Long Abstract Adhesion of Trim Tape to Automotive Finishes

In a given application trim parts are attached to autobody surfaces by a tape comprising a neoprene core double-faced with poly(buty1 acrylate) adhesive. Trim parts are received in automotive assembly plants with one side of the tape adhered in place and the other side protected by a release strip which is removed before use. The trim piece is applied with momentary pressure (0.1 MPa) from a roller to insure intimate contact. Initial adhesion must be sufficient to hold the trim part in place; functional attachment of the trim part depends on the tape adhesive for the duration of the car's use. Manufacturer's specifications do not provide for sanding of the painted surface prior to application of the trim part. It was necessary to reformulate the enamel to accommodate this by providing good adhesion at 30 minutes at 250°F and 60 minutes at 275°F conditions and to match the unsanded adhesion properties of a competitive product.     

耐高温皱纹纸压敏胶带的研制

采用100份的天然橡胶为主要弹性体、加入20份丙烯酸酯橡胶（ACM）、3-5份ZnO,0.8-1份硬酯酸制得混炼胶，在适量甲苯溶解上述混炼胶并加入60-80份的萜烯树脂、6-9份的2402酚醛树脂、8-12份改性剂及适量防老剂制得耐温压敏胶。将该胶涂布在耐温的皱纹纸上制得皱纹纸胶带，其粘性佳、耐高温、保持力强、无残胶、可用于电容器等电子元件的“编带“及机动车辆“烤漆保护“等生产环节。     

Theoretical analysis of the decay of shear strength of adhesion in metal/epoxy/metal joints in an aqueous environment

A theory for the decay of shear adhesion strength has been applied to lead-alloy/ epoxy/lead-alloy joints in water at 65°C, 75°C and 85°C. Theoretical values for the retention of wet shear strength over time coincided with experimental data. From experiments on wet shear adhesion strength and water absorption, it has been clarified that the following two cases exist: (1) in adhesive system A, the diffusion coefficient of water is greater at the interface than in the adhesive; (2) in adhesive system B, the diffusion coefficient of water is lower at the interface than in the adhesive, and water at the interface does not immediately contribute to adhesion failure — ie, there is a time lag between contact with water and bond breakage.     

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.     

Surface Chemical Characterization of Copper Oxide and its Relationship to Adhesion in Formed Epoxy/Copper Interfaces

Experiments have been performed to comprehensively analyze copper oxides formed from a chlorite oxidation bath on copper bar stock and to measure the adhesion of an epoxy casting resin to the corresponding oxidized surfaces. Temperature conditions for the bath ranged from 25 to 90°C with oxidation times between 0.25 and 20 minutes. Adhesion testing of the epoxy/copper systems was performed using a 3-point bend testing rig and measuring the ultimate force and displacement at the moment of sample failure near the epoxy/substrate interface. The flexure testing configuration used the resin as a stiffening rib which created a deviation in the force-deflection curve from that of the originally-oxidized copper bar stock. As the oxidation temperature increased above 50°C, there was higher cohesion of the oxide layer formed on the copper and that led to a higher measured force at failure. On copper samples oxidized at lower temperatures, failure occurs within the oxide as a part of the latter remains on the resin side and lower adhesion was measured.     

