Surface modification of polyethylene by radiation-induced grafting for adhesive bonding. V. Comparison with other surface treatments

Helium gas plasma treatment of low-density polyethylene (LDPE) yields much lower peel strength than oxidative treatment using chromic acid and oxygen gas plasma. The practical adhesion, the bondability retention, and the bond durability of oxidatively treated LDPE sheets, bonded with epoxy adhesives, have been compared with those of partially hydrolyzed LDPE–methyl acrylate surface grafts. The oxidized surfaces easily lose the bondability by light rubbing with tissue paper, solvent extraction, heat aging, and artifical weathering, whereas the grafted surfaces retain the bondability. The bondability loss is due to removal of the oxidized layer, and the bondability retention is due to retention of the surface homopolymer layer. Conventional antioxidants stabilize the grafted but not the oxidized surfaces against thermal oxidative degradation. The grafted LDPE joints have much higher bond durability in humid environments than those of the oxidized LDPE joints. The dry and wet peel strengths of oxidized LDPE joints are greatly improved by application of primers consisting of a base epoxy resin and organic solvents. An adhesion mechanism involving penetration of epoxy adhesives into the oxidized layers and subsequent reinforcement of the layers by curing of the penetrated epoxy is proposed.     

Preparation of high peel strength and high anti-aging epoxy adhesive that used for bonding aluminum alloy without surface treatment

In the case of bonding of aluminum alloy, surface pretreatment have been widely adopted for adherends so as to achieve superior adhesive performance. However, the strict surface treatment of the aluminum alloy cannot be implemented without special equipment and the mechanical properties, corrosion resistance and aging resistance of the common adhesives cannot meet the demand without surface treatment. Here, acrylic oligomer modified by carboxyl terminated organosilicon and nano alumina were used to modify an epoxy formulation based on a classical DGEBA monomer to produce a high peel strength epoxy adhesive that can be used without surface pretreatment. The peel strength and the shear strength of the adhesive could reach 7.18?N/cm and 18.75?MPa, respectively, and could be well maintained under ?70?°C and 100?°C. The novel adhesive also has good heat aging resistance, water resistance and artificial seawater resistance. SEM and XPS were used to investigate mechanism of aging resistance of modified adhesives without surface treatment.     

Surface modification of polyethylene by radiation-induced grafting for adhesive bonding. III. Oxidative degradation and stabilization of grafted layer

Vapor-phase mutual grafting of methyl acrylate (MA) onto polyethylene (PE) and subsequent saponification treatment produce a surface graft having a high adhesive bondability, which results from the presence of a hydrolized homopolymer layer (consisting of only monomer component) on an inner graft copolymer layer consisting of both PE and monomer components. The oxidative deterioration and the stabilization of the grafted surface layer have been investigated to clarify the long-term stability of the adhesive bondability. The bondability rapidly disappears with accelerated weathering followed by acetone extraction treatment, whereas it is kept unchanged during thermal-oxidative aging at 100°C. Microscopic and ATR infrared spectroscopic observations of the degraded surfaces show that the bondability loss is due to degradative removal of the surface homopolymer layer. The addition of combinations of conventional antioxidants and ultraviolet absorbers stabilizes the grafted surface layer against thermal-oxidative and photo-oxidative degradation and thus extends the bondability retention time. The stabilization is more effective in the grafts of carbon black-containing PE, where carbon black is present in the inner-graft copolymer layer.     

Reactive bonding of natural rubber to metal by a nitrile–phenolic adhesive

The mechanism of adhesive bonding of rubber to metal using an interlayer of bonding agent (adhesive) is discussed with respect to various physical and chemical events such as adsorption at the metal surface, chemical crosslinking within the adhesive, interdiffusion, and formation of interpenetrating networks at the rubber–adhesive interface. An investigation on the peel strength of a natural rubber (NR)–adhesive–metal joint, made by vulcanization bonding using nitrile–phenolic adhesive containing various concentrations of toluene diisocyanate–nitrosophenol (TDI–NOP) adduct, is presented. A single‐coat adhesive, consisting of a p‐cresol phenol formaldehyde resin, nitrile rubber (NBR), and vulcanizing agents in methyl ethyl ketone solvent, was selected for the study. Considerable improvement in the peel strength was obtained by the incorporation of TDI–NOP adduct into the nitrile–phenolic adhesive. The peel strength increases as the concentration of TDI–NOP adduct in the adhesive composition increases, then levels off with a transition from interfacial failure to cohesive tearing of rubber. The peel strength improvement is believed to be attributed to the interfacial reactions between the bonding agent and natural rubber, when TDI–NOP adduct is incorporated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2597–2608, 2001     

