Beiträge zur galvanisierung von polymeren, 7. Metallisierung von epoxidharzen mit hilfe von haftvermittlern

Epoxy resins can be coated with a metal after being covered with a platable adhesive. Such an adhesive consists of a partly epoxidized styrene-butadiene-styrene block copolymer, an epoxy prepolymer and an amine curer. The contents of these substances in the mixture and the nature of the amine influence the peel strength of the metal layer. The maximum peel strength with a value of about 45 N/25 mm was obtained after using a low molecular weight amine, while values of only about 10 N/25 mm could be obtained with amines of higher molecular weight.     

The Effect of Modification of an Epoxy Resin Adhesive with ATBN on Peel Strength

The effects of rubber content, rate of peel and temperature on peel strength of ATBN modified DGEBA based epoxy resin adhesives have been investigated. The fracture surfaces of peel test specimens and the distribution of rubber particles in cured bulk epoxy resin have been observed with SEM and TEM, respectively. The mechanical properties of bulk rubber modified epoxy resin have been also measured. The peel strengths increased with increasing rubber content, peel rate, and decreasing temperature. The peel strengths were superposed as a function of rate and temperature. Plots of the shift factors against temperature gave two straight lines, which followed an Arrhenius relationship. The region of temperature below the intersection of the two straight lines, temperature somewhat lower than T_g of epoxy adhesive, gave markedly high peel strengths and a stick-slip failure due to plastic deformation of the adhesive, and a number of micro holes produced by the rupture of rubber micro particles on the fracture surface. The region of temperature above the intersection gave lower peel strengths and an apparent interfacial failure with ductile fracture of the adhesive, and larger, shallow holes or no holes. From these results, the marked increase of peel strength was concluded to be mainly attributed to the plastic or viscoelastic deformation of epoxy matrix, the strong bond at the interface between rubber particles and epoxy matrix, and the dilation and rupture of a number of rubber particles.     

Effect of the physical and mechanical properties of epoxy resins on the adhesion behavior of epoxy/copper leadframe joints

In this study, the adhesion strength of three epoxy resins, which are used as basic materials for epoxy molding compound (EMC) in microelectronics, to copper leadframe was determined using the peel test. The epoxy resins used were O-cresol Novolac (OCN), dicyclopentadiene (DCPD), and biphenyl sulfide (BIPHS) epoxy resins. It was found that DCPD showed the highest peel strength and OCN had the lowest value. The difference in the peel strength was explained by investigating the physical and mechanical properties, as well as the surface properties of the epoxy resins. These properties included the surface energy, viscosity and gelation time, fracture toughness, and the coefficient of thermal expansion. As a result of the lower viscosity of BIPHS and DCPD than OCN epoxy resin, BIPHS and DCPD have a better peel strength than OCN. The DCPD resin has a better peel strength than BIPHS because of its higher fracture toughness.     

Surface modification of polyethylene by radiation-induced grafting for adhesive bonding. IV Improvement in wet peel strength

Adhesive joints of hydrolyzed methyl acrylate grafts, bonded with epoxy adhesives, yield extremely high peel strength (adherend failure) in dry conditions. However, when the joints are exposed to humid environments, the peel strenght rapidly decreases with exposure time and then reaches a constant value (wet peel strength). Since the locus of failure changes from the adherend to the homopolymer layer with decreasing peel strength, the decrease is due to a decrease in mechanical strength of the homopolymer layer itself, which results from its swelling by water absorption. Many attempts to reduce the swelling of the homopolymer layer or to strengthen the swollen homopolymer layer were unsuccessful except (1) priming with epoxy solutions consisting of a base epoxy resin and organic solvents which can dissolve not only epoxy resins but also hydrolyzed poly(methyl acrylate) and (2) partial etching of the homopolymer layer by photo-oxidative degradation. All the results on the improvement in wet peel strength can be explained in terms of the penetration of epoxy resins into the homopolymer layer and subsequent curing of the penetrated epoxy resin.     

