubber.     

电流密度对5,5-二甲基乙内酰脲体系电镀银的影响

采用5,5-二甲基乙内酰脲体系在黄铜及不锈钢基体上沉积厚度为6μm左右的银镀层,镀液组成和工艺条件为:硝酸银25 g/L,5,5-二甲基乙内酰脲80 g/L,烟酰胺60 g/L,碳酸钾40 g/L,复合光亮剂(包含2-巯基苯骈噻唑、1,4-丁炔二醇和十二烷基硫酸钠)2 mL/L,pH 10.5,温度60°C,电流密度0...     

Surface modification of polymeric materials by atmospheric plasma treatment

We have been able to generate the wide and stable plasma in open air (discharge distance, 35 cm; discharge-electrode length, 16 m at maximum) using a pulse with a high voltage and narrow wave form. This was applied to treat the surface of rather non-polar plastics intended for the improvement of adhesion of over-coated layers such as coatings, adhesives and printing inks. The treating system (APPS) consists of the apparatus for generating the plasma and the treating process. Polypropylene (PP) and tetrafluoroethylene perfluorovinyl ether copolymer (PFA) have been examined as typical examples of the plastics. The adhesion strength of urethane paint on PP molding and of a PFA film on steel was significantly improved by the APPS treatment. The characteristics of the surface layer were evaluated by means of scanning electron microscopy, electron spectroscopy for chemical analysis, atomic force microscopy, and contact angle measurement, and it was found that hydrophilic functional groups were introduced into the surface layer of the plastics. The level of the improvement changed with time after treatment; this is discussed from the viewpoint of functional group movement from the surface to the interior. Application of paints on PP bumpers by the electrostatic spray method was also accomplished. The use of a small amount of nitrogen-containing compound following APPS treatment decreased the electrical resistance of the PP surface from 10¹⁶ to 10¹¹ Ω, and highly effective electrostatic coatings of PP bumpers could be realized.     

PVC plastisols: Preparation,properties, and application

The engineering issues of plastisol preparation, composition, properties, and application are considered. Special attention has been paid to the adhesion characteristics of plastisol coatings.     

Processing of Polymer-Derived Ceramic Composite Coatings on Steel

Polymer-derived ceramic composites are being investigated as environmental barrier coatings to protect stainless steel from oxidation and carburization. Coatings have been produced using poly(hydridomethylsiloxane) as a preceramic polymer and titanium disilicide as an expansion agent. Processing parameters have been optimized and a relationship has been derived to predict the final coating thickness based on slurry viscosity and dip coating withdrawal speed. Microstructural analysis reveals a composite coating of oxidized filler particles in a silica matrix. A diffusion layer is visible at the coating–steel interface, indicating good bonding. The optimized coatings are ∼18 μm thick, and have some residual porosity and a density of 2.56 g/cm³.     

Plasticizer structure/performance relationships

Plasticizers for poly(vinyl chloride) may be organized into eight chemical families and by seven key performance criteria. Cost-effective general-purpose phthalates provide a base line for comparing all other plasticizers. The wide range of performance characteristics associated with various phthalate isomers substantiates the large proportion of phthalate esters that are utilized as plasticizers. This article summarizes plasticizer structural/performance relationships using quantitative comparisons of cost, plasticizing efficiency, plastisol solvation characteristics, dryblending, volatility, and low temperature performance properties in PVC. Some generalizations are also made concerning structural effects of the alcohol isomers used in the syntheses of the various types of plasticizer esters.     

Determination of Quasiequilibrium Work of Adhesion of Elastic Coatings

Present methods for the determination of adhesion bonding of elastic polymeric materials entail certain experimental difficulties. In particular, the necessity of strict centering of the test specimen, and the difficulty associated with application of a homogeneously distributed stress over the whole cross-sectional area (homogeneous detachment or shear), or the excessive expenditure of work resulting from polymer deformation (peel).^1,2

We are suggesting a method to determine the quasi-equilibrium work of adhesion during the peeling process for elastic polymeric coatings, the value of which, as was demonstrated experimentally, does not depend on the coating thickness, deformation or rate of peeling.     

Application of atactic polypropylene in technology of chemical foaming of PVC pastes

A preliminary study of the use of by-product atactic polypropylene as a replacement for plasticizer in chemically blown plastisol is presented. The effect of varying amounts of PP and plasticizer on the elastic property was studied. Atactic PP has been shown to be useful as a plasticizer substitute in plastisols in amounts apt. 10%.