Strength of Epoxy/Glass Interfaces after Hygrothermal Aging

The stability of epoxy/glass interfaces subjected to hygrothermal aging was assessed using a fracture-mechanics approach. An epoxy system consisting of diglycidyl ether of bisphenol F cured with 2-ethyl-4-methyl-imidazole was bonded to borosilicate glass adherends that were treated with various types of adhesion promoters to provide a variety of interfaces. Adhesive strength was measured under dry, as-processed conditions and as a function of exposure time to an 85°C/85% relative humidity (RH) environment. As expected, the strain-energy-release rate, G_c, dropped significantly with aging time for the bare epoxy/glass interface. The drop in G_c is assumed to be due to a loss of interfacial forces. The use of two silane-based adhesion promoters, 3-aminopropyltriethoxysilane (APS) and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECH) resulted in improved adhesive strength both before and after hygrothermal aging. The improvement in adhesive strength can be explained by the introduction of chemical bonds at the interface. The drop in G_c is assumed to be due to a loss of interfacial forces and hydrolysis of siloxane bonds. In addition to the use of organosilane-based adhesion promoters, a series of polyhydroxyaminoethers (PHAE) thermoplastic adhesive resins was also investigated as potential adhesion promoters. It was found that 2% PHAE in Dowanol® PM, a hydroxyl-group-containing solvent, was the best system for the PHAE-based adhesion promoters. Interestingly, both the acetic acid concentration in the solvent and maleic anhydride content in the PHAE resin were shown to affect the adhesive strength.     

The effects of thermoplastic poly(olefin) (TPO) morphology on subsequent paintability and thermal shock performance

Adhesion to thermoplastic olefin (TPO) substrates is strongly influenced by the type and amount of solvent contained within paint applied. Morphological changes in the TPO substrate are accomplished in the presence of solvent from the topcoat and vary depending upon paint bake times and temperatures. These morphological changes at and near the surface of TPO affect not only the paint adhesion to the substrate but also the cohesive integrity of the painted plastic composite. This paper attempts to delineate the influence of paint and paint processes on the adhesion/cohesion and mechanical properties of coated TPO parts, in particular, the performance of 2K topcoated TPO substrates under thermal shock conditions. It was found that the most important attribute contributing to thermal shock resistance of painted TPO parts was the bake temperature of the topcoat. A temperature of 250 °F in either the adhesion promoter bake or the topcoat bake is necessary to afford acceptable thermal shock performance. It is postulated that the rearrangement of poly(propylene) crystallites at the uppermost surface of the TPO under a 250 °F bake accounts for the increased cohesive strength of the painted composite.     

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     

Applied Research and Development of Adhesives for Bonding Filled Carboxyl Terminated Polybutadienes to Various Substrates

A one-year applied research and development program was conducted on the bonding of carboxy-terminated polybutadiene (CTPB) propellant to various substrate materials encountered in solid propellant rocket motors. Under this program, in addition to CTPB liners, liners were also prepared from polyesters, polyethers, polyurethanes, polyacetal polymers, and epoxy resins. The use of various crosslinkers, emulsifiers, wetting agents, fillers, and stabilizers was also evaluated.

Four optimized liner formuations with the best all-round properties were fully characterized. The optimized formulations represented an HC liner formulation with two Ievels of glycerol additive, an HC formulation with a sorbitol additive, and a Butvar polyacetal-type liner. A standard HC-polymer liner formulation, designated as TL-H-304, was used as a control.

Unaged liner peel and shear properties were measured at -65°F, 77°F, and 160°F. Samples, aged for 30 days at 160°F, were tested at 77°F only.

The liners were tested against propellant, steel, aluminum, magnesium, titanium, epoxy-fiberglass, phenolics, polyisoprene, and butadiene-acrylonitrile as substrate materials. The steel, titanium, and polyisoprene rubber substrates gave the best adhesive results.

The substitution of asbestos and Cab-O-Sil for the Thermax filler in the liner gave comparable adhesive results while the substitution of clay fillers gave poor results.

This program was performed while at the Elkton Division of the Thiokol Chemical Corporation in fulfillment of the requirement of Contract N123 (60530-53329A) U.S. NAVAL ORDNANCE TEST STATION, China Lake, California, reported previously in U.S. Naval Report NOTS-TP4283.     