The effect of nanoalumina silanisation in tetraglycidylether epoxy adhesive

The efficiency of different surface modifications on alumina nanoparticles on both filler dispersion and the final properties of the resulting adhesive nanocomposites have been investigated. A tetraglycidyldiaminodiphenylmethane (TGDDM) epoxy resin and three sample series of nanocomposites were prepared via in-situ incorporation of alumina nanoparticles into the reactor. The alumina/TGDDM nanocomposites were prepared individually using neat or non-treated alumina nanoparticles and two kinds of silane-grafted alumina nanoparticles, i.e., APS-treated alumina and GPS-treated alumina. The presence of different alumina nanoparticles in the epoxy matrices resulted in different states of nanofiller dispersion as revealed in SEM and AFM micrographs. It was elucidated that the silane treatment on alumina nanoparticles is crucial for the desired dispersion in the epoxy matrix. Besides, the appropriate filler dispersion resulted in improved thermal resistance and high degree of cure, especially for the adhesive nanocomposite containing APS-treated alumina nanoparticles. In adhesion tests, the shear strength was improved in both nanocomposites containing silane-grafted alumina with more pronounced values for the nanocomposite containing APS-treated alumina nanoparticles. The shear strength reached from 6.6 MPa for the neat epoxy adhesive to 10.2 MPa for the adhesive nanocomposite containing 5 wt % APS-treated alumina nanoparticles mainly due to high levels of dispersion of the high modulus alumina nanoparticles and effective interfacial interactions with the epoxy matrix. The adhesive peel strength of alumina/TGDDM nanocomposites showed a similar trend as in shear strength with more pronounced variations. A noticeable increase in the peel strength of the nanocomposites containing silane-grafted alumina nanoparticles appeared to correlate with greater levels of crack deflection and hence dissipation of fracture energy as observed in SEM pictures.     

Beiträge zur galvanisierung von polymeren, 10. Metallisierung von copolymeren aus acrylnitril und butadien nach vorbehandlung mit ozon

Copolymers containing acrylonitrile and butadiene can be coated with metal electroless. There is only a small influence on the metal-to-polymer-adhesion with the time of treatment with ozone. The adhesion increases with the content of acrylonitrile and with the molecular weight of the polymer. Peel strength values have been measured up to 150 N/25 mm because of the cohesive fracture inside the polymer. The highest values of adhesion have been measured on samples having nearly the same values of the critical surface tension like those of the electroless deposited nickel-layer. Caverns supporting a mechanical staying of the metal have not been observed.     

环氧增韧剂的合成及其在胶粘剂中的应用

为了开发新型的环氧增韧剂,合成了一系列环氧基封端的多元醇,对其在环氧树脂体系中的粘接性能进行了研究。试验结果表明,与未改性的环氧树脂体系相比,应用新型增韧剂改性的环氧树脂体系,其剪切强度提高59.8%,剥离强度提高108%。     

Effect of the microstructure of copper oxide on the adhesion behavior of epoxy/copper leadframe joints

The thermal oxidation of copper leadframe was carried out at 175°C and the adhesion behavior of the epoxy/copper leadframe joint was analyzed by investigating the microstructure changes of copper oxide with the thermal oxidation time of copper. The peel strength increased sharply at an early stage of oxidation (~20 min) followed by a slight increase. After further oxidation (120 min), the peel strength showed a slight decrease. The contact angles of water and diiodomethane decreased sharply at an early stage of oxidation with negligible change afterwards. As the oxidation time increased, X-ray photoelectron spectroscopy (XPS) results revealed that the chemical composition of copper oxide had changed (Cu/Cu₂O → Cu₂O → CuO); this change improved the wettability of the copper surface, which affected the peel strength. Increase of the surface roughness of copper oxide, investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM), causes the epoxy resin and copper oxide to undergo mechanical interlocking, which increases the peel strength. Failure analysis by SEM and XPS indicated that failure was largely in the copper oxide, and the amount of copper oxide on the peeled epoxy increased as the oxidation time increased, due to the weak mechanical strength of the oxide layer. However, a small portion of the epoxy resin was also fractured during the failure process, regardless of the oxidation time. Consequently, fracture proceeded mainly in the copper oxide close to the epoxy resin/copper oxide interface.     

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.     

