Improved adhesion of EVAs with different vinyl acetate contents treated with sulphuric acid

Four ethylene vinyl acetate copolymers (EVAs) containing 9, 12, 18 and 20 wt% vinyl acetate (VA) were treated with concentrated sulphuric acid to improve their adhesion to polychloroprene (PCP) adhesive. The tensile strength and Young's modulus of EVAs decreased as the VA content increased, due to the reduction in crystallinity of the polyethylene blocks in the copolymer. The modifications produced in the EVAs by treatment with sulphuric acid were followed using contact angle measurements (water, 25 °C), ATR-IR spectroscopy and scanning electron microscopy (SEM). Adhesive-bond strength was obtained by T-peel tests on treated EVA/polychloroprene adhesive joints. The vinyl acetate content in the EVA affected the extent, but not the nature, of the surface modification produced by treatment with sulphuric acid. The treatment produced both sulfonation and oxidation on the EVA surfaces. The higher the vinyl acetate content in the EVA, the more significant the modifications produced. Increased T-peel strengths of EVA/polychloroprene adhesive + 5 wt% polyisocyanate joints were obtained and a mixed failure (adhesion failure + cohesive failure in the adhesive) was produced. It was found that, to be effective, the treatment of EVAs must be carried out with 96 wt% sulphuric acid.     

Corona discharge treatment of EVAs with different vinyl acetate contents

Four ethylene vinyl acetate (EVA) co-polymers with different vinyl acetate (VA) contents (9–20 wt%) were treated with corona discharge to improve their adhesion to polychloroprene (PCP) adhesive. The thermal properties of the EVAs decreased as their VA content increased, caused by a decrease in crystallinity. The elastic and viscous moduli of the EVAs decreased and the temperature and modulus at the cross-over between these moduli decreased with increasing VA content. Contact-angle measurements (water), infrared spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to analyse the surface modifications produced in the corona-discharge-treated EVAs. The corona discharge treatment produced improved wettability and created roughness and oxygen moieties on the EVA surfaces. The higher the VA content and the higher the corona energy, the more significant modifications were produced on the EVA surface. The VA content also affected the T-peel strength values of treated EVA/polychloroprene + isocyanate adhesive joints, as the values increased with increasing VA content. Mixed failure modes (interfacial + cohesive failure in the EVA) were obtained in the adhesive joints produced with corona discharge treated EVAs containing more than 9 wt% VA. The accelerated ageing of the joints did not affect the T-peel strength values, but the locus of failure in most cases became fully cohesive in the EVA, likely due to the higher extent of curing of the adhesive.     

Surface modifications of EVA copolymers induced by low pressure RF plasmas from different gases and their relation to adhesion properties

Two ethylene vinyl acetate (EVA) copolymers (12 and 20 wt% of vinyl acetate,VA, content) have been treated with low pressure RF plasmas from non-oxidizing gases (Ar, N₂) and oxidizing gases (air, a mixture of 4N₂: 6O₂ (v/v), O₂ and CO₂). The formation of polar moieties on both EVAs was more noticeable by treatment with plasmas from non-oxidizing gases than from oxidizing ones (the higher the reactivity, the lower the difference with respect to untreated EVA surfaces). The surface etching with the non-oxidizing plasmas, giving rise to a high roughness, depends on the wt% of VA in the composition of the copolymer because of the different resistances of VA (low) and PE (high) to the non-oxidizing plasma particles bombardment. The adhesion properties obtained using a polyurethane adhesive (PU) showed high T-peel strength values and adhesion failure in EVAs treated with plasmas from oxidizing gases, due to roughness produced causing mechanical interlocking of the adhesive. Lower T-peel strength values were obtained with non-oxidizing plasmas: the values for EVA12 being, in general, lower than those obtained for EVA20. The durability of the treated EVAs/PU adhesive joints after ageing in humidity and temperature was quite good.     

