Dry‐peelable temporary protective coatings from waterborne self‐crosslinkable sulfourethane–silanol dispersions

Novel temporary protective coatings were prepared by the addition of release additives to waterborne polyurethane dispersions. New types of self‐crosslinkable sulfourethane–silanol (SUS) dispersions were utilized as the peelable coatings. These dispersions are stable, low‐volatility organic chemical (VOC) waterborne dispersions that spontaneously crosslink upon drying without extra additives or processing steps. Tensile strengths up to 6000 psi with elongations between 300–600% were obtained for the crosslinked films. The adhesion of the films to a variety of substrates can be controlled by the addition of hydrophilic additives, including glycerol, oligomers of glycerol, and poly(ethylene glycol) derivatives. Alternatively, hydrophobic additives that are water dispersible, such as paraffin waxes and sulfated castor oil, can also be used to control adhesion. In addition, this technique can be utilized for the release of films derived from a wide variety of waterborne urethane dispersions, including carboxylated polyurethane ureas. The removable coatings are useful for the temporary protection of plastic surfaces during thermoforming processes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1443–1449, 2004     

Corona-discharge Treatment of Polypropylene films-Effects of Process Parameters

Corona treatment of films, mainly polypropylene (PP)-copolymers, was studied at commercial levels in a 2.7 kVA treater. The films were produced on a flat-film extruder with chill rolls. Degree of treatment was characterized by power of the generator divided by web speed and width of film (m Ws/cm²).

The effectiveness of the treatment was measured in terms of the polar and dispersion components of surface-energy, the peel adhesion of pressure sensitive tape (similar to ASTM Adhesion Ratio) and the peel adhesion of polyurethane adhesives.

The polar component of surface energy is a measure of the effectiveness of corona pretreatment. For a given degree of treatment, the polar surface energy component becomes greater as the film cooling rate increases (and the degree of crystallization falls).

A comparison of homopolymers and copolymers does, however, reveal that even where these have the same density or the same degree of crystallization one cannot count on them having equally-sized polar components.

Peel strengths of pressure-sensitive tapes and polyurethane-bonded patches confirm the influence of cooling conditions on wetting properties.

Contrary to the case for tape adhesion, the polyurethane adhesive strengths reach their maximum value at much lower treatment intensities, i.e. with much lower polar surface energy components, and thus question the validity of the ASTM tests for adhesion properties.     

Adhesion between polyurethane coating and EPDM rubber compound

The effect of the bulk modification of the EPDM rubber compound on the adhesion performance with polyurethane coating (PU) was studied. Ethylene propylene diene monomer (EPDM) was bulk modified using maleated EPDM, polynorbornene (PNR) or different curatives to improve adhesion to polyurethane coating. The coating–rubber composite adhesion performance was examined by peel, crack and abrasion tests followed by microscopic investigation of fracture surfaces and their chemical nature. The adhesion between the coating and the rubber substrate was improved using maleated EPDM or PNR, as well as different curing systems. The crack stress for the delamination of the polyurethane coating from the flexible bulk-modified rubber surface follows the trend: maleated EPDM > PNR > different curing systems > control.     

Low‐temperature thermal graft copolymerization of 1‐vinyl imidazole on fluorinated polyimide films with simultaneous lamination of copper foils

A simple technique of thermal graft copolymerization of 1‐vinyl imidazole (VIDZ) on pristine and argon plasma pretreated fluorinated polyimide (FPI) films with simultaneous lamination of copper foils was demonstrated. The simultaneous thermal grafting and lamination process was carried out in the temperature range of 80–140°C under atmospheric conditions and in the complete absence of a polymerization initiator. Three different FPI samples of different chemical structures were employed in the present study. An optimum T‐peel strength about 15 N/cm was achieved for the copper/FPI laminate. The adhesion strength, however, decreased with increasing fluorine content in the FPI film. The onset of cohesive failure occurred in the FPI film for assemblies with T‐peel strength greater than 6 N/cm. The T‐peel strengths are reported as a function of the argon plasma pretreatment time of the FPI films and thermal lamination temperature. The adhesion strengths were compared to that of the similarly prepared copper/polyimide (Kapton HN) laminate. Time‐dependent water contact angle (Θ) measurements indicated that the surfaces of FPI films are significantly more hydrophobic and more resistant to water diffusion or hydration than the Kapton HN films. The surface compositions of the pristine FPI films, as well as the delaminated FPI films and copper foils were studied by X‐ray photoelectron spectroscopy. The thickness of the graft VIDZ polymer layer was in the order of 200 nm, as derived from the cross‐sectional view of the scanning electron micrograph. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1478–1489, 1999     