Peel strength of polyurethanes from oxypropylene polyols II. Effect of additives,isocyanate structure,and other factors

The study of factors influencing the adhesion properties of polyurethane coatings to aluminum has been continued. The data indicate that the addition of additives to polyurethanes can affect their peel strengths. The addition of epoxy resins, chlorinated paraffins, or sulfonamide–formaldehyde resins results in increased peel strengths; the use of a mixture of fatty acids resulted in reduced values. The isocyanate structure can also play an important role; those producing more flexible films (such as m-xylylene di-isocyanate) result in higher peel strength values. Other factors found to be of importance included the concentration of aromatic and aliphatic groups, the type of solvent used in casting the films, the crystallinity of the polyether glycols and the presence or absence of certain substituents, such as fluorine, in the polyurethane chain. Tracer studies have indicated that the mechanism of adhesion failure involves the breaking of the polymer-polymer as well as polymer–substrate bonds.     

Aging and performance of structural film adhesives. II. Comparison of two nitrile–epoxy systems

The room-temperature aging of two nitrile rubber–epoxy adhesives has been examined. Both are 121°C curing systems, based on DGEBA-type epoxy resins, one of which has been available for about 15 years while the other is a more recent development. It has been found that hydrolysis of the epoxide and polymerization both occur slowly, reducing the epoxide content and solubility. A major reduction in honeycomb peel strength of joints made with aged material was evident in the older system and to a lesser extent in the newer adhesive. This is a result of diminished adhesive flow. Tensile strength was less affected by aging.     

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).     

Electrophoretic deposition of carbon nanotubes onto carbon-fiber fabric for production of carbon/epoxy composites with improved mechanical properties

Carbon nanotubes (CNTs) have been deposited onto carbon-fiber fabric using electrophoretic deposition (EPD) prior to the infusion of epoxy resin for the production of carbon/epoxy composites. The carbon-fiber fabric employed for EPD was used in the as-received condition, in which the proprietary epoxy sizing-agent was present. CNTs were functionalized prior to EPD using ozone treatment for oxidation, followed by chemical reaction with polyethyleneimine. The CNT oxidation used a novel recirculating system which enabled ozonolysis to be conducted on large-volume solutions of CNTs in the presence of high-powered sonication, facilitating preparation of stable dispersions suitable for EPD. Significant increases in the shear strength and fracture toughness of the carbon/epoxy composites with the CNT treatment have been measured relative to composites without the CNT treatment. Analysis of fracture surfaces revealed interlaminar regions with high levels of CNTs and evidence of good adhesion between the carbon nanotubes and sized carbon-fiber, which is believed to have contributed to the measured improvement in mechanical properties.     

Spray Deposition Methods for Improving Interfacial Strength of Copper–Epoxy Systems

A simple spray method using a plain orifice atomizer has been developed for depositing γ-aminopropyltriethoxysilane (APS) from solutions in water and in methanol onto copper surfaces. The evaporative patterns of the sprayed droplets were studied to determine the distribution of deposited APS and the percent coverage of the surface. The peel strengths between copper foil and epoxy resin were measured with and without APS deposition. It was shown that the application of APS resulted in a considerable increase in interfacial adhesion. APS applied from a 1 wt% solution in methanol resulted in a higher peel strength than when applied from a 1 wt% aqueous solution; the opposite was true with 0.2 wt% APS solutions, indicating a trade-off between deposited APS film thickness and surface coverage. In all cases, a higher concentration of APS gives a higher peel strength. APS was very effective when chemisorption occurred at the surface but much less effective when only physisorption took place. A study of the fracture surfaces showed cohesive failure inside the epoxy layer, and that the deposited APS on the copper surfaces had a long-range effect which was seen deep into the epoxy layer, well away from the copper surface.     

Investigation of Steel/Epoxy Adhesion Durability Using Polymeric Coupling Agents. II. Factors Affecting Adhesion Durability

Ethylene mercaptoester (EME) copolymers containing 23-90 wt% mercaptoester units were employed separately as coupling agents in steel/epoxy peel adhesion systems. As coupling agent functionality is increased the initial adhesion strength of, the steel/EME/epoxy peel systems also increased, approaching a ten-fold improvement over controls for the EME 90 coupling agent. However, the degree of corrosion protection decreased significantly with increasing concentration of mercaptoester units. The best corrosion protection was obtained with the EME 23/epoxy resin system which protected the steel adherend for an average of 48 hours in 57°C water baths. Regardless of the coupling agent used, all of the peel specimens exhibited poor adhesion after 5-11 hours exposure to hot water. Information from hydrolysis stability, water absorption, locus of failure and internal stress analyses when pooled show that the observed adhesion loss is attributable to the effect of water on the epoxy resin used; failure occurred within the epoxy.     

