Preliminary Evaluation of Hybrid Titanium Composite Laminates

In this study, the mechanical response of hybrid titanium composite laminates (HTCL) was evaluated at room and elevated temperatures. Also, the use of an elastic-plastic laminate analysis program for predicting the tensile response from constituent properties was verified. The improvement in mechanical properties achieved by the laminates was assessed by comparing the results of static strength and constant amplitude fatigue tests with those for monolithic titanium sheet. Two HTCL were fabricated with different fiber volume fractions, resin layer thicknesses and resins. One panel was thicker and was poorly bonded in comparison with the other. Consequently, the former had a lower tensile strength, while fewer cracks grew in this panel and at a slower rate. Both panels showed an improvement in fatigue life of almost two orders of magnitude. The model predictions were also in good agreement with the experimental results for both HTCL panels.     

Preliminary Evaluation of Hybrid Titanium Composite Laminates

In this study, the mechanical response of hybrid titanium composite laminates (HTCL) was evaluated at room and elevated temperatures. Also, the use of an elastic-plastic laminate analysis program for predicting the tensile response from constituent properties was verified. The improvement in mechanical properties achieved by the laminates was assessed by comparing the results of static strength and constant amplitude fatigue tests with those for monolithic titanium sheet. Two HTCL were fabricated with different fiber volume fractions, resin layer thicknesses and resins. One panel was thicker and was poorly bonded in comparison with the other. Consequently, the former had a lower tensile strength, while fewer cracks grew in this panel and at a slower rate. Both panels showed an improvement in fatigue life of almost two orders of magnitude. The model predictions were also in good agreement with the experimental results for both HTCL panels.     

Plasma-Sprayed Aluminum and Titanium Adherends: III

The durability of aluminum and titanium adherends, plasma-sprayed with polymeric coatings, and bonded with an epoxy and a polyimide adhesive has been investigated. Organic-polymeric coatings were plasma-sprayed using epoxy, polyester, polyimide, and cyanate ester components. Durability was investigated using a wedge-type specimen by exposing the specimens to an environmental cycle that included low temperature, high relative humidity at elevated temperature, high temperature at atmospheric pressure in air, high temperature in a vacuum, and room temperature. The systems exhibiting durability comparable with that for adherends treated using standard solution methods, included aluminum or titanium coated with a bis-maleimide/cyanate ester (B-CE) or a bis-maleimide-LaRC TPI-1500^® (B-TPI) mixture and bonded with an epoxy or a polyimide adhesive. For these B-CE- and B-TPI-coated specimens, failure during exposure to the environmental cycle occurred in the adhesive, indicating a favorable adherend/plasma-sprayed coating interaction.     

AGING CHARACTERIZATION OF ADVANCED POLYMER SYSTEMS

Aging of three advanced polymer systems used as adhesives in the aerospace industry is characterized by Fourier transform infrared spectroscopy (FTIR) with attenuated total reflectance (ATR-FTIR), dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS).Since significant changes in mechanical properties were observed for AF191, FM®73, and FM®5 bonded joints, the purpose of this work was to identify whether there is any chemical and physical degradation for the adhesives used in these joints. Each of the adhesives has been evaluated after exposing to Hot/Wet and Hot/Dry environments for 5000 h. They were also thermally cycled in conditions that represent subsonic and supersonic cruise. Hot/wet exposures demonstrated a greater amount of possible degradation than hot/dry or thermally cycled exposures. The hot/wet aging condition resulted in more pronounced O-H, C-H, and N-H infrared absorptions, reduced glass transition temperature of adhesives, and reduced tensile and fracture properties of corresponding bonded systems. Overall, these adhesives were chemically very stable under the environments to which they were exposed, even though some of the joints showed reduced fracture toughness due to the exposure. Additional work is needed to understand the mechanism causing the change in joint properties when exposed to these environments.     

