钴盐对钢丝帘线与橡胶粘合性能的影响

对环烷酸钴，硼酰化钴，新癸酸钴等钴盐粘合增进剂对高和低铜质量分数钢丝帘线与橡胶粘合性能的影响进行了研究。结果表明，胶料中加入钴盐能够提高强伸性能和与钢丝帘线的初始粘合唱 力及耐盐水老化能力。     

Analysis of the Molecular Structure at the PPS/Copper Interphase and its Role in Adhesion

X-ray photoelectron spectroscopy (XPS) was used to examine the interfacial chemistry in polyphenylene sulfide (PPS)/copper bonded laminates. Several surface pretreatments were studied including a simple methanol wash, two acid etches, thermal oxidation and chemical oxidation. Peel test analysis showed poor adhesion to the methanol-washed and acid-etched foils, giving a peel strength of only 3-5 g/mm. XPS analysis of the failure surfaces revealed a large amount of inorganic sulfide at the interface with reduction of the copper oxide. Chemical oxidation using an alkaline potassium persulfate solution gave a matt-black surface consisting of primarily cupric oxide. These samples showed improved adhesion and XPS analysis of the failure surfaces revealed fracture through a mixed PPS/cuprous oxide layer. A simple thermal oxidation yielded a cuprous oxide surface layer and laminates bonded to these surfaces showed a more than ten-fold increase in peel strength. XPS analysis of the failure surfaces showed much lower amounts of interfacial copper sulfide and it was postulated that excess sulfide at the interface was responsible for the poor adhesion observed for other pretreatments.     

Adhesion enhancement of diamond coating on minor Al-modified copper substrate

We report on the enhanced interfacial adhesion of diamond coating on copper substrate modified by a small fraction of Al. For pure copper substrate, the diamond coating formed tends to crack and delaminate, primarily caused by a slight accumulation of detrimental graphite intermediate layer and thermal stress induced by mismatch of the coefficients of thermal expansion. Additions of 1 and 3 at.% Al to the copper substrate gradually decrease the intermediate graphitic phase. At the higher Al concentration, an aluminium oxide forms at the coating–substrate interface, and graphitic/amorphous carbon is completely inhibited, leading to significantly enhanced interfacial adhesion of diamond coating. The electron structure of copper is not observed to significantly alter on this Cu–Al dilute alloy. The alumina barrier layer preferentially formed on copper surface is believed to play a key role in preventing graphitization and adhesion enhancement.     

Effect of Tetrachlorobenzoquinone on the Adhesion between Rubber Compound and Brass-plated Steel Cord

The adhesion between tetrachlorobenzoquinone (TCBQ)-loaded rubber compound and brass-plated steel cord was studied to understand the role of TCBQ as an adhesion promoter. With loading of TCBQ in the rubber compound the cure rate became slow, but the change in physical properties was not significant. An improvement of the adhesion was obvious with low loading of TCBQ at the range of 0.5 phr while an adverse effect was observed with high loading at 2 phr. The addition of TCBQ for the improvement of adhesion has a greater effect before aging because TCBQ contributes to form a large surface area of copper sulfide via accelerated copper diffusion into the rubber bulk. However, higher TCBQ loading as well as longer aging time leads to a great extent of copper migration into the rubber and excess growth of zinc oxide layer, resulting in decreased adhesion. The adhesion interphase before aging, between a thin brass film and a rubber compound, investigated using AES showed no difference except that sulfur increased with increasing TCBQ loading. On the other hand, the adhesion inter-phase was changed after humidity aging. The copper content decreased at the adhesion interphase while it increased in the rubber layer with increasing addition of TCBQ.     