Surface modifications on eva treated with sulphuric acid

In this study, treatment with sulphuric acid was used to increase the adhesion of an ethylene-vinyl acetate copolymer containing 20 wt% vinyl acetate (EVA20). The treatment with sulphuric acid improved the wettability of EVA20 due to thecreation of different oxygen and sulphonic acid moieties on the surface. The treatment also created cracks and heterogeneities on the EVA20 surface, and enhanced T-peel strength values of EVA20/polychloroprene adhesive+5 wt% isocyanate joints were obtained. The loci of failure of the joints were mixed, i.e. , adhesional and cohesive in the adhesive. Peel strength values of both as-received and sulphuric acid-treated EVA20/polychloroprene adhesive joints increased after ageing at 50°C and 95 wt% relative humidity for 72 because the complete cure of the adhesive was thereby was produced. The durability of the EVA20 treated with sulphuric acid was monitored between 15 min and 5 years. High peel strength values were obtained for times up to 61 days; the joints produced with the treated EVA20 five years after treatment showed lower peel strength value due to the creation of a weak boundary layer produced by reaction of the residual sulphuric acid on the surface with EVA20. On the other hand, different experimental variables in the treatment of EVA20 with sulphuric acid were considered. The optimum treatment conditions for EVA20 were obtained by immersion in highly concentrated sulphuric acid (96 wt%) for one minute followed by neutralisation with ammonium hydroxide.     

SURFACE MODIFICATIONS ON EVA TREATED WITH SULPHURIC ACID

In this study, treatment with sulphuric acid was used to increase the adhesion of an ethylene-vinyl acetate copolymer containing 20 wt% vinyl acetate (EVA20). The treatment with sulphuric acid improved the wettability of EVA20 due to thecreation of different oxygen and sulphonic acid moieties on the surface. The treatment also created cracks and heterogeneities on the EVA20 surface, and enhanced T-peel strength values of EVA20/polychloroprene adhesive+5 wt% isocyanate joints were obtained. The loci of failure of the joints were mixed, i.e. , adhesional and cohesive in the adhesive. Peel strength values of both as-received and sulphuric acid-treated EVA20/polychloroprene adhesive joints increased after ageing at 50°C and 95 wt% relative humidity for 72 because the complete cure of the adhesive was thereby was produced. The durability of the EVA20 treated with sulphuric acid was monitored between 15 min and 5 years. High peel strength values were obtained for times up to 61 days; the joints produced with the treated EVA20 five years after treatment showed lower peel strength value due to the creation of a weak boundary layer produced by reaction of the residual sulphuric acid on the surface with EVA20. On the other hand, different experimental variables in the treatment of EVA20 with sulphuric acid were considered. The optimum treatment conditions for EVA20 were obtained by immersion in highly concentrated sulphuric acid (96 wt%) for one minute followed by neutralisation with ammonium hydroxide.     

UV-Ozone Surface Treatment of SBS Rubbers Containing Fillers: Influence of the Filler Nature on the Extent of Surface Modification and Adhesion

SBS rubbers containing different loadings of calcium carbonate and/or silica fillers were surface treated with UV-ozone to improve their adhesion to polyurethane adhesive. The surface modifications produced on the treated filled SBS rubbers have been analyzed by contact angle measurements, ATR-IR spectroscopy, XPS and SEM. The adhesion properties have been evaluated by T-peel strength tests on treated filled SBS rubber/polyurethane adhesive/leather joints. The UV-ozone treatment improved the wettability of all rubber surfaces, and chemical (oxidation) and morphological modifications (roughness, ablation, surface melting) were produced. The increase in the time of UV-ozone treatment to 30 min led to surface cleaning (removal of silicon-based moieties) due to ablation and/or melting of rubber layers and also incorporation of more oxidized moieties was produced. Although chemical modifications were produced earlier in an unfilled rubber for short time of treatment with UV-ozone, they were more noticeable in filled rubbers for extended length of treatment, mainly for S6S and S6T rubbers containing silica filler. The oxidation process seemed to be inhibited for S6C and S6T rubbers (containing calcium carbonate filler). On the other hand, the S6S rubber containing silica filler and the lowest filler loading showed the higher extent of modification as a consequence of the UV-ozone treatment. The UV-ozone increased the joint strength in all joints, more noticeably in the rubbers containing silica filler, in agreement with the greater extents of chemical and morphological modifications produced by the treatment in these rubbers. Finally, the nature and content of fillers determined the extent of surface modification and adhesion of SBS rubber treated with UV-ozone.     