Polymer/clay aerogel‐based glass fabric laminates

Laminates of polymer/clay aerogels and glass fabric sheets were prepared with varying epoxy adhesion application levels. A poly(amide‐imide) and an epoxy (1,4‐butanediol diglycidyl ether/2,6‐diaminopyridine) were chosen as the two “foam core” polymers; both single‐layered and double‐layered glass fiber laminates were investigated. The adhesion between polymer clay aerogels and glass fibers was quantified using the T‐peel method. The peel strength properties were found to increase as adhesive loading increased up to an optimal value, after which peel strength declines. Flexural and compressive testing of the laminates was also performed as a way of measuring mechanical strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect on the toughness and adhesion properties of epoxy resin modified with silyl-crosslinked urethane microsphere

In order to give a toughness and improve adhesion properties of the cured epoxy system, modified epoxy resins, which have pre-reacted urethane microspheres formed using dynamic vulcanization method in liquid diglycidylether of bisphenol A, were prepared. It was found that the size of the particles decreased to sub-micro order with increase in solubility of urethane oligomers in epoxy resin, and coefficient of variance in the particle size distribution resulted in less than 15%. Fracture energy G_1c of the cured system was highly improved. Lap shear strength and peel strength were also improved. These mechanical and adhesion properties do not depend on any curing condition of epoxy resin because of the existing stable particles in the epoxy resin before curing.     

Chemical modification of Kevlar fiber surfaces and of model diamides

Organic reactions of aromatic diamides as models for PPTA fibers have been investigated to select reagents and conditions suitable for surface-controlled heterogeneous reactions on Kevlar filaments and fabrics. Amine functional groups have been incorporated into fiber surfaces by bromination followed by ammonolysis and by nitration followed by reduction. Modification of filaments has been attained without impairment of fiber properties. Preliminary experiments have also shown that the presence of amino groups on Kevlar fabric can provide remarkably improved peel strength and apparent interlaminar shear strength in epoxy laminates, suggesting a significant role of covalent bonding in improving adhesion in aramidepoxy composites.     

Surface modification of polyethylene by radiation-induced grafting for adhesive bonding. I. Relationship between adhesive bond strength and surface composition

A number of vinyl monomers have been surface grafted onto a polyethylene sheet by the mutual irradiation in monomer vapor and by a trapped-radical technique. The surface composition of the grafted sheets has been determined by means of ATR infrared spectrophotometry and compared with the peel strength of the joints bonded with conventional structural adhesives. In the methyl acrylate grafts followed by a saponification treatment, only the surfaces having graft compositions of more than 80 mole-% methyl acrylate give a high peel strength. A similar relationship between peel strength and surface composition is found in the surface grafts of vinyl acetate, acrylic acid, acrylamide, and methylolacrylamide. It is concluded that the formation of a surface with such a high monomer content is a necessary condition for the strong adhesive bonding of grafted polyethylenes at bonding temperatures below the softening point. Moreover, the adhesive bondability of the highly modified surfaces with epoxy adhesives is significantly enhanced by the introduction of carboxy and carbamyl radicals.     

Investigation of Steel/Epoxy Adhesion Durability Using Polymeric Coupling Agents III. Influence of Coupling Agent Layer Thickness

Steel/epoxy peel specimens were prepared using ethylene-mercaptoester (EME) copolymer coupling agents (90 wt% mercaptoester units) applied in thickness ranging from 25 to 350 Å. An optimum thickness of approximately 140 Å, which corresponded to an over 200% increase in peel strength when compared to 50 Å thick samples, was determined from ellipsometry and 90° peel strength measurements. The corrosion protection obtained was essentially independent of coupling agent thickness.