Adhesion promotion of the polyimide–copper interface using silane-modified polyvinylimidazoles

In order to promote the interfacial adhesion strength between polyimide (PI) and copper, the copper surface was treated with polyvinylimidazole (PVI) or silane-modified PVIs. They were prepared by the copolymerization of 1-vinylimidazole (VI) with the following silane coupling agents: 3-(N-styrylmethyl-2-amino-ethylamino)propyltrimethoxysilane (STS), vinyltrimethoxy silane (VTS), allyltrimethoxy silane (ATS), and γ-methacryloxypropyltrimethoxysilane (γ-MPS). The mole ratio of the silane coupling agent to VI was fixed at 1 : 1. The lap shear strengths between PI and copper were measured at the following different bonding temperatures: 290, 320, 350, and 380°C. In each case, the maximum adhesion strength was obtained at 350°C. VTS-modified PVI showed the best performance on adhesion promotion of the PI–copper interface. Fourier transform infrared spectroscopy was applied to investigate the thermo-oxidative degradation of PI and oxidation of copper. In addition, scanning electron microscopic analysis and contact angle measurements were performed for the investigation of the interaction between PI and silane-modified PVIs. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1343–1351, 1998     

Adhesion properties of phosphate‐ and siloxane‐containing polyurethane dispersions to steel: An analysis of the metal–coating interface

Polyurethane dispersions containing phosphate and siloxane groups in the main chain were investigated as possible self‐assembling metal coatings. Improved adhesion of the polymer to the metal was observed because of the formation of an insoluble metal phosphate layer at the metal–coating interface. The neutralizing amine of the dispersions affected the formation of this metal phosphate, and the metal phosphate formation was dependent on the curing temperature and boiling point of the amine used for neutralization. A crosscut comparative study of adhesion proved that the phosphate‐containing coatings had better adhesion because of the formation of ionic bonds at the metal–coating interface. A solid‐state adhesion prediction method based on thermodynamic considerations was used. The results of the solid‐state adhesion method correlated well with that obtained from the crosscut adhesion test method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 900–907, 2003     

高初粘力EPDM/金属界面胶粘剂的研究

在三元乙丙橡胶胶粘剂AE-2基础上,探索了提高EPDM/金属界面胶粘剂初粘力的途径,考察了增粘树脂HX,HY-209,GMA,TX和R11等对胶粘剂初粘力的影响,重点研究了增粘树脂HX用量对EPDM/金属界面粘接性能的影响,确定了高初粘力EPDM/金属界面胶粘剂AE-9配方组成。结果表明,加入增粘树脂HX后EPDM/金属界面胶粘剂初粘力效果最好。胶粘剂AE-9粘接性能优异,剥离强度达到4.0 MPa以上,粘接试样经80℃×180 d热空气老化试验后粘接强度没有降低,老化性能优异。     

Adhesion Between Rubber Compound and Copper-Film-Plated Steel Cord

Four copper-film-plated steel cords (abbreviated hereafter as copper-plated cord) with different thickness of copper film from 32 to 90 nm were prepared and their adhesion properties with rubber compound were investigated. Adhesion properties improved with the decrease in the thickness of the copper film. Unaged pull-out force and rubber coverage of copper-plated cords were inferior to those of brass-plated cord, but adhesion degradation was significantly slower on copper-plated cords resulting in better adhesion after humidity aging of 15 days and salt solution aging of 5 days. The excellent adhesion stability of copper-plated cords can be explained by the suppression of the excessive growth of copper sulfide and the inhibition of dezincification due to the small amount of copper plating and the lack of metallic zinc at the outer surface.     

Surface Chemical Characterization of Copper Oxide and its Relationship to Adhesion in Formed Epoxy/Copper Interfaces

Experiments have been performed to comprehensively analyze copper oxides formed from a chlorite oxidation bath on copper bar stock and to measure the adhesion of an epoxy casting resin to the corresponding oxidized surfaces. Temperature conditions for the bath ranged from 25 to 90°C with oxidation times between 0.25 and 20 minutes. Adhesion testing of the epoxy/copper systems was performed using a 3-point bend testing rig and measuring the ultimate force and displacement at the moment of sample failure near the epoxy/substrate interface. The flexure testing configuration used the resin as a stiffening rib which created a deviation in the force-deflection curve from that of the originally-oxidized copper bar stock. As the oxidation temperature increased above 50°C, there was higher cohesion of the oxide layer formed on the copper and that led to a higher measured force at failure. On copper samples oxidized at lower temperatures, failure occurs within the oxide as a part of the latter remains on the resin side and lower adhesion was measured.     