Influence of surface treatments on topography and bond strength of densely-sintered zirconium-oxide ceramic

The aim of this study was to evaluate the effect of surface treatments on the roughness and bond strength of dental materials containing MDP to zirconium oxide ceramic. Forty square-shaped zirconium-oxide ceramic blocks (Lava Zirconia, 3M-ESPE) were treated as follows: (CT) polished only; (SB) sandblasting (110 µm aluminum oxide particles) or (SC) silica coating (110 µm particles). Roughness of treated surface was measured using a profilometer (Ra) and by atomic force microscope (AFM). Two resin luting agents were used after silane application: self-adhesive (Rely X U200, 3M-ESPE) and dual cure (Rely X Ultimate, 3M-ESPE). The samples were submitted to microshear bond strength test. The failure analysis was performed. Data were submitted to ANOVA and Tukey test (α=0.05). Bond strength results ranged from 20.44 (CT+Ultimate) to 34.37 MPa (SC+U200) after 24 h and from 12.03 (CT+Ultimate) to 27.44 MPa (SC+U200) after 12 months of storage with SC statistically superior to the other treatments. Mean values of roughness varied from 0.07 (CT) to 0.85 µm (SC). The both resin luting agents showed similar results to all surface treatment groups. Silica coating provided the best treatment of the ceramic surface.     

Glass bond adhesive strength improvement by DCSBD atmospheric-pressure plasma treatment

A novel type of dielectric barrier discharge, the so called Diffuse Coplanar Surface Barrier Discharge (DCSBD), has been used for the treatment of glass surfaces prior to their bonding with a UV-curing acrylate adhesive. The DCSBD is a source of diffuse, atmospheric-pressure “cold” plasma with power densities reaching ~ 100 W/cm³ even in strong electronegative gases (e.g. pure oxygen) without any admixture of helium or argon. The plasma is generated in a thin, ~ 0.5 mm thick layer suitable for the treatment of flat materials like glass or polymeric foils. The plasma treatment of glass results in an overall decrease in organic contamination of the surface and, possibly, in an increase in the surface density of –OH groups promoting reactions on the glass surface, both effects being beneficial for adhesive properties of the glass surface. Plasma treated adhesive joints have been subjected to mechanical testing according to the ISO 4587 standard. Results indicate more than 45% improvement in the plasma treated joints adhesive strength, when compared to the untreated reference joints. Moreover, the different cleaning protocols used indicate, that it will be possible to substitute distilled water instead of ethanol in the cleaning procedure, which is a rather expensive and hazardous chemical.     

Process optimization of solvent based polybenzimidazole adhesive for aerospace applications

The use of adhesive bonding for high temperature applications is becoming more challenging because of low thermal and mechanical properties of commercially available adhesives. However, the development of high performance polymers can overcome the problem of using adhesive bonding at high temperature. Polybenzimidazole (PBI) is one such recently emerged high performance polymer with excellent thermal and mechanical properties. It has a tensile strength of 160 MPa and a glass transition of 425 °C. Currently, PBI is available in solution form with only 26% concentration in Dimethyl-acetamide solvent. Due to high solvent contents, the process optimization required lot of efforts to form PBI adhesive bonded joints with considerable lap shear strength. Therefore, in present work, efforts are devoted to optimize the adhesive bonding process of PBI in order to make its application possible as an adhesive for high temperature applications. Bonding process was optimized using different curing time and temperatures. Epoxy based carbon fiber composite bonded joints were successfully formed with single lap shear strength of 21 Mpa. PBI adhesive bonded joints were also formed after performing the atmospheric pressure plasma treatment of composite substrate. Plasma treatment has further improved the lap shear strength of bonded joints from 21 MPa to 30 MPa. Atmospheric pressure plasma treatment has also changed the mode of failure of composite bonded joints.     