UV curable pressure‐sensitive adhesives for fabricating semiconductors. II. The effect of functionality of acrylate monomers on the adhesive properties

In an attempt to control the adhesive properties of acrylic copolymer‐based pressure‐sensitive adhesives, a series of multifunctional acrylate monomers were added and UV cured. The adhesive compound with a difunctional monomer had increased peel strength after UV curing. On the other hand, the compound with a tri‐ or more functional (polyfunctional) monomer had markedly decreased strength after UV curing. Those adhesives containing any polyfunctional monomer also showed much higher storage modulus than an adhesive containing a difunctional monomer. The greater volume contraction of UV‐cured polyfunctional monomer suggested microvoids at the interface between the adhesive layer and the adherent, resulting in poor strength. Estimated values of the peel strength of UV‐cured adhesives according to the theoretical equations proved that the strength is approximately inversely proportional to the elastic moduli. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2889–2895, 2004     

Studies on the adhesion behavior of water-based adhesives blended with asan gum

The influence of asan gum, a locally available waste material obtained from the Terminalia alata tree, in blends with waterborne natural rubber adhesive and poly(vinyl acetate), on the lap shear strength and the peel strength has been investigated. Both the strength values increase, even with a small quantity of the gum. At a higher gum content, both these parameters, however, decrease. Fourier Transform Infrared studies reveal that there is no covalent bonding between the gum and the adhesives, although some hydrogen bonding exists in the poly(vinyl acetate) blend. Morphological studies reveal mechanical interlocking of the adhesive in the substrates. The pseudoplastic nature of the gum-modified waterborne adhesives has been confirmed from rheological studies using a Brookfield viscometer. The higher lap shear and peel strength values of the gum-modified adhesives compared to the control adhesives are attributed to the higher shear modulus of the former. The 100% modulus and tensile strength of the adhesives blended with the gum are also higher, compared to their controls.     

室温固化丙烯酸结构胶的研究

为了满足快速粘接的需要,采用甲基丙烯酸环氧酯和烯类单体制备了一种室温快速固化的结构胶。研究了复合稳定剂对胶体稳定性的影响。测试了粘接时间对粘接强度的影响。结果表明：复合稳定剂用量在0．02％以上时,胶体能稳定贮存一年以上;粘接强度在固化初期明显增长,12h达到最高强度的90％以上;胶体无气味,使用方便,固化速度快,强度增长快,粘接强度高。该结构胶能满足快速粘接、特别适合动荷载情况下快速粘接的使用要求,具有良好的市场前景。     

Stress Analysis of Adhesively Bonded Electroprimed Steel Lap Shear Joints

Structural applications for adhesive bonding have been increasing in recent years due to improvements in the types of adhesives available and in improved knowledge of bonding procedures. Consequently, there exists a demand for precise numerical modeling of adhesive joint behavior, particularly along bondline interfaces where low surface energy adhesives contact high surface energy metallic oxides. The purpose of the present study is to determine the effect of electrodeposited organic paint primer (ELPO) on the stress and strain distributions within an adhesively bonded single-lap-shear joint. Initial experimental studies have shown that bonding to ELPO-primed steel adherends has enhanced strength and durability characteristics compared to conventional bonds to unprimed steel surfaces. Recent studies based on finite element analysis of varied single-lap-shear joint moduli and thicknesses, and subsequent testing of joints with two different adhesive moduli, have indicated the mechanisms involved in this phenomenon. The presence of the ELPO-primer reduced peak peel and shear stresses and allowed for more uniform stress distribution throughout the joint.     