Surface Mechanical Properties of the Spore Adhesive of the Green Alga Ulva

The mechanical properties of the adhesive produced by spores of the green, marine, fouling alga Ulva linza are reported. Atomic force microscopy studies were performed and nanoindentation data were analyzed using a model for an asymmetric indenter. Freshly secreted adhesive is characterized by multiple layers. We found that the modulus of the outer ∼600-nm thick layer was about 0.2 ± 0.1 MPa, whereas the modulus of the inner layer was about 3 ± 1 MPa. Older adhesive showed the formation of a “crust” of harder material with a yield strength of ∼20 MPa at a loading rate of 2.5 × 10^-6 N · s^-1. Mechanical properties under tension are also described, and extension profiles that showed either constant or nonlinear force changes with tip-sample separation were observed. Models for both kinds of behavior are described. The work of adhesion between poly-dimethylsiloxane (PDMS)-coated AFM tips and the adhesive was determined to be less than 1.5 mJ · m^-2.     

PEEL ADHESION PROPERTIES OF AIR-DRIED PHARMACEUTICAL PRESSURE SENSITIVE ADHESIVE

The performance of a pharmaceutical pressure sensitive adhesive, whose liquid formulation is based on a multicomponent mixture of solvents, has been examined during two peel adhesion types of tests (90° dynamic adhesive strength peel test and 180° release liner peel test). The experiments were carried out under various drying temperatures, initial coating thickness, and types of backing film and release liner. The results show that the peel force depends mainly on the dry film weight of the tested adhesive. The type of the backing film which is used to form the adhesive also affects its peel adhesion properties.     

Medical-grade acrylic adhesives for skin contact

Pressure-sensitive acrylic adhesives for application to skin are made from 2-ethylhexyl acrylate, isooctyl acrylate or n-butyl acrylate copolymerized with polar functional monomers such as acrylic acid, methacrylic acid, vinyl acetate, methyl acrylate, N-vinylcaprolactam, or hydroxyethyl methacrylate. Functional comonomers increase cohesive strength, provide surface polarity, and enhance wear performance. Tack, adhesion to skin, adhesive transfer to skin, and wear performance of the adhesive are governed by the molecular weight, glass transition temperature, and the viscoelastic behavior of the adhesive. Viscoelastic properties of the adhesive as measured by the Williams plasticity number (WPN), dynamic storage modulus (G′), dynamic loss modulus (G″), and tan δ are important polymer properties for good wear performance. Sweating skin, a moist environment, and physical activity are the most important factors influencing the failure of an adhesive tape during wear. A medicalgrade adhesive for application to human skin should be hypoallergenic. Medical-grade adhesives are utilized in making surgical tapes for holding dressings in place, adhesive bandages, adhesive dressings to cover wounds, and surgical operating drapes.     

An Experimental Investigation of the Wall Deposition of Milk Powder in a Pilot-Scale Spray Dryer

A pilot-scale, co-current spray dryer has been used to investigate the effect of varying the swirl vane angle for the inlet air, inlet air temperature and liquid feed flowrate on the wall deposition flux of skim milk powder. The spray dryer was a cylinder-on-cone unit with a diameter of 0.8 m and a height of 2 m. It was fitted with adjustable swirl vanes surrounding a Delavan GA1 two-fluid atomizer. Swirl vane angles of 0, 25, and 30°, inlet air temperatures of 170, 200, and 230°C and feed flowrates of 1.4, 1.6 and 1.8 kg h^-1 were used. Inlet air swirl was found to significantly influence the wall deposition flux, with the highest swirl vane angle of 30° giving rise to the largest wall deposition flux. The difference between the particle and sticky-point temperatures of the skim milk powder was also found to be important in influencing the wall deposition flux. The wall deposition flux was the highest, at 16 g m^-2 h^-1, when the outlet particle temperature was furthest above the sticky-point temperature, and this occurred at the lowest value of the inlet air temperature (170°C) and highest product moisture content. No significant effect on the wall deposition flux was evident when using a nonstick food grade material (nylon), adhesive tape or stainless steel as the surface materials for the wall deposition tests. Therefore, it is likely that cohesion occurs at a similar rate to adhesion in the wall deposition of milk powder. Grounding the spray dryer also did not have a significant effect on the wall deposition flux. Relating the wall deposition flux to the sticky-point curve in this way suggests that the same trends (increased wall deposition fluxes above the sticky-point curve) may apply for other materials as well.     