Mechanical behaviour of adhesively bonded polyethylene tapping tees

The mechanical properties of adhesively bonded MDPE joints were studied. The lap-shear joints were prepared using PE80 polyethylene gas pipe and four adhesive types; two acrylic and two epoxy resins. The key mechanical properties of lap shear strength and impact resistance were investigated as a function of adhesive type and surface preparation technique. Mechanical abrasion of the PE80 surface increased the strength of the bonds from 40 to 460% for the four adhesives, with the best performing acrylic adhesive having a lap-shear strength of 1.76 MPa and impact strength of 2.5 kJ/m². When used to bond PE80 tapping tees to PE80 gas pipe, the acrylic adhesive produced a gas tight seal at both the standard test pressure of 0.4 MPa and at an increased pressure of 0.8 MPa, and outperformed the PE80 tapping tee during shear testing and withstood a maximum of 10 cycles of 175 J during impact testing. These results highlight the potential of adhesive bonding as a method of joining PE80 tapping tees to PE80 gas pipe.     

High-performance nanoadhesive bonding of titanium for aerospace and space applications

In this investigation, attempts are made to prepare high-performance nanoadhesive bonding of titanium for its essential applications to aviation and space. The high-performance nanoadhesive is prepared by dispersing silicate nanoparticles into the ultra-high-temperature-resistant epoxy adhesive at 10 wt% ratio with the matrix adhesive followed by modification of the nanoadhesive after curing under high-energy radiation for 6 h in the pool of SLOWPOKE-2 nuclear reactor with a dose rate of 37 kGy/h to promote crosslink into the adhesive. Prior to bonding, the surfaces of the titanium sheets are mechanically polished by wire brushing, ultrasonically cleaned by acetone and thereafter the titanium sheets are modified by plasma ion implantation using plasma nitriding. The titanium surface is characterized by X-ray photoelectron spectroscopy (XPS). The thermal characteristics of the epoxy adhesive and the high-performance nanoadhesive are carried out by thermal gravimetric analysis (TGA). The TGA studies clearly shows that for the basic adhesive there is a weight loss of the adhesive, however, in the case of epoxy–silicate nanoadhesive, there is almost 100% retention of weight of the adhesive, when the adhesive is heated up to 350 °C. Lap shear tensile strength of the joint increases considerably, when the titanium surface is modified by plasma-nitriding implantation. There is a further massive increase in joint strength, when the plasma-nitriding implanted titanium joint is prepared by nanosilicate–epoxy adhesive and further modification of the adhesive joint under high-energy radiation results a further significant increase in joint strength. In order to simulate with aviation and space climatic conditions, the joints are separately exposed to cryogenic (?196 °C) and elevated temperature (+300 °C) for 100 h and thermal fatigue tests of the joints are carried out under 10 cycles by exposing the joint for 2 h under the above temperatures. When the joint completely kept at ambient condition and the joint strength compared with those joints exposed to aviation and space climatic conditions, it is observed that the joint could retain 95% of the joint strength. Finally, to understand the behavior of the high-performance silicate–epoxy nanoadhesive bonding of titanium, the fractured surfaces of the joints are examined by scanning electron microscope.     

Effect of thermal cycling on tensile properties of degraded FML to metal hybrid joints exposed to sea water

In the present paper, the mechanical properties of hybrid bonded bolted joints between Fiber metal laminate (FML) and stainless steel adherends are investigated using experimental tensile tests. Three and five layered FMLs were fabricated using 430 stainless steel sheets and fiberglass prepreg layers. The adherends were bonded by AD-314 resin mixed with HA-34 hardener as adhesive and steel bolt was used for the mechanical fastening. The specimens were immersed into the sea water for 30 days and degradation of the mechanical strength of the joints was studied. Thermal cycles including heating (40 °C to100 °C) and cryogenic (−100 °C to −40 °C) cycles were applied in order to study their effects on the strength of the degraded joints. The failure mode for the adhesive bond was mixed failure and that of the bolted joint was the net-tension failure. The results showed 52% strength recovery in hybrid joints subjected to heating cycles. Cryogenic cycles also caused a 50% improvement in the tensile strength of the hybrid joints. In addition, the joint stiffness and absorbed energy of the specimens were improved significantly for both heating and cryogenic cycles. Moreover, the effect of FML stacking sequence on the results was also investigated. The results revealed that the mechanical fastening failure load for 5 layered FML joint is more affected by thermal cycles in comparison with 3 layered FML joint.     