Stress Analysis of Adhesively Bonded Electroprimed Steel Lap Shear Joints

Structural applications for adhesive bonding have been increasing in recent years due to improvements in the types of adhesives available and in improved knowledge of bonding procedures. Consequently, there exists a demand for precise numerical modeling of adhesive joint behavior, particularly along bondline interfaces where low surface energy adhesives contact high surface energy metallic oxides. The purpose of the present study is to determine the effect of electrodeposited organic paint primer (ELPO) on the stress and strain distributions within an adhesively bonded single-lap-shear joint. Initial experimental studies have shown that bonding to ELPO-primed steel adherends has enhanced strength and durability characteristics compared to conventional bonds to unprimed steel surfaces. Recent studies based on finite element analysis of varied single-lap-shear joint moduli and thicknesses, and subsequent testing of joints with two different adhesive moduli, have indicated the mechanisms involved in this phenomenon. The presence of the ELPO-primer reduced peak peel and shear stresses and allowed for more uniform stress distribution throughout the joint.     

The peel ply surface treatment for adhesive bonding of composites: A review

This paper reviews existing literature related to the peel ply surface treatment of composite materials. A peel ply fabric is used as a removable layer in a composite lay-up and ripped off to modify the surface for adhesive bonding. A peel ply can affect the elemental composition of a surface and it is possible to distinguish between either a polyester or a polyamide peel ply treatment for a specific composite system and application. However, consistent and generalised relationships between the compositional modification or the surface energy and adhesive or resin adherence to treated surfaces are not probable. A compositional analysis and surface energy measurements are affected by the fractured matrix, peel ply fibre cavities and revealed reinforcements. Only a few recent studies have presented results for the regions of the matrix fracture and fibre cavities separately. Resin-impregnated peel plies, namely tear plies, offer additional tailorability for composite surface treatments, but related research is scarce.     

Polymeric reaction of polymer-monomer system irradiated by low energy electron beam. III. Adhesive property of pressure sensitive adhesive

Application of low-energy electron beam to nonsolvent-type pressure-sensitive adhesive is investigated. Adhesive properties such as peel strength, dead load strength, and ball tack were closely related to the reaction behavior (gel fraction and graft efficiency) of the acrylate polymer-monomer system. The reaction behavior is eluciadated by combining the measurements of gel fraction, infrared spectrum of gel, and molecular weight distribution detected by gel permeation chromatogrophy. It was found that the adhesive property of electro beamcured adhesives depends on the molecular weight of added polymer, monomer concentration, and irradiation dose. Graft polymerization and moderate crosslinking by electron beam irradiation especially contribute to superior high adhesive properties.     

Unique adhesive properties of pressure sensitive adhesives from plant oils

We report novel insights into the adhesive performance of bio-based pressure sensitive adhesives (PSAs). Three different homopolymers based on renewable fatty acid methyl esters were characterized in terms of their mechanical and adhesive properties. The polymers display the typical dependence of adhesive properties on molecular weight and degree of crosslinking, as quantified by shear modulus, tack and peel measurements. The absolute values of characteristic adhesion parameters are in the range of commercially available petrochemical PSAs. Curing of applied PSA films at elevated temperature results in a pronounced maximum in tack and peel strength at a critical curing time, which corresponds to a change from cohesive to adhesive failure. Thus, demand-oriented tailoring of adhesive properties can be achieved via an appropriate choice of curing time. Moreover, these bio-based adhesives offer improved adhesion on hydrophobic substrates and high water-resistance without any whitening, thus rendering them an attractive alternative to conventional petroleum-based products. These peculiar features are attributed to the high hydrophobicity of the used monomers.     

Effect of adhesive thickness and surface roughness on the shear strength of aluminium one-component polyurethane adhesive single-lap joints for automotive applications

Adhesively bonded technology is now widely accepted as a valuable tool in mechanical design, allowing the production of connections with a very good strength‐to‐weight ratio. The bonding may be made between metal–metal, metal–composite or composite–composite. In the automotive industry, elastomeric adhesives such as polyurethanes are used in structural applications such as windshield bonding because they present important advantages in terms of damping, impact, fatigue and safety, which are critical factors. For efficient designs of adhesively bonded structures, the knowledge of the relationship between substrates and the adhesive layer is essential. The aim of this work, via an experimental study, is to carry out and quantify the various variables affecting the strength of single-lap joints (SLJs), especially the effect of the surface preparation and adhesive thickness. Aluminium SLJs were fabricated and tested to assess the adhesive performance in a joint. The effect of the bondline thickness on the lap-shear strength of the adhesives was studied. A decrease in surface roughness was found to increase the shear strength of the SLJs. Experimental results showed that rougher surfaces have less wettability which is coherent with shear strength tests. However, increasing the adhesive thickness decreased the shear strength of SLJs. Indeed, a numerical model was developed to search the impact of increasing adhesive thickness on the interface of the adherend.     