Interlaminar Bond Strength and Failure Mechanisms in Commercial Flexible Polymer-Metal Laminates

An alternative to the 180° “T” peel test (called simply the “T-peel test” in the USA) was developed by Cropper and Young for the measurement of interlaminar bonding in three-ply polypropylene-aluminium-polyester laminates used in food packaging applications. The effect of temperature on the interlaminar bond strength of three laminate systems has since been studied. In particular, the effect of temperature on both the failure mode and on the adhesive's appearance after testing has been determined. It is shown that as the temperature is raised about 23°C, the laminating adhesive begins to soften and the failure mode changes from almost exclusively adhesive failure at the polyurethane adhesive-aluminium interface to cohesive failure of the polyurethane adhesive itself. The change in the failure mode is accompanied by the appearance of a meniscus instability. The temperature at which the meniscus instability patterns become more prominent correspond to the temperature at which the maximum interlaminar bond strength is attained.

It is thought that this new test can be used to characterise the behaviour of laminating adhesives more fully, both in their change in appearance with temperature, and in their effectiveness in bonding layers together as temperatures are increased above ambient conditions.     

Polyetherimide Adhesive

High-temperature adhesives which can be adhered at adhesive temperatures lower than those of conventional polyimide adhesives were investigated. Polyetherimide (PEI), developed by General Electric Co., is one such promising low curing temperature adhesive because it melts at temperatures lower than those used for conventional polyimides. Lap shear adhesive strength was investigated in a 75 μm-thick PEI film using steel test pieces. 350 kgf/cm² was achieved after curing for 1 hour at 270°C and 150 kgf/cm² was achieved at the test temperature of 200°C. PEI adhesive dissolved by N, N-dimethylformamide exhibited a high adhesive strength of 240 kgf/cm² after curing for 2 hours at 200°C. In addition, it was found that PEI could be used at much lower adhesive pressures than those of conventional polyimide adhesives.     

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.     

A Water Soluble Hydrated Metal Oxide primer for Adhesively Bonded Joints

Weight saving and manufacturing cost benefits have led to the increase in use of adhesively-bonded structures in the automotive, aerospace and marine industries. In order to be a viable alternative to, for example, metal fasteners, these adhesive bonds should maintain the strength typical of conventional fastener systems. In many applications, the bonds are put under a variety of environmental and mechanical stresses. For example, frequently these bonds are exposed over long periods of time to wet environments which can result in a loss of bond strength. The loss of strength can result from the extension of cracks and other deformations that occur in the adhesive or metal oxide which are accelerated by the moist environment. As a result of this deficiency, extensive research and development efforts have been undertaken to define methods and identify materials which improve bonded joint performance in humid conditions. For example, it is known that surface preparation is important in the bonding of aluminum and titanium, and cleanliness in the bonding of ceramic articles. Thus, it is essential that, before bonding, the adherend is cleaned and chemically pretreated to produce a surface which in combination with the adhesive develops the bond strengths which meet application requirements. The normal procedure after surface treatment is to apply a corrosion-inhibiting primer by a spray technique for surface protection prior to bonding and to insure resin penetration into the oxide structure which provides improved environmental resistance. A major drawback of spray application is the large volume of organic solvent (normally MEK) emitted to the atmosphere. A successful alternative is the recently-developed electrodeposited primer by Northrup Corp., which consists of water solubilized primer particles which migrate in an electric field to a conductive work piece where they are deposited in a dense, continuous coating.¹ The primer was developed for use with 121°C (250°F) curing epoxy adhesives. An Air Force sponsored contract is currently under way, the objective of which is to develop an electrodeposited water-based primer for use with 177°C (350°F) curing epoxy systems.² A water-based epoxy primer system for application using the more conventional spray techniques has also been decribed.³     

Epoxy–novolac interpenetrating network adhesive for bonding of plasma-nitrided titanium

This investigation highlights rationale to synthesize epoxy–novolac adhesive by novel interpenetrating network (IPN) technique. Physicochemical characteristics of the plain adhesive and IPN adhesive were carried out by Fourier transform infrared spectroscopy and thermal gravimetric analysis. Performing lap-shear test carried out plasma-nitrided titanium was fabricated with these adhesives and mechanical property of these adhesives. The blend of epoxy and novolac was optimized at 4:1 ratio, and the formation of IPN was confirmed by the suppression of creep with reference to neat epoxy and its swelling behavior. The adhesive with IPN shows significantly higher thermal stability than epoxy and leaves higher amount of residuals at the elevated temperature. Due to surface modification of titanium by plasma nitriding, wetting characteristics of titanium increases considerably and consequently, there was a significant increase in lap-shear strength adhesively of bonded titanium substrate.     