Adhesion Between Rubber Compounds and Copper-film-coated Steel Plates

Three copper-film-coated steel plates (abbreviated hereafter as copper-coated plate) with different thicknesses of copper film 30 to 90 nm were prepared and their adhesion properties to rubber compounds were examined. The high adhesion of copper-coated plates to the rubber compound containing resinous bonding additives was obtained at normal and over-cure conditions The copper-coated plate containing an amount of copper coating sufficient to plate the surface with a uniform copper layer showed better adhesion than that having a small amount of copper coating on its surface. The stability against green humidity aging and the cause for the high adhesion of the copper-coated plate were discussed compared with those of the brass plate.     

Adhesion Between Rubber Compounds and Copper-film-coated Steel Plates

Three copper-film-coated steel plates (abbreviated hereafter as copper-coated plate) with different thicknesses of copper film 30 to 90 nm were prepared and their adhesion properties to rubber compounds were examined. The high adhesion of copper-coated plates to the rubber compound containing resinous bonding additives was obtained at normal and over-cure conditions The copper-coated plate containing an amount of copper coating sufficient to plate the surface with a uniform copper layer showed better adhesion than that having a small amount of copper coating on its surface. The stability against green humidity aging and the cause for the high adhesion of the copper-coated plate were discussed compared with those of the brass plate.     

Study on brown oxidation process with imidazole group,mercapto group and heterocyclic compounds in printed circuit board industry

The adhesion strength of the interface between copper foil and resin is an important technological parameter for applications in microelectronics. In this study, a new brown oxidation solution of copper foil, including the recipe composition and reliability tests, was fully discussed. We provided an overview of brown oxidation process used in the semi-flexible printed circuit boards production industry by investigating the brown oxide film. The morphology of the copper oxide film was changed from lamellar structure to honeycomb structure with the increasing of oxidation time. The peel adhesion strength of the Cu/polyimide laminates was increased from about 2–16 N/cm by altering the immersion time and the concentration of inhibitors in brown oxidation solution. Scanning electron microscopy, peel tests and X-ray diffraction indicated that the higher adhesion strength was resulted from the rougher surface and the proper etching depth of copper foil, which was caused by chemical reactions on the interface surface of copper foil.     

Studies on Adhesion Between Natural Rubber and Polyethylene and the Role of Adhesion Promoters

Studies on adhesion between natural rubber (NR) and polyethylene (PE) with different levels of interaction (physical and chemical) have been carried out. Ethylene propylene diene rubber (EPDM) and chlorinated polyethylene (CPE) were used as physical promoters and epoxidised natural rubber/modified polyethylene (ENR/PEm) and sulfonated ethylene propylene diene rubber/modified polyethylene (S-EPDM/PEm) were used as chemical adhesion promoters. The failure surfaces were examined with the help of scanning electron microscopy (SEM), optical photography and electron spectroscopy for chemical analysis (ESCA) techniques.

The peel strength between natural rubber and polyethylene as measured in this study is 140 J/m². With the incorporation of physical promoters such as EPDM, the peel strength increases twenty fold because of structural similarity of EPDM with PE and the rubbery nature of EPDM. Similarly, the other promoters show significant improvement in peel strength. At high temperature and low rate of peeling, the nature of failure is mainly “stick-slip” for joints with interaction promoters. The average peel strength increases with increase in test rate and decrease in test temperature for most of the joints. All the data could be shifted onto a master curve indicating that the increase in strength is a result of viscoelastic dissipation. NR/EPDM/PE and NR/CPE/PE systems, however, behave in a different way probably because they alter the nature of crack propagation at or near the interface. ESCA results of the peeled PE surface show a chemical shift of C_1S peak. SEM photographs also indicate interaction at the interface when modifiers are used. An increase in crystallinity of PE from 30% to 64% and modulus increase the peel strength of NR/PE joints by a factor of four. The results of peel strength measurement at 90° are lower than those at 180°. Lap shear results are in line with peel strength.     

