Flexible Backbone Aromatic Polyimide Adhesives

Continuing research at Langley Research Center on the synthesis and development of new inexpensive flexible aromatic polyimides as adhesives has resulted in a material identified as LARC-F-SO₂ with similarities to polyimidesulfone (PISO₂) and other flexible backbone polyimides recently reported by Progar and St. Clair. Also prepared and evaluated was an endcapped version of PISO₂. These two polymers were compared with LARC-TPI and LARC-STPI, polyimides researched in our laboratory and reported in the literature.

The adhesive evaluation, primarily based on lap shear strength (LSS) tests, involved preparing adhesive tapes, conducting bonding studies and exposing lap shear specimens to 204°C air for up to 1000 hrs and to a 72-hour water boil. LSS tests at RT, 177°C and 204°C were performed before (controls) and after these exposures. The type of adhesive failure as well as the Tg was determined for the fractured specimens.

The results indicate that LARC-TPI provides the highest LSSs, 33 MPa at RT, 30 MPa at 177°C, and 26 MPa at 204°C. LARC-F-SO₂, LARC-TPI and LARC-STPI all retain their strengths after thermal exposure for 1000 hrs and PISO₂ retains greater than 80% of its control strengths.

Most of the four adhesive systems showed reduced strengths for all test temperatures although they still retained a high percentage of their original strength (<60%) except for one case.

The predominant failure mode was cohesive with no significant change in the Tgs.

Although the LARC-F-SO₂ could not be prepared in diglyme alone as the solvent, the properties of the resulting adhesive were notable. The darkening of the adhesive during bonding was typical of systems which utilize amide solvents.     

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 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.     

Adhesive Evaluation for New Forms of LARCTM-TPI

LARC^TM-TPI is a linear aromatic polyimide that was developed at NASA Langley Research Center in the 1970's and subsequently licensed to Mitsui Toatsu Chemicals, Inc., (MTC) in Japan. This company has made it easier to process for use in application as a structural adhesive or as a composite matrix resin. The present forms that exist are (1) high melt viscosity or Low Flow Grade (LFG); (2) medium melt viscosity or Medium Flow Grade (MFG); and (3) low melt viscosity or High Flow Grade (HFG). As expected, the low melt viscosity material is the easiest to process but has poor toughness; the high melt viscosity material is very tough but is more difficult to process. Because of these two extreme situations we have worked closely with MTC to develop an optimized system. This work has resulted in the medium melt viscosity material as well as two other modified or blended medium-flow variations.

These novel forms of LARC^TM-TPI have resulted in adhesives that can be melt processed at pressures as low as 0.01 MPa (15 psi) at temperatures between 343-371°C (650-700°F). Evaluation of adhesive performance has been accomplished using lap shear specimens and evaluating flow, wet out and shear strength. Initial strengths for these optimized materials range from 20.7-41.4 MPa (3000-6000 psi) at room temperature and 13.8-20.7 MPa (2000-3000 psi) at elevated test temperatures.     

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.     

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.     

Adhesive evaluation of bisimide additives in LARC-TPI

Studies at NASA Langley Research Center had shown that the processability of aromatic polyimides can be improved by the addition of bis(amide acids) or bisimides to LARC-TPI. These low-molecular-weight additives apparently lower the melt viscosity of aromatic polyimides without affecting their glass transition temperatures. Well-consolidated, fiber-reinforced composites have been fabricated using this technology. LARC-TPI can be processed as a thermoplastic polyimide to form high strength bonds. However, this is generally accomplished by processing at relatively high bonding pressures, i.e. 2.07 MPa (300 psi). This paper covers the investigation of the effects of two bisimide additives to LARC-TPI adhesive in an attempt to improve the bonding process by lowering the viscosity of the material to achieve improved bond strength properties at lower bonding pressures. The results indicate some improvement in room temperature lap shear strength for the doped adhesives for the lowest bonding pressure, 0.34 MPa (50 psi), but some decrease in elevated temperature strength (232°C) for the phthalic anhydride-p-phenylenediamine-phthalic anhydride (C-PDA) system. The aniline-pyromellitic dianhydride-aniline (C-PMDA) system, bonded at 2.07 MPa (300 psi), exhibited comparable strengths to LARC-TPI after thermal and water boil exposures. The high flow exhibited by the additive in the melt state was not effective in lowering the viscosity of the more viscous LARC-TPI at the additive levels investigated.     