A Test Method for Accelerated Humidity Conditioning and Estimation of Adhesive Bond Durability

The ability to determine the durability of adhesive bonds remains an elusive task, especially when the service environment involves exposure to diluents such as water. Moisture continues to be of major concern for many adhesive bond systems for a number of reasons including:

1) many adhesives are hydrophilic, picking up significant amounts of moisture over time;

2) most adhesives and some adherends allow moisture permeation, eventually reaching the adhesive/adherend interface;

3) the high surface energies of metallic and certain other substrates result in moisture migrating to the adherend surfaces and displacing the adhesive from the substrates, and possibly oxidizing the adherend, etc., and

4) absorbed moisture induces swelling stresses which can reduce the bond strength.

Recognition of this susceptibility to moisture has led to extensive studies aimed at evaluating the effects of moisture, developing an understanding of the responsible mechanisms, and predicting the performance of adhesive bonds subjected to humid environments. While some studies have focused on the effect of humidity on neat adhesive samples, most studies have recognized the significance of the adhesive/adherend interactions, and have evaluated strength of actual bonded joints. Unfortunately, the time required for typical bonded geometries to reach moisture equilibrium can be quite long. Single lap joints (SLJ) and double cantilever beam (DCB) specimens with a width of 25mm may take several years to equilibrate, depending on the temperature and adhesive. Such lengthy conditioning times hamper the development of improved adhesives, and may delay the acceptance of these adhesives because of the time required to certify them. Methods to accelerate the conditioning of test specimens would be of significant benefit to adhesive formulators and users.     

The Effect of Temperature on the Strength of Adhesively-Bonded Composite-Aluminium Joints

Different materials have different coefficients of thermal expansion, which is a measure of the change in length for a given change in temperature. When different materials are combined structurally, as in a bonded joint, a temperature change leads to stresses being set up. These stresses are present even in an unloaded joint which has been cured at say 150°C and cooled to room temperature. Further stresses result from operations at even lower temperatures.

In addition to temperature-induced stresses, account also has to be taken of changes in adhesive properties. Low temperatures cause the adhesive to become more brittle (reduced strain to failure), while high temperatures cause the adhesive to become more ductile, but make it less strong and more liable to creep.

Theoretical predictions are made of the strength of a series of aluminium/CFRP joints using three different adhesives at 20°C and 55°C. Various failure criteria are used to show good correlation with experimental results.     

Adhesion Studies of Mixtures of Ethyl Cyanoacrylate with a Difunctional Cyanoacrylate Monomer and with other Electron-deficient Olefins

Alkyl cyanoacrylate instant adhesives are widely used because of their fast cure speed and versatility on a large number of substrates. Recent performance improvements, such as increased thermal resistance, resulted from the addition of latent acids and polymers, which do not copolymerize with the adhesive monomer, to the adhesive formulations. However, use of these additives can increase fixture time or reduce the final adhesive strength.

Two methods for possibly improving alkyl cyanoacrylate instant adhesives, without loss of cure speed or adhesive properties, could be either crosslinking the alkyl cyanoacrylate monomer with a dicyanoacrylate or copolymerizing it with a second 1, 1 disubstituted electron-deficient olefin. A crosslinker. 1,4 butanediol dicyanoacrylate (BDDCA) and two monofunctional monomers, diethyl methylenemalonate (DEMM) and N,N diethyl-2-cyanoacrylamide (DECA), were prepared, in good purity, for adhesion studies with ethyl cyanoacrylate (ECA). Crosslinking ECA with BDDCA does improve solvent resistance, as determined by solvent swelling experiments. Glass fixture times are approximately the same for ECA, crosslinked ECA, the pure monomers, and monomer mixtures with ECA, while steel fixture times are generally slower. Crosslinking ECA with BDDCA does not improve lap-shear adhesion, either at room temperature or after thermal exposure at 121°C. Lap-shear strength data, before and after heat exposure, revealed that the ECA/DEMM and the ECA/DECA monomer mixtures exhibit weaker lap-shear adhesive strength than ECA alone.     

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.     