Miscibility and adhesive properties of EVA‐based hot‐melt adhesives. II. Peel strength

A series of ethylene vinyl acetate copolymers (EVA) were blended with some tackifier resins that were made from wood extracts, and possible relations between their miscibility and properties as hot‐melt adhesives (HMA) were investigated. From our previous report on miscibility of various EVA‐based HMAs, we chose some blends that represent some of the typical miscibility types and investigated their peel strengths. When the blends were miscible at testing temperatures, the temperature at which the maximum value of peel strength was recorded tended to move toward higher temperature as tackifier content of blends increased. This result corresponds to the storage modulus of the blends whose curves tended to move toward higher temperature as tackifier content of blends increased when blend components were miscible as well as their maximum values of tan δ, or glass transition temperatures. It was characteristic for peel strength that there existed second peaks on peel strengths curves at ～ 100°C, which adhesive tensile strengths for the blends did not have. In terms of relationship between miscibility and HMA performances, we suggest that there are several factors other than miscibility that affect absolute values of peel strength more directly than miscibility; this idea has to be investigated further in the a future study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 726–735, 2002     

Crosslinked acrylic pressure‐sensitive adhesives. I. Effect of the crosslinking reaction on the peel strength

For pressure‐sensitive adhesives (PSAs) composed of poly(co‐ethyl acrylate‐2‐ethylhexyl acrylate‐2‐hydroxyethyl methacrylate) as a base resin and polyisocyanate as a crosslinker, the relationship between the crosslinking reaction and peel strength was investigated. A 90° peel test of cured PSA films under various storage conditions was carried out. At the same time, the isocyanate (NCO) consumption in these PSA films was monitored by attenuated total reflectance/Fourier transform infrared spectroscopy. The peel strength of the PSA compounded with the crosslinker decreased as the NCO groups were consumed. The elevation of the aging temperature promoted the crosslinking reaction and increased the decrement in the peel strength. The peel strength of noncrosslinked and crosslinked PSA films increased with the contact time. A high storage temperature made the increment in the peel strength increase. The addition of the crosslinker to the PSA films reduced the increment in the peel strength. Furthermore, PSA films with residual NCO groups possessed stronger peel strengths than fully cured films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1493–1499, 2003     

Peeling of heterogeneous thin films: Effect of bending stiffness,adhesion energy,and level of heterogeneity

The peeling behaviour of a heterogeneous thin film bonded to a rigid substrate was investigated by using both experiments and finite element modeling. The enhancement in peel force was studied specifically for heterogeneous thin films with periodic stiff and compliant portions along the length. Peel tests with homogeneous thin films (uniform film thickness) showed that the maximum peel force can be observed before the onset of steady state peeling process. Moreover, this maximum peel force was observed to be a function of the bending stiffness of the film and adhesion energy at the film-substrate interface. For the heterogeneous thin films, maximum peel force can be observed either before the onset of steady state or when the peel front traverses from compliant to the stiff portion of the film. The three-dimensional finite element model, based on cohesive zone technique was developed, which provided further insight into the enhancement in peel force. The maximum force was shown to be dependent on the level of heterogeneity in addition to adhesion energy and bending stiffness as was observed with homogeneous films. The improvement in peel force was found to be prevalent at relatively low adhesion energy. This study may be helpful for the better design of homogeneous and heterogeneous thin film-substrate systems having improved bonding strength.     