Surface modification of polyethylene by radiation-induced grafting for adhesive bonding. IV Improvement in wet peel strength

Adhesive joints of hydrolyzed methyl acrylate grafts, bonded with epoxy adhesives, yield extremely high peel strength (adherend failure) in dry conditions. However, when the joints are exposed to humid environments, the peel strenght rapidly decreases with exposure time and then reaches a constant value (wet peel strength). Since the locus of failure changes from the adherend to the homopolymer layer with decreasing peel strength, the decrease is due to a decrease in mechanical strength of the homopolymer layer itself, which results from its swelling by water absorption. Many attempts to reduce the swelling of the homopolymer layer or to strengthen the swollen homopolymer layer were unsuccessful except (1) priming with epoxy solutions consisting of a base epoxy resin and organic solvents which can dissolve not only epoxy resins but also hydrolyzed poly(methyl acrylate) and (2) partial etching of the homopolymer layer by photo-oxidative degradation. All the results on the improvement in wet peel strength can be explained in terms of the penetration of epoxy resins into the homopolymer layer and subsequent curing of the penetrated epoxy resin.     

Peel resistance of adhesive joints with elastomer–carbon black composite as surface sensing membranes

The peel resistance of four adhesives (“J-B Weld” by J-B Weld (adhesive A), 3 M Scotch-Weld DP 125 Gy (adhesive B), Loctite PL Premium (3x) Construction Adhesive (adhesive C), and Henkel Hysol EA9394 (adhesive D)) is investigated for their bonding performance of a styrene‐ethylene/butylene‐styrene– carbon black (SEBS–CB) composite membrane used in structural health monitoring (SHM) applications. Tests are performed on membrane samples bonded on four common structural materials, namely aluminium, steel, concrete, and fiberglass, to obtain the peel resistance of adhesives. Results show that adhesive B has the highest strength for aluminium, steel, and fiberglass substrates, and that adhesive C has the highest strength for the concrete substrate. The performance is also evaluated versus adhesive cost, a critical variable in SHM applications. Here, adhesive C performed best for all substrates. Lastly, membrane residuals resulting from the peel tests are compared. Tests show that Adhesive B resulted in the highest residual percentage for aluminium, while adhesive C performed better for all other substrates. However, membrane residuals for adhesive C do not show a positive correlation with the peel resistance.     

Viscoelastic and adhesive properties of single‐component thermo‐resistant acrylic pressure sensitive adhesives

Poly(butyl acrylate‐vinyl acetate‐acrylic acid) based acrylic pressure sensitive adhesives (PSAs) were synthesized by solution polymerization for the fabrication of high performance pressure sensitive adhesive tapes. The synthesized PSAs have high shear strength and can be peeled off substrate without residues on the substrate at temperature up to 150°C. The PSAs synthesized in the present work are single‐component crosslinked and they can be used directly once synthesized, which is convenient for real applications compared to commercial multi‐component adhesives. The results demonstrated that the viscosity of the PSAs remained stable during prolonged storage. The effects of the preparation conditions such as initiator concentration, cross‐linker amount, organosiloxane monomer amount and tackifier resin on the polymer properties, such as glass transition temperature (T_g), molecular weight (M_w), surface energy and shear modulus, were studied, and the dependence of the adhesive properties on the polymer properties were also investigated. Crosslinking reactions showed a great improvement in the shear strength at high temperature. The addition of tackifier resin made peel strength increase compared to original PSAs because of the improvement of the adhesion strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40086.     