The Adhesively Bonded Aluminium Joint: The Effect of Pretreatment on Durability

The interface in aluminium bonded structures can be revealed by ultramicrotomy and subsequently studied by transmission electron microscopy. By these means, the more usual surface pretreatments encountered, have been characterised in depth.

A similar examination has been effected following exposure of bonded joints (floating roller peel specimens) to 85% relative humidity at 70°C. Although a drop in peel performance is noted over the exposure time, interfacial examination reveals little damage to the adhesive or adherend. Possible mechanisms for bond strength reduction are discussed: subtle undermining of the alumina film and disruption of physico-chemical bonds across the interface. Both are initiated by moisture reaching the alumina film, either passing along the interface itself or travelling through the adhesive matrix. Also considered are the effects of surface pretreatment and “oxide” penetration, by the adhesive, on durability.

The effect of priming the adherend surface prior to bonding, using a heavily strontium chromate filled adhesive primer, is mentioned and its possible influence on durability is briefly discussed.     

Primers for Bonding Polyolefin Substrates with Alkyl Cyanoacrylate Adhesive

Polyolefins, such as polypropylene and polyethylene, are among the most commonly-utilized plastics in the world, but, because of their non-polar surfaces, are among the most difficult to bond with adhesives. A surface treatment is required before adhesive application to achieve good adhesion.

Alkyl cyanoacrylates are widely used instant adhesives, e.g. Super Glue^®, for bonding a variety of substrates, such as metal, plastics, glass, wood, and leather. It would be desirable to bond polyolefins with these adhesives because of their availability and ease of use. Amines and ammonium carboxylates, possessing long alkyl chains, were evaluated as adhesion promoting primers for alkyl cyanoacrylate adhesives on polyolefins.

Among trialkyl amines, trialkylammonium carboxylates, and tetraalkylammonium carboxylates, trialkylammonium carboxylate primers produced an adhesive bond so strong that the failure occurred at the polyolefin substrate. Trialkylammonium carboxylate primers also demonstrated excellent performance retention over prolonged atmospheric exposure prior to application of the adhesive. Trialkyl amines and tetraalkylammonium carboxylates also promoted adhesion but lost maximum effectiveness on exposure to the atmosphere. The cause of the deterioration in amine primer effectiveness over prolonged exposure was identified to be trialkylammonium bicarbonate formation and/or diffusion of the primer into the polyolefin surface.     

Flexibilized Copolyimide Adhesives

Two copolyimides, LARC-STPI and STPI-LARC-2, with flexible backbones were prepared and characterized as adhesives. The processability and adhesive properties were compared to those of a commercially available form of LARC-TPI.

Lap shear specimens were fabricated using adhesive tape prepared from each of the three polymers. Lap shear tests were performed at room temperature, 177°C, and 204°C before and after exposure to water-boil and to thermal aging at 204°C for up to 1000 hours.

The three adhesive systems possess exceptional lap shear strengths at room temperature and elevated temperatures both before and after thermal exposure. LARC-STPI, because of its high glass transition temperature provided high lap shear strengths up to 260°C. After water-boil, LARC-TPI exhibited the highest lap shear strengths at room temperature and 177°C, whereas the LARC-STPI retained a higher percentage of its original strength when tested at 204°C [68% versus 50% (STPI-LARC-2) and 40% (LARC-TPI)].

These flexible thermoplastic copolyimides show considerable potential as adhesives based on this study and because of the ease of preparation with low cost, commercially available materials.     

Atmospheric pressure plasma surface modification of titanium for high temperature adhesive bonding

In this investigation surface treatment of titanium is carried out by plasma ion implantation under atmospheric pressure plasma in order to increase the adhesive bond strength. Prior to the plasma treatment, titanium surfaces were mechanically treated by sand blasting. It is observed that the contact angle of de-ionized water decreases with the grit blast treatment time. Optical microscopy and scanning electron microscopic (SEM) analysis of untreated and atmospheric plasma treated titanium are carried out to examine the surface characteristics. A substantial improvement in the surface energy of titanium is observed after the atmospheric pressure plasma treatment. The surface energy increases with increasing exposure time of atmospheric pressure plasma. The optimized time of plasma treatment suggested in this investigation results in maximum adhesive bond strength of the titanium. Unmodified and surface modified titanium sheets by atmospheric pressure plasma were adhesively bonded by high temperature resistant polyimide adhesive. The glass transition temperature of this adhesive is 310 °C and these adhesively bonded joints were cured at high temperature. A substantial improvement in adhesive bond strength was observed after atmospheric pressure plasma treatment.     

