The Effect of Moisture Content in Epoxy Film Adhesives on their Performance. III: Bulk Properties

Humidity absorbed by epoxy film adhesives during low temperature storage or exposure to atmosphere may result in reversible changes and irreversible modifications. Vacuum treatment may partially remedy the reversible changes. The consequences of vacuum drying are manifested in enhancement of both the peel and shear properties of bonded joints (Part I and Part II of this series of papers) and the thermal, physical and mechanical properties of the bulk adhesive, characterized in the present study.

Experimental results have shown that the bulk properties of structural epoxy based adhesives are highly correlated with the aging processes caused by water absorption in the prepolymerized adhesive. Applying the vacuum process is harmful to fresh unaged adhesive due to devolatization of low molecular species of the film adhesive.

The characterization of bulk properties for the purpose of following the aging and recovery processes is advantageous, since the bulk is independent of geometrical and interfacial effects which dominate in the case of property evaluation of the adhesive in a bonded joint.     

Room Temperature Curing Epoxy Adhesives for Elevated Temperature Service

Room Temperature curing compositions of epoxy resins with high temperature service capability (95-120°C) were formulated and evaluated. The compositions were based on selected high functionality atomatic epoxy polymers and multicomponent poly amine curing agent systems. Toughening was achieved by addition of a rubbery phase either by prereaction of the epoxy resin with carboxyl terminated (CTBN) or by amine terminated (ATBN) poly butadiene acrylonitrile. The latter elastomeric component served as a part of the poly amine curing agent.

Best results were achieved with an adhesive formulation comprising tetra glycidyl-4-4'-diaminodiphenylmethane (TGDDM) and triglycidyl ether of p-aminophenol with triethylenetetramine and addition of ATBN with a felt carrier.

Lap shear strengths of aluminum/aluminum specimens primed by silane coupling agent in the order of 22 MPa at 25°C and 11 MPa at 120°C with T-Peel strengths of 1.6N/mm at 25°C and 0.52 N/mm at 120°C, were obtained.

The thermal behaviour and transitions, the chemical and mechanical properties, the microstructure and morphology of the selected adhesive formulation were studied, using DSC, Gehman, FTIR, mechanical testing and SEM analysis, respectively.

Experimental results showed that the selected compositions could develop good high temperature (120°C) properties while cured at room temperature. Furthermore, their high temperature performance compares favorably or even exceeds that of commercially available room-temperature-curing adhesive compounds, and are competitive with elevated temperature cured film adhesives.     

The Effect of Silane Coupling Agents on the Durability of Titanium Alloy Joints

An aqueous solution of γ-glycidoxypropyltrimethoxysilane (GPS) applied to titanium alloy adherends greatly improved bond durabilities compared to alloy surfaces that were only abraded and solvent cleaned, γ-aminopropyltriethoxysilane (APS) also gave improved durability but was not so effective.

Three epoxy adhesives differed considerably in their responses to the five metal pretreatments that were compared. Overall, a sodium hydroxide anodise treatment gave the highest resistance to crack growth in the wedge test.     

Silane Coupling Agents as Adhesion Promoters for Aerospace Structural Film Adhesives

The performance of eight organofunctional silane coupling agents as adhesion promoters for the bonding of aluminium with two 121°C and two 177°C curing structural film adhesives was investigated and compared to the chromic acid (FPL) etch pre-treatment process and two non-chemical pretreatments. Aspects considered were shear strength of joints at ambient and elevated temperatures and durability, as judged by the wedge test.

The epoxy silane, γ-glycidoxypropyltrimethoxy silane, was found to be a very efficient adhesion promoter with all film adhesives evaluated. The cationic styryl silane, a neutral diamine monohydrochloride, showed promise with two adhesive systems. Four other neutral silanes were less effective.

Performance of amine functional silanes was mixed. Although the shear strength of joints with the primary amine silane at its natural pH of ∼10.3 was relatively good, durability was poor. However, good durability was obtained if the primer was first adjusted to pH 8 with hydrochloric acid, but not if acetic or phosphoric acids were used. Diamine silane was not an effective adhesion promoter at either its natural pH or when acidified with hydrochloric acid.     