一种新型可生物降解聚酯压敏胶的制备与性能

以丁二酸、己二酸、1,3丙-二醇、1,4丁-二醇为单体,C-94为催化剂,丙三醇为交联剂,制备了一种新型的、可生物降解的四元无规共聚酯压敏胶,使用核磁共振波谱仪测定了共聚酯中各单元的组成比例,并对其黏弹性、初黏性、持黏性、180°剥离强度等进行了表征,考察了交联剂用量对压敏胶性能的影响。实验结果表明,丙三醇质量分数为0.6%时,压敏胶性能较佳。     

Properties of UV-curable solvent-free pressure sensitive adhesive

In this study, the effects of methyl methacrylate (MMA), trimethylolpropane triacrylate (TMPTA), difunctional silicone urethane acrylate oligomer, and UV-dose on the adhesive properties of UV-curable pressure-sensitive adhesives (PSAs) were investigated, for further optimizing the adhesive properties to meet the requirements on high holding power and low peel strength. The results illustrated that increasing the MMA content decreased the peel strength and improved the holding power. The variation of TMPTA content from 1 to 10 wt% significantly enhanced the holding power from 1?h to above 120?h. The gel fraction increased with increasing TMPTA content. This increment was caused by the cross-linking of TMPTA after UV exposure. The peel strength of UV-curable PSAs was reduced to zero when oligomer content was more than 40 wt%, whereas the holding power was significantly enhanced from 5?h to above 120?h as the oligomer content increased up to 70 wt%. When the UV-dose increased, the peel strength decreased and the holding power increased. Therefore, UV-curable PSAs with very low peel strength and high holding power above 120?h were successfully synthesized and they possessed desirable features which could be fabricated to meet the specific requirements for industrial applications.     

Effects of surface modification by oxygen plasma on peel adhesion of pressure‐sensitive adhesive tapes

Surfaces of poly(isobutylene) (PIB) and poly(butylacrylate) (PBA) pressure‐sensitive adhesive tapes were treated by oxygen plasma, and effects of surface modification on their adhesive behavior were investigated from the viewpoint of peel adhesion. The peel adhesion between PIB and PBA pressure‐sensitive adhesive tapes and stainless steel has been improved by the oxygen plasma treatment. The surface‐modification layer was formed on PIB and PBA pressure‐sensitive adhesive surfaces by the oxygen plasma treatment. The oxygen plasma treatment led to the formation of functional groups such as various carbonyl groups. The treated layer was restricted to the topmost layer (50–300 nm) from the surface. The GPC curves of the oxygen plasma‐treated PBA adhesive were less changed. Although a degradation product of 1–3% was formed in the process of the oxygen plasma treatment of the PIB adhesive. There are differences in the oxygen plasma treatment between the PIB and PBA adhesives. A close relationship was recognized between the amount of carbonyl groups and peel adhesion. Therefore, the carbonyl groups formed on the PIB and PBA adhesive surfaces may be a main factor to improve the peel adhesion between the PIB and PBA adhesive and stainless steel. The peel adhesion could be controlled by changing the carbonyl concentration on the PIB and PBA adhesive surfaces. We speculate that the carbonyl groups on the PIB and PBA adhesive surface might provide an interaction with a stainless steel surface. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1392–1401, 2000     

Anionomeric waterborne poly(urethane semicarbazide) dispersions and their adhesive properties

Aqueous polyurethane dispersions were prepared from isocyanate‐terminated ionic polyurethane prepolymers by chain extension with dihydrazides. These water‐borne dispersions had excellent adhesive properties and were used to bond leather and canvas. The base polymers were varied with respect to (1) the ionic content with the same chain extender and (2) the nature of the chain extender with the ionic content kept constant. Studies on the particle size and viscosity revealed that the ionic content had an influence on the aforementioned properties: the particle size decreased and the viscosity increased with increasing ionic content. The polarity of the films cast from the dispersions were determined with contact‐angle measurements: hydrophilic character was exhibited by all the compositions. X‐ray studies revealed that the increase in the ionic content led to increasing intensities of the diffraction peaks due to increased secondary forces of bonding. The tensile strength measurements showed that the films were highly elastomeric and had good mechanical strength, which varied with the composition. A shear strength and peel strength analysis of specimens obtained through the bonding of leather to leather, leather to canvas, and canvas to canvas revealed that the waterborne dispersions were excellent adhesives for bonding leather surfaces. Thus, a very efficient, ecofriendly waterborne dispersion of polyurethane that could find applications in bonding leather in the footwear industry was prepared successfully. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008