Some Effects of Heat Processing on Adhesively Bonded Automotive Steel

During a program to develop new structural adhesives that would meet the processing requirements of the current automotive “high heat” bake cycles, substantial differences in performance were noted between the “standard” cold rolled steel (CRS) of SAE1008 and certain Drawing Quality steels (DQSK).

In parallel tests, certain DQSK test specimens (bonded with 200°C heat cycle) failed consistently in the interfacial region, while the CRS samples failed center of bond.

The surface characteristics of the steels and failed adhesive specimens were examined with ESCA, AUGER, and ISS spectroscopic methods. The metal failure surfaces of the DQSK samples were shown to contain relatively high levels of silicon and oxygen, and smaller amounts of boron, with a lower concentration of iron, as compared to CRS which shows iron surface with minor contaminations.

In subsequent testing, with other samples of DQSK SAE1008, this effect was not observed. These samples did not exhibit the same levels of contamination. It is suggested that certain DQSK processes may involve processing steps that are detrimental to the surface properties of the rolled sheet stock.     

Soy-oil-based waterborne polyurethane improved wet strength of soy protein adhesives on wood

Soy-oil-based waterborne polyurethane (WPU) is used to improve wet strength in shear test of wood bonded with an adhesive of soy protein isolate (SPI) by dispersing WPU into SPI slurry. WPU׳s effects on the physiochemical properties of WPU-SPI adhesives are characterized through Fourier transform infrared spectrum, transmission electron microscopy, thermal analysis, contact angle, and mechanical strength. Wet strength of the WPU-SPI adhesives increases by 65% compared to SPI control. Moreover, the microstructure of WPU has effects on the interactions between WPU and SPI. In this study, smaller and more uniform distributed WPU0002 is easier to interact and form stronger crosslinking network with protein than WPU0500. The stronger interaction between WPU0002 and protein results in increased viscosity and bond strength. The WPU-SPI blended adhesives show significantly improved wet strength, demonstrating their potential as wood adhesives.     

Plasma-Sprayed Aluminum and Titanium Adherends: II. Durability Studies for Wedge Specimens Bonded with Polyimide Adhesive

The durability of plasma-sprayed metals bonded with a polyimide adhesive has been studied. Metal adherend surfaces were prepared for adhesive bonding by plasma-spraying inorganic powders on aluminum and titanium. The plasma-sprayed materials included Al₂O₃, AlPO₄. MgO, and SiO₂ on aluminum, and TiO₂, TiSi₂, MgO, and SiO₂ on titanium. The coatings were sprayed at two different thicknesses. Durability studies of samples prepared in a wedge-type geometry were carried out. Bonded specimens were maintained in an environmental cycle that included exposure to the conditions; low temperature, - 20°C; relative humidity at elevated temperature, 70% RH at 66°C; elevated temperature (160°C) in air, high temperature (160°C) in vacuum (130 torr, 0.2 atm.), and room temperature. Crack growth rate and mode of failure were determined. The results of the durability tests indicate that thin coatings (25 μm) of plasma-sprayed materials perform better than thicker (150 μm) coatings. The crack growth rate for thin coatings (25 μm) of Al₂O₃, AlPO₄, SiO₂, and MgO plasma-sprayed on aluminum was equivalent to that for phosphoric acid anodized aluminum. Similarly, the durability performance for titanium samples prepared with a 25 μm-thick TiO₂, TiSi₂, and SiO₂ plasma-sprayed coatings was equivalent to that for a Turco®-prepared titanium surface. Although the evaluation of durability as a function of surface chemistry was an objective of the study, it was not possible to evaluate the effect, since most failures occurred within the adhesive (cohesive failure) during the environmental tests. That failure occurred in the adhesive indicates that the coating-adherend and the coating-adhesive interactions are sufficiently robust to prevent interfacial failure under the experimental conditions investigated.