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.     

Effect of Molecular Weight on Processing and Adhesive Properties of the Phenylethynyl-Terminated Polyimide LARC™-PETI-5

Three different molecular weight versions of the phenylethynyl-terminated polyimide LARC™-PETI-5 were synthesized. The materials synthesized had theoretical number average molecular weights of 2500, 5000, and 10000 g mol. Differential Scanning Calorimetry (DSC) was performed on the dry powder form of these materials to establish cure conditions which result in high glass transition temperatures. Lap shear specimens were prepared from adhesive tape made from each material and with the thermal cure conditions determined from the DSC data. The tensile shear data established which processing conditions provided the best adhesive strengths. Titanium tensile shear strengths as high as 52.6 MPa (7630 psi) at RT and 35.2 MPa (5100 psi) at 177°C were determined. Processing temperatures as low as 316°C and pressures as low as 0.17 MPa (25 psi) resulted in good adhesive properties. The tensile shear properties of these materials were unaffected by hydraulic fluid. The molecular weight of LARC™-PETI-5 has an important effect on the bonding pressures required to obtain good tensile shear strengths. The effect of molecular weight on the utility of PETI-5 to be used as a primer to maintain surface quality for bonding was also investigated.     

The Adhesion of Evaporated Copper to Dow Cyclotene 3022®, Determined by Microscratch Testing

The mechanical integrity, stability, and strong interfacial adhesion between Cu, a high conductivity metal, and Dow Cyclotene 3022^®, a low permittivity polymer, are important for their application in future high-speed microelectronic devices. In the present study, Cu was deposited by both evaporation and sputtering, and various Cyclotene surface modifications were carried out. These modifications included low pressure N₂ plasma and Ar⁺ treatments and the use of a Ti interlayer. The adhesion was evaluated by use of the microscratch test, and complemented by an adhesive tape peel test and XPS. The N₂ plasma treatment was found to lead to a dramatic increase in adhesion, which was influenced to a minor extent by the adhesion promoter that was used at the Cyclotene/Si substrate interface. This significant Cu/Cyclotene adhesion enhancement is interpreted in terms of the chemical groups present at the Cyclotene surface and the bonds formed on Cu deposition.     

Physico-Chemical Criteria for Maximum Adhesion. Part II: A New Comprehensive Thermodynamic Analysis

In this paper, two parameters defined as the relative work of adhesion [W_A/γ_L] and the relative interfacial energy [γ_SL/γ_L] have been examined for their assumed usefulness in correlating the thermodynamic properties of the components of the system substrate/ adhesive with its practical performance (strength). It is shown that the minimum value of [γ_SL/γ_L] relevant to conditions for the maximum adhesion becomes zero only for those systems (relatively rare) for which interaction factor Φ₀ is equal to 1.0.

Several transition points were identified for boundary conditions acquired at θ = 0° and θ = 90° which can be used to predict the properties and performance of an adhesive joint. These transition points are: a_MIN—energy modulus of the system (E. M. S.), relevant to the minimum interfacial energy; a_S—E. M. S. where self-spreading of adhesive occurs; a_CRIT—E. M. S. relevant to conditions under which the thermodynamic work of adhesion becomes negative and the system exhibits a tendency for self-delaminating or has “zero-strength”; a_CF—E. M. S. beyond which the geometry of the interface at any interfacial void or boundary of the joint may be regarded as a crack tip.

It is shown that only in those systems for which Φ₀ = 1.0 can a minimum contact angle of 0° indicate a condition for the maximum strength. If Φ₀ is known, the optimum contact angle can be estimated and hence the optimum surface energy of the substrate (adjusted by surface treatment, etc.) for the maximum adhesion.     