UV-Curable Transparent Adhesives for Fabricating Precision Optical Components

UV-curable transparent epoxy adhesives have been specifically developed for the fabrication of optical communictions precision devices. The newly developed adhesives using cylohexane type fluoro-epoxy as the base resin and speherical quartz filler have extremely low volume shrinkage of 1.2% during curing and the cured adhesives have low thermal expansion coefficient of less than 2 × 10^-5/°C. Sheets of the adhesives are colorless and transparent to visible light because the refractive index of the epoxy matrix resin is matched to that of the quatz filler. These highly transparent adhesives can be cured to a depth of more than 5 mm by using 10 mW/cm² UV-irradiation for 30 min. They also have high adhesive strength and good durability. Therefore, they can be used in the fabrication of optical components that require submicron positioning accuracy.     

A Stress Singularity Approach for the Prediction of Fatigue Crack Initiation in Adhesive Bonds. Part 1: Theory

Since crack initiation in adhesive bonds tends to occur near the interface corners where the stress fields are singular, we define a fatigue initiation criterion using stress singularity parameter, Q (a generalized stress intensity factor) and the singular eigenvalue, λ.

Hattori et al., successfully used a generalized stress intensity factor to characterize the static strength of bimaterial interfaces. We show that this criterion is only appropriate for situations in which the adhesive contact angle is no larger than 90° and the modulus ratio (adhesive to adherend) is smaller than 0.1. Fortunately, these conditions are often met in real joints, permitting the use of a single eigenvalue approach. We then extend this criterion to the case of fatigue arising from mechanical, thermal, or hygroscopic cycling.

In preparation for Part 2 (experimental), the special case of an epoxy wedge on a flat aluminum substrate is considered. The singularity is analyzed both analytically and numerically. The scale of the region dominated by the singularity is found to be of the order of 100 μm. The size of the plastically yielded zone near the apex is found to decrease extremely rapidly as the stress intensity factor goes down, thereby increasing the applicability of the method at the low stress levels often encountered in fatigue.     

Hygrothermal Properties of Epoxy Film Adhesives

The hygrothermal response of high performance epoxy film adhesives, in their bulk state, has been characterized over a wide range of temperatures, following exposure to a combination of humidity (95% R.H.) and heat (50°C).

Experimental results have indicated that the testing temperature has a pronounced effect on both tensile modulus and strength of the adhesives, while the effect of moisture content varies with respect to the adhesive type. The moduli of the film adhesives, which have a wide range of glass transition temperatures (T_g), have been related to both moisture level in the adhesive and testing temperature. This has been accomplished by employing a dimensionless temperature, which incorporates the wet and dry T_g and the testing, as well as a reference, temperature. The strength properties have shown a higher degree of scatter using the abovementioned dimensionless temperature.

Scanning electron microscopy of the fracture surfaces have shown a good agreement between the effects of moisture and the mechanical properties. Adhesives which exhibited good moisture resistance, as manifested by the stability in their tensile properties, showed minor changes in their fracture surfaces regardless of moisture conditioning. Distinctively, the effect on strength properties has been correlated with typical moisture-induced fracture mechanisms.     

Influence of Fabrication Residual Thermal Stresses on Rubber-toughened Adhesive Tubular Single Lap Steel-Steel Joints under Tensile Load

The tensile load bearing capability of adhesively-bonded tubular single lap joints which is calculated under the assumption of linear mechanical adhesive properties is usually much less than the experimentally-determined because the majority of the load transfer of adhesively-bonded joints is accomplished by the nonlinear behavior of rubber-toughened epoxy adhesives. Also, as the adhesive thickness increases, the calculated tensile load bearing capability with the linear mechanical adhesive properties increases, while, on the contrary, the experimentally-determined tensile load bearing capability decreases.

In this paper, the stress analysis of adhesively-bonded tubular single lap steel-steel joints under tensile load was performed taking into account the nonlinear mechanical properties and fabrication residual thermal stresses of the adhesive. The nonlinear tensile properties of the adhesive were approximated by an exponential equation which was represented by the initial tensile modulus and ultimate tensile strength of the adhesive.

Using the results of stress analysis, the failure criterion for the adhesively-bonded tubular single lap steel-steel joints under tensile load was developed, which can be used to predict the load-bearing capability of the joint. From the failure criterion, it was found that the fracture of the adhesively-bonded joint was much influenced by the fabrication residual thermal stresses.     