Adhesion of glass/epoxy composites influenced by thermal and cryogenic environments

Little information regarding the effects of prior thermal and cryogenic conditionings on hydrothermal and mechanical behavior, for varied volume fractions of constituent phases in polymer matrix fiber composites, has been published to date. The present experimental investigation uses flexural test to assess the effects of thermal and cryogenic treatments, and concurrently followed hydrothermal aging on quality of adhesion of multilayered laminates for 55, 60, and 65 wt % of E-glass fiber-reinforced epoxy composites. The specimens were conditioned at 80°C and −80°C temperatures for different time durations, and thereafter they were immediately immersed in boiling water for an hour. Water absorption rates were evaluated for those conditioned specimens in such environment. Absorption study in hydrothermal aging showed a remarkable variation for the two cases of prior conditionings. The shear strength values were compared with the test value of as-cured samples. Degradation of mechanical property was found to be less prevalent during hydrothermal aging, with a prior conditioning at 80°C temperature compared to −80°C treated glass/epoxy composites. Improved shear strength for almost all conditions of thermal conditioning in the initial stages has highlighted better adhesion influenced by postcuring phenomena during thermal or cryogenic conditioning. It was also observed from water absorption data that high temperature conditioning contributed more strengthening effect and better adhesion at the interfaces. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1943–1949, 2006     

Adhesion concepts in dentistry: tooth and material aspects

Adhesion concepts require understanding of substrate material properties, surface conditioning methods and chemical interactions, formation of interfaces/interphases between different material combinations, changes at interfaces with time, failure mechanisms and failure modes of the interfaces as a consequence of aging phenomenon. In dentistry, different methods are being used to test adhesion of resin-based materials to various biological and artificial substrates that require individual conditioning protocols. Variations among specimen configurations, material properties and chemical compositions of adhesives, test methods and test conditions all have effect on adhesion of similar or dissimilar substrates. Selection of the test, its proper execution, as well as the interpretation of the data through chemistry of the materials involved is of importance. Although adhesion to enamel is not a major concern today, effective adhesion to dentin requires several steps where failure in any of these consecutive events might result in failure of the whole system after long-term clinical use. Test methodologies used for assessment of mechanical behavior of materials in engineering may not directly apply to tooth–material combinations in dentistry. The objective of this review on adhesion in dentistry is to summarize current materials and methods used in dental materials testing and to summarize the current state-of-the-art in adhesion durability and quality with respect to the material type.     

Enhancing the Adhesion Retention by Controlling the Structure of the Adhesion Interphase between Rubber Compound and Metal. Part II. Effect of Zinc Borate

The adhesion between zinc borate-containing rubber compounds and brass-plated steel cords was studied to understand the role of zinc borate as an adhesion promoter. No improvement in adhesion after cure was shown with loading of zinc borate in the range 0.5–2 phr, while enhancement of adhesion retention after humidity aging was observed with loading of zinc borate in the range 0.5–2 phr. The adhesion interphase between the brass-plated steel cord and the rubber compound subjected to humidity aging treatment showed, using AES, a stabilized depth profile by a moderate loading of zinc borate, resulting in enhancement of adhesion retention. For the high loading of zinc borate, copper sulfide layer and zinc oxide layer grew excessively in the adhesion interphase under humidity aging.     

Influence of Cure Conditions on the Adhesion of Rubber Compound to Brass-plated Steel Cord. Part I. Cure Temperature

The effect of the cure temperature of rubber compound on the adhesion with brass-plated steel cord was investigated in conjunction with the formation, growth and degradation of the adhesion interphase formed between the rubber compound and brass-plated steel cord. With increasing cure temperature from 130°C to 190°C, the pull-out force after cure decreased linearly. This decrease in adhesion force at higher temperature may be explained by the limitation of the mass transfer of vulcanizing agents into the adhesion interphase and/or rubber compound near the adhesion interphase, resulting in a deficiency of sulfur due to the fast cure of the rubber compound which significantly retards the diffusion of vulcanizing chemicals. Also, at a high temperature, an adhesion interphase with a ZnS-rich layer, which may act as a barrier to copper diffusion for the formation of the adhesion interphase of copper sulfide, was formed. After thermal aging of the adhesion samples, the pull-out force decreased in comparison with that of the unaged. The decrease of pull-out force after thermal aging stemmed mainly from the decline of the tensile properties after thermal aging. The adhesion property after humidity aging was completely different from that after thermal aging. With increase in the cure temperature to 160°C, the pull-out force increased. But further increase in the cure temperature caused a decline in pull-out force. This phenomenon can be explained by the degradation of the adhesion interphase. At lower cure temperatures, a severe growth of copper sulfide and a large extent of dezincification were observed in the adhesion interphase. At higher cure temperatures, a significant growth of copper sulfide in the adhesion interphase appeared. The proper formation of the adhesion interphase and good physical properties of the rubber compound at a moderate cure temperature can result in high retention of adhesion properties.     