Evaluation of a thermoplastic polyimide (422) for bonding GR/PI composite

A hot-melt processable copolyimide designated 422 previously synthesized and characterized as an adhesive at NASA Langley Research Center for bonding Ti-6A1-4V has been used to bond Celion 6000/LARC-160 composite. Comparisons are made for the two adherend systems. A bonding cycle was determined for the composite bonding and lap shear specimens were prepared which were thermally exposed in a forced-air oven for up to 5000 h at 204°C. Lap shear strengths (LSSs) were determined at room temperature, 177°C, and 204°C. After thermal exposure to 5000 h at 204°C, room temperature and 177°C LSSs decreased significantly; however, a slight increase was noted for the 204°C test. Initially the LSS values were higher for the bonded Ti-6AI-4V than for the bonded composite; however, the LSS decreased dramatically between 5000 and 10 000 h of 204°C thermal exposure. Longer periods of thermal exposure up to 20 000 h resulted in further decreases in LSSs. Although the bonded composite retained useful strengths ( > 11.1 MPa) for exposures up to 5000 h, based on the poor results of the bonded Ti-6A1-4V beyond 5000 h, the 422 adhesive bonded composites would most likely also produce poor strengths beyond 5000 h exposure. Adhesive bonded composite lap shear specimens exposed to boiling water for 72 h exhibited greatly reduced strengths at all test temperatures. The percent retained after water boil for each test temperature was essentially the same for both systems.     

Transmission and Mechanical Properties of Optical Adhesives

The optical, mechanical and durability performance of selected epoxy, polyester, UV-curable acrylic, cyanoacrylate and silicone adhesives were evaluated and measured for bonding applications of optically transparent glasses in the visible and infra-red regions of the electromagnetic spectra.

From the initially selected adhesives only the UV-curable modified acrylic, two-component silicone and room temperature cured epoxy, were found to be of high performance characteristics, having good transmission properties and enhanced endurance in a combination of heat and humidity and following thermal cycling.

Sodium chloride substrates served as adherends for the transmission characterization of the optical adhesives, due to their high transmission properties in the 0.4-10 m μ spectral range. A modified lap shear specimen was designed for studying the mechanical properties and failure mechanisms of the adhesives and their durability in a humid and not environment. Finally, a two-piece glass doublet was used for investigating the optomechanical characteristics of the optical adhesive following environmental conditioning and thermal shock cycling.

Due to the inherent C-C bond, polymer adhesives are limited in utility, as far as transparency is concerned, close to 3.5 μm and in most of the 8-12 μm spectral range.     

Initial evaluation of novel polyamide-imides and their copolymers as adhesives

—An adhesive screening study was performed at NASA Langley Research Center on two linear aromatic polyamide-imide (PAI) homopolymers and two linear aromatic PAI copolymers. The homopolymers were made with either of two amide diamines, 3,3'- or 4,4'-diaminobenzanilide (DABA), and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA). The two copolymers studied were prepared with a combination of 3,3'-DABP and amide diamines. These aromatic PAIs possess high thermal stability because of intermolecular hydrogen bonding and chain stiffness. Lap shear strength (LSS) tests, conducted at room temperature, 177, 204 and 232°C, were the primary criterion for evaluation of the polymers as adhesives. Included in the study were measurements of the glass transition temperature made on fractured specimens for each bonding condition and a visual determination of the type of bond failure for specimens at each test temperature. Of the four adhesive candidates investigated, the best LSS values were obtained with the PAI copolymer identified as LARC-TPI(25% 3,3'-DABA). However, the LSS values were higher for the LARC-TPI polyimide with which the adhesive strengths were compared. The combination of a high molecular weight and the increased interchain electronic interaction associated with the amide group appears to contribute to the poor flow properties observed.     

Water-Resistant Oxide Layers at the Interface of Zinc/Epoxy Bonded Joints

The durability properties of bonded lap shear joints made from an epoxy/dicyandiamide adhesive and zinc metal coupons have been investigated. The metal coupons were anodized in sodium hydroxide solutions before bonding. The influence of the anodizing conditions on the morphology and composition of the oxide layers has been studied using SEM and TEM imaging analyses as well as X-ray photoelectron spectroscopy. The hydrolytic stability of the bonded joints has been assessed by storing the joints in water at 70 °C or 90 °C for periods of time up to 5 weeks. Polypropylene has been used as a model adhesive to study the influence of mechanical interlocking effects on the performance of the bonded joints. Depending on the anodizing conditions, the improved durability properties have been attributed either to „mechanical interlocking effects“ or to the higher hydrolytic stability of the oxide layers generated during the anodizing treatment.

Some of the results gained from the anodization of zinc have been extrapolated to hot-dipped galvanized steel. Bonded joints made from hot-dipped galvanized coupons anodized under smooth conditions (2% NaOH) displayed residual shear strengths of up to 70% higher than specimens simply degreased after immersion test. The generation of stable oxide layers as well as the suppression of intergranular corrosion phenomena at the metal/adhesive interface can explain the improved durability properties.     

An Iterative Solution for the Torque Transmission Capability of Adhesively-Bonded Tubular Single Lap Joints with Nonlinear Shear Properties

The adhesively-bonded tubular single lap joint shows large nonlinear behavior in the load-displacement relationship, because structural adhesives for the joint are usually rubber-toughened, which endows adhesives with nonlinear shear properties. Since the majority of load transfer of the adhesively-bonded tubular single lap joint is accomplished by the nonlinear behavior of the adhesive, its torque transmission capability should be calculated using nonlinear shear properties. However, both the analytic and numerical analyses become complicated if the nonlinear shear properties of the adhesive are included during the calculation of torque transmission capabilities.