Multifunctional NIR-reflective and self-cleaning UV-cured coating for solar cell applications based on cycloaliphatic epoxy resin

We report here a simple, cheap and scale up process for obtaining a multifunctional coating with both, IR reflective and hydrophobic properties. These coatings can be applied on solar devices in order to limit their overheating under operating conditions. The system is based on UV-curable epoxy coating containing IR-reflective fillers and a silicone additive to modify the surface properties with a good hydrophobicity enhancement. The filler dispersion into the epoxy UV-curable resin did not significantly influence the photocuring rate, while a slight decrease of the final epoxy group conversion was evidenced. The optical properties of the obtained coatings have been evaluated by UV–vis–NIR spectroscopy showing that the films act as good “filters” in the NIR region, giving rise to a reduction of the absorbed heat and of the working temperature of the cells. A pronounced increase of hydrophobicity for the films containing the silicone additive was observed. The optical properties were not affected by the addition of the silicone additive.     

Synthesis and characterization of UV-curable dual hybrid oligomers based on epoxy acrylate containing pendant alkoxysilane groups

This work involves the synthesis of novel hybrid oligomers based on a UV-curable epoxy acrylate resin (EA). The EA resin was modified with various amount of 3-isocyanatopropyl trimethoxysilane (IPTMS) coupling agent. The modification percentage of the hybrid oligomer was varied from 0 to 50 wt.%. UV-curable, hard and transparent organic–inorganic hybrid coatings were prepared on Plexiglas substrates and their characterization was performed by the analyses of various properties such as hardness, gloss, tape adhesion test and stress–strain test. Results from the mechanical measurements show that the properties of hybrid coatings improve with the increase in modification ratio. The thermal behavior of coatings was also evaluated. It is observed that the thermal stability of epoxy acrylate coatings is enhanced with incorporation of siloxane. Gas chromatography/mass spectrometry analyses showed that the initial weight loss obtained in thermogravimetric analysis is due to the degradation products of the photoinitator and the acrylic acid moiety of acrylic monomers.     

Improvements of the structural,thermal, and mechanical properties of structural adhesive with functionalized boron nitride nanoparticles

Investigations on the production and development of nanoparticle-reinforced polymer materials have been attracted attention by researchers. Various nanoparticles have been used to improve the mechanical, chemical, thermal, and physical properties of polymer matrix composites. Boron compounds come to the fore to improve the mechanical and thermal properties of polymers. In this study, mechanical, thermal, and structural properties of structural adhesive have been examined by adding nano hexagonal boron nitride (h-BN) to epoxy matrix at different percentages (0.5, 1, 2, 3, 4, and 5%). For this purpose, nano h-BN particles were functionalized with 3-aminopropyltriethoxysilane (APTES) to disperse the h-BN nanoparticles homogeneously in epoxy matrix and to form a strong bond at the matrix interface. Two-component structural epoxy adhesive was modified by using functionalized h-BN nanoparticles. The structural and thermal properties of the modified adhesives were investigated by scanning electron microscopy and energy dispersion X-ray spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis techniques. Tensile test and dynamic mechanical analysis were performed to determine the mechanical properties of the adhesives. When the results obtained from analysis were examined, it was seen that the nano h-BN particles functionalized with APTES were homogeneously dispersed in the epoxy matrix and formed a strong bond. In addition that, it was concluded from the experimental results that the thermal and mechanical properties of adhesives were improved by adding functionalized nano h-BN particles into epoxy at different ratios.     

Durability of Adhesive Bonds to Zinc-Coated Steels: Effects of Corrosive Environments on Lap Shear Strength

The effects of corrosive environments on adhesive bonds to electro-galvanized, zinc/aluminum alloy coated, coated electro-galvanized, and cold-rolled steels have been investigated. Bonds prepared using a rubber-modified dicyandiamide-cured epoxy adhesive, an epoxy-modified poly(vinyl chloride)-based adhesive, an acrylic-modified poly(vinyl chloride)-based adhesive a one-part urethane adhesive, and a two-component epoxy-modified acrylic adhesive were exposed under no-load conditions to constant high humidity or cyclic corrosion exposure for 50 days or 50 cycles (10 weeks) respectively.

Over the course of this study, exposure to constant high humidity had little effect on lap shear strength for any of the systems studied. Bond failures were initially cohesive, and with few exceptions remained so.