The Adhesion of Evaporated Copper to Dow Cyclotene 3022®, Determined by Microscratch Testing

The mechanical integrity, stability, and strong interfacial adhesion between Cu, a high conductivity metal, and Dow Cyclotene 3022^®, a low permittivity polymer, are important for their application in future high-speed microelectronic devices. In the present study, Cu was deposited by both evaporation and sputtering, and various Cyclotene surface modifications were carried out. These modifications included low pressure N₂ plasma and Ar⁺ treatments and the use of a Ti interlayer. The adhesion was evaluated by use of the microscratch test, and complemented by an adhesive tape peel test and XPS. The N₂ plasma treatment was found to lead to a dramatic increase in adhesion, which was influenced to a minor extent by the adhesion promoter that was used at the Cyclotene/Si substrate interface. This significant Cu/Cyclotene adhesion enhancement is interpreted in terms of the chemical groups present at the Cyclotene surface and the bonds formed on Cu deposition.     

Adhesion properties of lactic acid based hot melt adhesives and their storage stability in different packaging applications

Adhesion properties and the stability during the use life of the package for two biodegradable hot melt adhesives were evaluated. Adhesives were based on poly (L-lactide) (PLLA) and poly(-caprolactone) (PCL) with molar ratio 81:19. One sample was stabilized by end-capping the terminal hydroxyl groups with acetic anhydride. The other sample was unmodified. Reference adhesive that was used in the studies, was a conventional non-biodegradable hot melt adhesive based on poly(ethylene-co-vinylacetate) (EVA).

Materials, which were bonded with these hot melt adhesives, were typical biodegradable packaging materials: a pigment-coated cardboard, a similar cardboard extrusion laminated with film type PLLA and an uncoated cardboard. The storage stabilities of the copolyester films and bonded structures were monitored during an eight week period at room (23°C) and at low (−18°C) temperatures.

Changes in molecular weight and crystallinity of the copolyesters were measured with gel permeation chromatography (GPC) and differential scanning calorimetry (DSC), respectively. Mechanical strength of the adhesive bonds was measured by a tensile testing instrument. Fracture surfaces of the adhesive bonds were subjected to microscopic studies.

Initial adhesion properties of the copolyesters were similar to those of EVA and better in case of PLLA-laminated cardboard. Both biodegradable copolyester samples degraded during the studied period; however, end-capping of the copolymer retarded this degradation rate.     

Direct Observation of Cavitation and Fibrillation in a Probe Tack Experiment on Model Acrylic Pressure-Sensitive-Adhesives

The adhesion mechanisms of two acrylic Pressure-Sensitive-Adhesives on a stainless steel probe are investigated with a custom-designed probe tack apparatus. Our setup allows the simultaneous acquisition of a nominal stress and strain curve, and the observation of the adhesive film from underneath the transparent substrate. The temperature was varied in the range -20°C to 50°C and the debonding rate in the range 1-10000 μm/s. For all conditions we observed, upon debonding, the formation of cavities at or near the interface between the probe and the film. These cavities initially grew predominantly in the plane of the film but, at higher values of nominal strain, the walls between the cavities were stretched in the direction normal to the plane of the ifim to become a fibrillar structure. The transition from a cavitated structure to a fibrillar one was only found within a time-temperature window of rheological properties of the adhesive, while the adhesion energy was found to be mainly related to the elongational properties of the adhesive. The maximum tensile stress observed in the probe tack experiment was directly related to the appearance of the cavities and showed a good correlation with the shear modulus of the adhesive, while the adhesion energy was found to be mainly related to the elongational properties of the adhesive. The presence of 2% acrylic acid as a comonomer had a negligible effect on the maximum stress but a very important one on the formation of a fibrillar structure and on the locus of failure.