Mechanical factors in the adhesion of polyethylene to aluminium

The adhesion of low-density polyethylene to porous anodic films on aluminum was studied using the 180° peel test. Relative values of bond strengths, obtained by using polymer with and without antioxidant and by forming the bond in air or in vacuo, indicated that good adhesion could be obtained, despite previous evidence to the contrary, in conditions where oxidation of the polyethylene was suppressed. The relation between peel strength and anodic film thickness and film-forming voltage implied that the polyethylene entered pores in the film during bond formation. This was supported by the change of the category of the adhesion to one dependent upon polymer oxidation when the pores in the anodic film were sealed prior to bond formation. It is suggested that the mechanism of adhesion to porous anodic films on aluminum involves keying of the polymer into the pores in the film.     

Effect of the NCO/OH ratio on the properties of Mesua Ferrea L. seed oil‐modified polyurethane resins

A series of polyurethane resins with varying NCO/OH ratios (0.8–2.0) has been synthesized from the monoglyceride of Mesua Ferrea L. seed oil, poly(ethylene glycol) (M_n, 200 g mol^?1) and 2,4‐toluene diisocyanate in the presence of dibutyl tin dilaurate as the catalyst. The effects of the NCO/OH ratios of the synthesized resins on the physical properties, such as hydroxy values, acid values, saponification values, iodine values, specific gravities and isocyanate values have been studied. The formation of the polyurethane resins was confirmed by viscosity measurements, and FTIR, UV and ¹H NMR spectroscopic studies. Performance characteristics, such as impact resistance, flexibility, gloss, hardness, adhesive strength and chemical resistance, of the cured resins were investigated as a function of the varying NCO/OH ratios, with an influence of these ratios being observed for most of the above properties. Thermogravimetric analysis (TGA) demonstrated that the thermal stabilities of the cured resins increased with an increase in the NCO/OH ratios. The amounts of char residues at 550 °C were also found to be greater for higher NCO/OH ratios of the oil‐modified polyurethane resins. Copyright © 2005 Society of Chemical Industry     

Studies on PI/PI adhesion strength

The adhesion of polyimide to polyimide was studied by measuring the peel strength of various polyimide–polyimide composites. Different factors such as diffusion of polyamic acid to polyimide substrate, contact angle, wettability, and the thermal expansion coefficient of polyimide films and the presence of siloxane can affect this adhesion and are discussed in this article. © 1994 John Wiley & Sons, Inc.     

Interlayer delamination and adhesion of coextruded films

Efforts to evaluate interlayer adhesion of coextruded films are often hampered by the inability to initiate delamination. On the other hand, interlayer delamination was often noticed at cut or trimmed edges of coextruded films. In this study, a test method was developed by first initiating delamination by uniaxial stretching and then measuring interlayer adhesion by peel test. Delamination was initiated by uniaxial stretching under controlled conditions for samples with double‐neck geometry. The double‐neck geometry was designed to create a specimen for the subsequent 180° peel test. Peel force was used to quantify interlayer adhesion of coextruded films based on polycarbonate and its copolymers. With this two‐step technique, coextruded films with peel force as high as 5300 N/m or 30 lb./in. were quantified. In addition, effects of copolymer composition and coextrusion processing condition on interlayer adhesion of these coextruded films were clearly demonstrated. A great deal of variation of interlayer adhesion across film surface was also revealed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3901–3909, 2004     

Adhesion in Solid Propellant Rocket Motors

Plasma treatment of EPDM-based rocket motor insulation materials may change the peel strength between these materials and polyurethane polymers by a factor of 0.1 to 10. The matching of surface energies seems to be important for this adhesion process. The surface tension of the components was measured to between 30 and 50 mNm^-1. The total surface energy of the insulation could be increased from 27.2 mNm^-1 to ca. 70 mNm^-1 by the plasma process. Maximum peel strength could be obtained by a treatment of less than 1 min, whereas in most cases longer times gave lower values. In some cases very long treatment also gave good strength, probably due to a rougher surface structure. The rate of cure of the polymer was important for the adhesion process as lower rates of cure correlated with higher peel strengths, which can be explained by diffusion of the polymer's components into the insulation.     