Effect of the type of plasma on the polydimethylsiloxane/collagen composites adhesive properties

Polydimethylsiloxane (PDMS) films were treated with either oxygen (O₂), nitrogen (N₂) or argon (Ar) plasma between 40 W and 120 W for 5–15 min and their surface properties studied by contact angle measurements, infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Lower contact angles and increases in surface roughness, assessed by SEM and AFM, were observed for all used gases when plasma power and time increased, with argon treatment being the one that showed the most significant change in roughness.PDMS/collagen type I composites obtained after treating PDMS with oxygen at 80 W for 13 min or nitrogen and argon at 80 W for 14 min showed a peel strength of 0.1N/mm (oxygen plasma), 0.08 N/mm (nitrogen plasma) and 0.09 N/mm (argon plasma). In all cases, peel strength was higher than that measured for the untreated bilayer composite. An increase in adhesion strength, after oxygen and nitrogen plasma, was mostly attributed to chemical interaction between functional groups introduced on the PDMS surface and the functional groups on collagen as detected by FTIR. In contrast, the high peel strength observed on PDMS treated with argon plasma was attributed to its increased roughness which in turn increased mechanical interlocking. The properties of these composites render them suitable for adhesive free skin substitutes.     

Study on the fatigue strength of AA 6082-T6 adhesive lap joints

A research study on the fatigue behaviour of aluminium alloy adhesive lap joints was carried out to understand the effect of surface pre-treatment and adherends thickness on the fatigue strength of adhesive joints. The adherend material used for the experimental tests was an aluminium alloy 6082-T6 in the form of thin sheets, and the adhesive used was a high strength epoxy (Araldite 420 A/B). The surface preparation included an abrasive preparation (AP joints) and sodium dichromate–sulphuric acid etch (CSA joints).A maximum fatigue strength was obtained for the CSA surface treatment with a 1.0 mm adherends’ thickness. The fastest fatigue damage was related with a high surface roughness and a high stress perpendicular to adhesive surface, which helps to promote the adhesive failure. A numerical analysis was also performed to understand the effect of the adherends thickness on the stress level. Results showed an increase of the out-of-plane peak stresses with the increase of adherends thickness.     

Enhanced adhesion of epoxy-bonded steel surfaces using O2/Ar microwave plasma treatment

Steel surfaces have been modified using low pressure microwave plasma to enhance its adhesion with an epoxy adhesive. Optimization of the wettability of the surface was done using contact angle measurements for varying plasma parameters. Maximum wettability (19.9°) was obtained at 1000 W microwave power with 20 min of treatment time, −50 V sample bias and 1.67% O₂/Ar gas flow rate ratio. Enhanced wettability of the steel surface was attributed to increased surface roughness and oxide deposition. Using atomic force microscopy, surface roughness was observed to increase from 64.4 nm for the untreated surface to 76.7 nm for the O₂/Ar plasma treated surface. Deposition of oxides on the steel surface was also confirmed by the energy dispersive x-ray spectroscopy. Moreover, the increase in the total surface energy to 53.2 mN/m for the O₂ plasma treated steel surface supported the enhancement of its wettability, and hence, the adhesion with epoxy. Based on tensile test results, the adhesion strength of epoxy-bonded O₂/Ar plasma treated surfaces at optimum settings was increased to 3816.0 N, which is significantly higher compared to 3038.3 N for the epoxy-bonded untreated surfaces.     

Crack healing and strength recovery in SiC/spinel nanocomposite

The crack healing behavior and the strength recovery of the newly introduced SiC/spinel nanocomposite were investigated. SiC/spinel nanocomposite containing 27.26 wt% SiC was prepared by the ball milling of talc, graphite and aluminum powders with subsequent annealing at 1200 °C for 1 h in a vacuum. The SEM results showed that the surface cracks produced by Vickers indenter on the prepared SiC/spinel pellets can be completely healed after sintering at 1545 °C for 1 min in air atmosphere. Furthermore, an almost complete strength recovery of the specimens can be obtained in those samples heat treated at 1550 °C for 1 min, as evaluated by diametral tensile strength (DTS) test. The formations of mullite and aluminosilicate glassy phases are the major factors which are responsible for the crack healing and strength recovery in the structure. It was found that the healing efficiency of those specimens healed at 1550 °C for 1 min is 99%.     