In this paper, in order to obtain the torque transmission capabilities easily, an iterative solution which includes the nonlinear shear properties of the adhesive was derived using the analytic solution with the linear shear properties of the adhesive. Since the iterative solution can be obtained very quickly due to its simplicity, it has been found that it can be used in the design of the adhesively-bonded tubular single lap joint.     

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.     

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.     

Hygrothermal Properties of Adhesively Bonded Joints and Their Correlation with Bulk Adhesive Properties

The combined effects of heat (50[ddot]C) and humidity (95% R.H.) on the lap shear and T-peel strengths of 120[ddot]C, 150[ddot]C and 215[ddot]C service epoxy film adhesives have been characterized. Experimental results have indicated that effects of hygrothermal conditioning on lap shear and peel properties vary with exposure time and final testing temperatures and type of adhesive tested. In the cases where cohesive failure was observed in the shear and peel specimens, a correlation could be established between the bulk properties of the adhesives (tensile strength and elongation) and their adhesively bonded joint properties (shear and peel). When testing was carried out at room temperature, a general correlation between the tensile elongation and T-peel or shear could be obtained. At below freezing temperatures, lap shear strength seemed to be correlated with bulk tensile strength while peel correlated with bulk tensile elongation. At elevated temperatures, the relative contributions of bulk strength and elongation were the decisive factors as far as shear and peel strengths are concerned.     

Heat-resistant thermoplastic/ chromic acid anodized Ti-6Al-4V single lap bond evaluation

Structural, heat-resistant thermoplastic adhesives were evaluated in single lap bonds. The amorphous thermoplastics tested were polyphenylquinoxaline, glass filled Ultem polyetherimide, unfilled Ultem polyetherimide, and Victerex polyethersulfone. The adherend was chromic acid anodized Ti-6Al-4V, tested unprimed and primed with Lica 44 titanate. Initial bond strengths were similar for all adhesives. In general, Lica 44 titanate primer did not affect bond strength. Bond strength was not influenced by 170°C ageing, but 232°C ageing did decrease bond strength when polyphenylquinoxaline was the adhesive. Failure occurred primarily in the adhesive fillet and propagated into the unprimed or primed anodic oxide/polymer interphase.     

Chemistry and Adhesive Properties of Phenylethynyl-Terminated Phenylquinoxaline Oligomers

As part of a program to develop high performance/high temperature structural resins for potential aeronautical applications, phenylethynyl-terminated phenylquinoxaline oligomers were prepared, characterized, thermally cured and the cured resins were evaluated as adhesives. The phenylquinoxaline oligomers were prepared by conventional and aromatic nucleophilic displacement routes and chain terminated with mono or di(phenylethynyl) groups. The oligomers were melt pressed into thin films, compression molded into tensile and compact tension specimens, and fabricated into titanium-to-titanium single lap shear adhesive specimens. The oligomers were generally compression molded for 1 hr at 350°C under pressures ranging from 0.10 to 1.4 MPa. The phenylquinoxaline oligomer prepared via aromatic nucleophilic displacement exhibited better processability and higher tensile shear strengths than those of the oligomers prepared via the conventional synthetic route. The synthesis, physical and mechanical properties of these oligomers and their cured polymers are presented.     

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.     

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.     

Comparison of the Degradation Mechanisms of Zinc-Coated Steel, Cold-Rolled Steel, and Aluminium/Epoxy Bonded Joints

The durability properties of bonded lap shear joints made from an epoxy/dicyandiamide adhesive and zinc, zinc-coated steel, two different aluminium alloys or cold-rolled steel metal coupons have been investigated. The influence of the dicyandiamide content of the adhesive on the durability properties-has been assessed by salt spray testing or by storing the joints in water at 70°C or 90°C for periods of time up to five weeks. The degradation products formed during ageing of the epoxy adhesive in water have been investigated using high performance liquid chromatography (HPLC) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). The degradation mechanisms of aluminium/epoxy bonded joints have been thoroughly studied using X-ray photoelectron spectroscopy.

The performances of the bonded joints under a pure corrosive environment have been found to be little influenced by the quantity of dicyandiamide in the adhesive. When the bonded joints were aged in hot water, the stability of the interface toward an excess of dicyandiamide directly followed the sensitivity of the oxide layer at high pH values. Optimal durability properties without peel strength losses of the adhesive were aehieved both with zinc and aluminium-coated substrates by reducing the quantity of dicyandiamide in the epoxy adhesive by 20% (the initial dicyandiamide content in the commercial adhesive being ca. 9%, with respect to the epoxy resin).