雷达天线罩应急快速修补胶的研究

对不同种类固化剂、增韧剂、稀释剂及其用量对环氧树脂性能的影响进行了考察,并对环氧树脂在不同温度、湿度下固化的性能进行了研究。结果表明,曼尼希改性胺在高湿条件下固化性能最佳;随着增韧剂A用量的增加,体系的剪切强度和剥离强度先增加后降低;稀释剂A的含量增大,体系的黏度下降,但粘接强度也随之下降。研制的胶黏剂室温剪切强度约20MPa、90度剥离强度为2～3．5kN／m,固化2h剪切强度就达4～10MPa,可用于雷达天线罩的快速修补及材料的结构粘接。     

Adhesion to Sodium Naphthalenide Treated Fluoropolymers. Part III. Mechanism of Adhesion

Adhesion of fluoropolymers to copper and to other polymers is examined using a range of fluoropolymer types (PTFE, PFA, extruded, skived and cast films), surface modification techniques such as sodium naphthalenide (Na/naphth), acid stripping and lamination to produce surfaces of controlled roughness, and three tests of adhesion (90 degree peel tests, torsional shear tests and stripping of transmission electron microscopy (TEM) replicas). A combination of chemical and physical modification is required to produce good adhesion, with the relative importance of each dependent upon the specific adhesion test used. For relatively smooth-surfaced films, Na/naphth appears to function by increasing both the chemical functionality and the mechanical integrity of a surface layer. Untreated PTFE and PFA show interfacial failure and negligible adhesion. Smooth-surfaced PTFE with superficial surface modification, e.g. after lamination to shiny copper foil or after acid stripping of defluorinated material, often fails by fibrillation of the fluoropolymer surface. For short sodium etch times, adhesion is improved and the failure mode is interfacial. For long etch times, there is a mixed mode of failure. Fibrillation in smooth-surfaced PFA systems was not observed. Adequate adhesive strength in these systems could only be achieved by an increase in the surface roughness. The best adhesion could be achieved by surface roughening, followed by Na/naphth treatment. For such PTFE surfaces plated with copper, peel and shear tests showed a mixed mode of failure, with copper and fluoropolymer found on both failure surfaces by x-ray photoelectron spectroscopy (XPS) and energy dispersive x-ray spectroscopy (EDS). Extensive fibrillation occurred at the locus of failure. Provided chemical modification is adequate to allow wetting, the roughness of the surface dominates the properties of the adhesive bond. Prolonged Na/naphth treatment (e.g. one hour) causes a reduction in peel strengths.     

Effect of nanosilica on the properties of polyester‐based polyurethane

Polyester‐based polyurethanes with embedded nanosilica particles were prepared. The viscosity of polyester resins without and with nanosilica was determined by rheoviscometry. The morphology and mechanical and optical properties of the polyurethane coatings were studied intensively with a transmission electron microscope, a pendulum hardness tester, a scanning probe microscope, an Instron testing machine, an abrader and an ultraviolet–visible spectrophotometer. The viscosity of the polyester resins increased as the nanosilica content increased. Nanosilica could basically be dispersed into the polyester and its polyurethane on a nanoscale. The addition of a small amount of nanosilica increased the hardness, abrasion resistance, and tensile properties of the polymer films. However, these mechanical properties could be worsened at higher nanosilica contents. The ultraviolet–visible spectra showed that the absorbance and reflection of ultraviolet–visible light by the polyurethane films increased as the nano‐SiO₂ content increased, especially at wavelengths of 290–400 nm. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 189–193, 2003     

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.     