Low temperature tensile lap-shear testing of adhesively bonded polyethylene pipe

This work studies the lap-shear strength performance of polyethylene pipeline bonded with acrylic adhesive in the temperature range -10 to +20 °C. Single lap shear test samples were firstly prepared at 20 °C under various clamping pressures and curing times to determine suitable conditions under which to prepare and test further samples at temperatures of -10, -5, 0, +5 and +20 °C. It was found that a decrease in curing/testing temperature to zero degrees resulted in a steady reduction in the lap-shear strength performance of the bonded joints from a mean value of 2.72 MPa at +20 °C to 1.15 MPa at 0 °C. Below zero degrees the strength of the bonded substrates was significantly reduced; no samples bonded at -5 °C had sufficient strength to test and only one sample bonded -10 °C was tested, which had very low strength of 0.105 MPa.     

Preparation and performance of ceramizable heat-resistant organic adhesive for joining Al2O3 ceramics

Ceramizable heat-resistant organic adhesive (CHA) was prepared by using preceramic polymer polysiloxane as matrix, TiB₂ ceramic powder and low melting point glass powder as additives. The curing mechanism, thermal stability properties, phase composition after pyrolysis, structural evolution of bonding layer and bonding mechanism of the adhesive were investigated by FTIR, TGA-DSC, XRD, SEM, FESEM and bonding strength tests. Results of bonding tests showed the maximum shear strength of the joints was 21 MPa when heat treatment at 1200 °C for 2 h in air. Polysiloxane resin acted as crosslinking adhesive at low temperatures and tended to convert to ceramic bonding layer at high temperatures, resulting from ceramization reaction with active fillers. The formation and growth of ceramic phase after heat treatment enhanced the thermal stability and bonding performance of the adhesive at high temperature.     

Hygrothermal ageing of adhesive joints with nanoreinforced adhesives and different surface treatments of carbon fibre/epoxy substrates

The effect of water absorption on the strength of single lap adhesive joints subjected to accelerated hygrothermal ageing (55 °C, 95% relative humidity, 800 h) was analysed. Two different variables were studied: the surface treatment of the carbon fibre/epoxy laminates (peel ply, grit blasting and atmospheric pressure plasma) and the addition of carbon nanofillers (0.5 wt% nanofibres and 0.25 wt% nanotubes) to the epoxy adhesive. The joint strength and the failure mode of the joints were investigated. Furthermore, the amount of water absorbed by the adhesive was determined.Adhesive joints with peel ply-treated laminates exhibit an increase in their strength, which is attributed to a relaxation of stresses in the adhesive/laminate interface; with grit blasting, this property remains almost constant. Plasma treatment provides the worst ageing behaviour because this treatment results in a surface with a higher surface free energy, which is more susceptible to environmental attack. The nanoreinforcement of the adhesive has a beneficial effect: it decreases the amount of absorbed water.     

Rapid diffusion bonding of WC-Co cemented carbide to 40Cr steel with Ni interlayer: Effect of surface roughness and interlayer thickness

WC-Co cemented carbides were rapidly diffusion bonded to 40Cr steels with pure Ni as interlayers by utilizing plasma activated sintering (PAS). The bonding was carried out at 750 °C for 13 min under a pressure of 40 MPa. It was found that the roughness of the initial surfaces still plays an important effect on the microstructure and mechanical behavior of the joints diffusion bonded by PAS irrespective of the electric current applied during bonding. The adoption of smoother original surfaces was significantly favorable to eliminate the interfacial interstices and microvoids. Correspondingly, the shear strength of the diffusion bonded joints increased with decreasing surface roughness. Additionally, the effect of interlayer thickness on the shear strength of the joints was also evaluated, and the results showed that the strength decreased sharply when thicker interlayer was employed. A maximum value of shear strength, 293.07 MPa, was obtained when the original surfaces was ground with P1200 grit SiC paper and at the same time 50 µm thick interlayer was used. In this case, the fracture initiated and run predominantly along the bonding interfaces instead of in the WC-Co substrate.