Bond strength retention under the cyclic corrosion exposure conditions employed was strongly dependent on adhesive composition and on substrate type. On galvanized substrates, lap shear strengths for the poly(vinyl chloride)-based adhesives were reduced by 90-100% during the course of the corrosion exposure, and a change in the mode of bond failure (from cohesive to interfacial) was observed. On the coated electro-galvanized steel substrate, the poly(vinyl chloride)-based adhesives showed about 50% retention in lap shear strength and a cohesive failure throughout most of the corrosion test. The dicyandiamide-cured epoxy adhesive used in this study generally showed the best lap shear strength retention to zinc-coated substrates; bonds to cold-rolled steel were severely degraded by corrosion exposure. The performance of the acrylic and urethane adhesives were intermediate to the dicyandiamide-cured epoxy and poly(vinyl chloride)-based adhesives in strength retention.     

Aging Process of Metal/Epoxy Laminates Investigated with X-ray Photoelectron Microscopy and Spectroscopy

In this article we describe the application of X-ray photoelectron spectroscopy to epoxy/dicyandiamide laminates on zinc galvanized steel which were aged under different environmental conditions involving high humidity and temperatures.

X-ray photoelectron microscopy allows us to identify the distribution of chemical elements with a lateral resolution of 10μm. Areas selected in the microscopy mode were then analyzed in the spectroscopy mode in order to get information on the local chemical composition.

We compared the spectroscopic features of the aged but freshly delaminated surfaces of samples stored under ambient conditions at room temperature with samples exposed to the “Kataplasmann” and the “KWT” test, respectively. Furthermore, a comparison was made with a model sample which was prepared in vacuum and on which the curing process was investigated.

Though there is no substantial loss in the lap-shear strength of the samples, we find drastic spectroscopic changes in the Kataplasma and KWT treated samples compared with the sample kept at room temperature. We conclude that the chemical changes induced by these tests cause an internal interphase boundary between the epoxy/metal interface and the bulk adhesive along which delamination occurs. Comparison with the behavior of the water-vapor-treated model sample gives evidence that hydrolysis is the main reaction in these tests.

The results described here complement our former study.¹     

Dielectric and pyroelectric properties of triglycine sulphate-polystyrene composites

A composite of Triglycine sulphate (TGS) and polystyrene has been fabricated by mixing different particle size TGS powders (75 μm to 400 μm) and polystyrene solution. The dielectric constant has been measured in the frequency range 0.1 to 100 KHz, and the pyroelectric current measurements were made by the Byer and Roundy direct method. Specific heat of the composite was determined by the differential them analysis (DTA) technique.

Particle size dependance of dielectric constant, pyroelectric coefficient and responsivity have been studied. Anomalies in ε' and P_y were observed even in the composite with the lowest particle size of TGS (75 μm). The surface effects have much greater influence on electrical properties but thermal properties are, not affected. This is indicated by a decrease in ε' and P^y with decreasing particle size of TGS, while specific heat of composite is almost independent of particle size.     

Nonlinear Analysis of theTorque Transmission Capability of Adhesively Bonded Tubular Lap Joints

Calculated torque transmission capability of adhesively bonded tubular lap joints using linear elastic material properties is usually much less than the experimentally-determined one because the majority of the load transfer of the adhesively bonded joints is accomplished by the nonlinear behavior of rubber-toughened epoxy adhesives.

Although the adhesively bonded tubular double lap joint has better torque transmission capability and reliability than the single lap joint, the nonlinear analytic or numerical analysis for the adhesively bonded tubular double lap joint has not been performed because of numerical complications.

An iterative solution that includes the nonlinear shear behavior of the adhesive was derived using the analytic solution. Since the iterative solution can be obtained very quickly due to the simplicity of the algorithm, it is an attractive method of designing adhesively bonded tubular single and double lap joints.     

聚氨酯改性环氧树脂光学结构胶的研制

采用自制的端异氰酸基聚醚型聚氨酯预聚体对环氧树脂进行改性,对其添加量对改性树脂的性能的影响进行了考察,并与A-12胶黏剂的性能做了综合对比。结果表明环氧树脂增韧改性后对多种材料都具有良好的粘接性能,其中冲击强度由未改性时的12．1kJ／m^2提高到24．4kJ／m^2,剥离强度由1．4kN／m提高到3．4kN／m,断裂伸长率由5．2％提高到14．8％;其耐高低温交变性能好,-60～100℃循环5次玻璃未炸裂,并具有优异的耐介质性能。     

Factors Affecting the Durability of Ti-6Al-4V/Epoxy Bonds

Factors influencing the durability of Ti-6Al-4V/epoxy interphases were studied by determining chemical and physical properties of Ti-6Al-4V adherend surfaces and by characterizing the strength and durability of Ti-6Al-4V/epoxy bonds.