Influence of Cure Conditions on the Adhesion of Rubber Compound to Brass-plated Steel Cord. Part I. Cure Temperature

The effect of the cure temperature of rubber compound on the adhesion with brass-plated steel cord was investigated in conjunction with the formation, growth and degradation of the adhesion interphase formed between the rubber compound and brass-plated steel cord. With increasing cure temperature from 130°C to 190°C, the pull-out force after cure decreased linearly. This decrease in adhesion force at higher temperature may be explained by the limitation of the mass transfer of vulcanizing agents into the adhesion interphase and/or rubber compound near the adhesion interphase, resulting in a deficiency of sulfur due to the fast cure of the rubber compound which significantly retards the diffusion of vulcanizing chemicals. Also, at a high temperature, an adhesion interphase with a ZnS-rich layer, which may act as a barrier to copper diffusion for the formation of the adhesion interphase of copper sulfide, was formed. After thermal aging of the adhesion samples, the pull-out force decreased in comparison with that of the unaged. The decrease of pull-out force after thermal aging stemmed mainly from the decline of the tensile properties after thermal aging. The adhesion property after humidity aging was completely different from that after thermal aging. With increase in the cure temperature to 160°C, the pull-out force increased. But further increase in the cure temperature caused a decline in pull-out force. This phenomenon can be explained by the degradation of the adhesion interphase. At lower cure temperatures, a severe growth of copper sulfide and a large extent of dezincification were observed in the adhesion interphase. At higher cure temperatures, a significant growth of copper sulfide in the adhesion interphase appeared. The proper formation of the adhesion interphase and good physical properties of the rubber compound at a moderate cure temperature can result in high retention of adhesion properties.     

Surface Modification of a Photo-Definable Epoxy Resin with Polydopamine to Improve Adhesion with Electroless Deposited Copper

Abstract

This paper describes the influence of polydopamine surface modifications on the adhesion strength of electroless deposited copper on roughened epoxy resin substrates. The surfaces are characterized with XPS and ToF-S-SIMS. Next, a thorough investigation of the copper–epoxy interface is performed using SEM. Both the polydopamine modification and the variation of the electroless plating bath temperature lead to new insights into the different contributions of chemical and physical adhesion to the overall adhesion strength.     

Interfacial behavior of polyimide/primer/copper system by preoxidation of the primer

The copolymers of vinyl imidazole (VI) and vinyl trimethoxy silane (VTS) were applied as the corrosion inhibitors and the adhesion promoters for the polyimide/copper system at elevated temperatures. The mol ratios of VI to VTS were 100 : 0, 70 : 30, 30 : 70, and 0 : 100. Preoxidation of the primer was performed to improve the reactivity of the primer on poly(amic acid). A peel test was performed to evaluate the adhesion strength of the polyimide/primer/copper system after heat treatment at 400°C in a nitrogen atmosphere. The effect of the preoxidation of the primer on corrosion protection and adhesion promotion were investigated by Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The adhesion strength of the polyimide/primer/copper system depended on not only the chemical interaction between polyimide and the preoxidized primer, but also the thermal stability of the primer. It showed the highest value when the mol ratio of VI to VTS was 30 : 70. The primer layer reduced or suppressed copper diffusion into the polyimide layer. The degree of corrosion protection by the primer was affected by its thermal stability and its reactivity on copper. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2518–2524, 2000