Ti-6Al-4V adherend surfaces were oxidized either by chemical etch or anodization. Four principal pretreatments were studied: chromic acid anodization (CAA), sodium hydroxide anodization (SHA), phosphate fluoride acid etch (P/F) and TURCO basic etch (TURCO). The oxides were characterized by SEM, STEM, profilometry, contact angles and XPS.

All adhesive bonding was carried out using a structural epoxy, FM-300U. Both lap shear and wedge test samples were tested in hot, wet environments. The results lead to the conclusion that the interfacial area between the adhesive and adherend is the primary factor affecting bond durability.     

Electrorheological properties of BaTiO3 suspensions

Electrorheological (ER) fluids based on a silicone oil matrix with a high dielectric constant particulate component, BaTiO₃, were evaluated. Particle size effects were examined with a commercial BaTiO₃ (0.35μm in size) and a hydrothermally prepared BaTiO₃ powder with an average particle size of 0.07μm. The commercial powder exhibited an ER response to DC fields, but above a critical field strength rheological properties dropped off drastically. The relative magnitude of yield stresses, at field levels below the critical field strength, are comparable with current literature values. Hydrothermally prepared BaTiO₃ powder exhibited minimal ER response to applied DC fields.

Optical microscope studies of dilute suspensions (∼1-2 volume percent) were used to correlate fibril formation with ER measurements. Under applied DC fields, turbulent flow dominated above 6.25kV/cm and ER properties diminished. Increased frequency led to an increase in the degree of fibril formation with a maximum level occurring around 6OHz.

In response to AC fields, both types of BaTiO₃ powders showed a strong frequency dependence. Maximum shear stress for a given field strength resulted at about 60Hz. Optical microscopy showed an increase in fibril formation with increased AC field strength (60Hz). Turbulent flow did not appear with increased AC field (60Hz) at all field strengths evaluated (≤20kV/cm). All suspensions exhibited a linear relationship between yield stress and the square of applied electric field, which is characteristic of dipole-dipole interactions.     

Strength Analysis of Adhesively-Bonded Tubular Single Lap Steel-Steel Joints Under Axial Loads Considering Residual Thermal Stresses

The static tensile load bearing capability of adhesively-bonded tubular single lap joints calculated using linear mechanical adhesive properties is usually far less than the experimentally-determined one because the majority of the load transfer of adhesively-bonded joints is accomplished by the nonlinear behavior of the rubber-toughened epoxy adhesive

In this paper, both the nonlinear mechanical properties and the residual thermal stresses in the adhesive resulting from joint fabrication were included in the stress calculation of adhesively-bonded joints. The nonlinear tensile properties of the adhesive were approximated by an exponential equation which was represented by the initial tensile modulus and ultimate tensile strength of the adhesive.

From the tensile tests and the stress analyses of adhesively-bonded joints, a failure model for adhesively-bonded tubular single lap joints under axial loads was proposed.     

Improvement of the Durability of Zinc-Coated Steel/Epoxy Bonded Joints

The durability properties of bonded lap shear joints made from an epoxy/dicyandiamide adhesive and hot-dipped galvanized (G2F) or electroplated-phosphated (EZ2) steel have been investigated. The degradation mechanisms have been studied after three accelerated ageing tests: the “cataplasme humide” (“C.H.T.”), immersion (“I.T.”), and salt spray (“S.S.T.”) tests. X-ray photoelectron spectroscopy (XPS) analysis of fracture surfaces after ageing have shown that anodic dissolution of the zinc-coating is responsible for debonding in all cases and that intergranular corrosion phenomena account for poorer performances of the hot-dipped galvanized substrate during “C.H.T.” and “I.T.” Silane coupling agents were successfully used as primers on both substrates to increase the hydrolytic stability of the metal/adhesive interface. XPS results indicate that both the interfacial dissolution of the phosphate coating of EZ2 and intergranular corrosion of G2F are delayed for silane-primed specimens. The observed improvements do not appear to depend on the nature of the silane coupling agents. Alkylsilanes have been found to perform as well as silanes having a group capable of reacting with the epoxy/dicyandiamide system.

Additional tests were carried out in view of the possible application of organosilane reagents as additives in corrosion-protective oils. Good durability properties have been obtained by priming the metal coupons with a standard oil/silane mixture prior to bonding.

When corrosion was the controlling degradation mechanism as is the case during the salt spray test, silane treated specimens did not generally perform better than control specimens.