Electroplating on crystalline polypropylene. II. Injection molding and adhesion

This paper describes the effect of injection molding conditions (melt temperature, mold temperature, and fill time) and etch conditions on metal adhesion in electroplated isotactic polypropylene (PP). It is found that injection molding PP homopolymer produces a lamellar surface morphology which can consistently develop after-plated peel strengths of 30 lb/in or better as measured by the Jacquet peel test. Surface etching of PP homopolymer prior to plating develops crack patterns characteristic of injection molding; a directional crack pattern is always evident in specimen surfaces crystallized under shear. The surface pattern is developed in the oxidative process by swelling of amorphous material, followed by oxidative dissolution and oxidative stress cracking. Additionally, the depth and number of the surface cracks is a function of the solvent swell and acid etch times. Crack depth increases in lamellar surfaces as the sample immersion times are increased; however, as crack depth increases, crack density decreases. Metal-to-polymer adhesion, as measured by the peel test, represents a balance between crack depth and diminished surface strength incurred in the oxidative cracking process. Although peel adhesion usually increases with crack depth, overetching may actually reduce adhesion even though the crack depth has been increased. Any advantage from deeper cracks may, therefore, be offset by a loss in the surface strength of the polymer. Comparison of the surface and cross-sectional crack patterns in TiO₂-filled PP indicates that the surface morphology is similar to that of unfilled polymer. Molding conditions that produce the desired morphology is similar to that of unfilled polymer. Molding conditions that produce the desired morphology are important for high peel adhesion values but appear to be less critical than in unfilled PP. A propylene–ethylene copolymer (90/10) developed 12–15 lb/in. peel adhesion—50% lower than for the filled and unfilled homopolymer when molded under similar conditions; peel adhesion in this composite system is, however, relatively insensitive to changes in molding conditions. Aging of 2–3 weeks after plating is required for maximum peel adhesion in all samples studied.     

Low dielectric,fluorinated polyimide copolymers

Copolymers of fluorinated polyimides and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) have been prepared as films and composite laminates. The addition of BPDA was used as a means to achieve insolubility, making the polymers suitable as aircraft matrix resins. Glass transition temperatures, thermooxidative stabilities, and tensile strengths were increased with increasing BPDA content in the copolymers. Although the addition of BPDA did increase the UV cutoff and decrease the percent transmission slightly, the optical transparency of the polymers was still excellent. Dielectric constants of the copolyimide films ranged from 2.6 to 2.9. Astroquartz II laminates made with these resins had dielectric constant of 3.3–3.4. Flexural strength on unidirectional specimens were in the 1.24–1.41 GPa range and flexural moduli were 41 GPa. © 1994 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Surface modification of plasma‐pretreated high density polyethylene films by graft copolymerization for adhesion improvement with evaporated copper

Surface modification of Ar plasma‐pretreated high density polyethylene (HDPE) film via UV‐induced graft copolymerization with glycidyl methacrylate (GMA) and 2‐hydroxyethylacrylate (HEA) was carried out to improve the adhesion with evaporated copper. The surface compositions of the modified HDPE surfaces were characterized by X‐ray photoelectron spectroscopy (XPS). The adhesion strengths of evaporated copper with the graft‐copolymerized HDPE films were affected by the Ar plasma pretreatment time, the monomer concentration used for graft copolymerization, and the graft concentration. Post‐treatments, such as plasma post‐treatments after graft copolymerization and thermal treatment (curing) after metalization, further enhanced the adhesion strength of the Cu/HDPE laminates. The T‐type peel strengths of the laminates involving the graft‐modified and plasma posttreated HDPE films were greater than 15 N/cm. The enhanced adhesion strength resulted from the strong affinity of the graft chains for Cu and the fact that the graft chains were covalently tethered on the HDPE surface. XPS characterization of the delaminated surfaces of the Cu/HDPE laminates revealed that the failure mode of the laminates with T‐peel adhesion strengths greater than 5 N/cm was cohesive in nature.     

Electroless plating of copper on fluorinated polyimide films modified by surface graft copolymerization with 1‐vinylimidazole and 4‐vinylpyridine

Electroless plating of copper via a tin‐free activation process was carried out effectively on two types of fluorinated polyimide (FPI) films modified by UV‐induced surface graft copolymerization with N‐containing monomers, such as 1‐vinylimidazole (VIDz) and 4‐vinyl pyridine (4VP). The graft copolymerization of VIDz and 4VP was carried out on the argon (Ar) plasma‐pretreated FPI films via a solvent‐free process under atmospheric conditions. X‐ray photoelectron spectroscopy (XPS) results showed that the VIDz graft‐copolymerized FPI surface (the VIDz‐g‐FPI surface) and 4VP graft‐copolymerized FPI surface (the 4VP‐g‐FPI surface) were much more susceptible to the electroless deposition of metals via the Sn‐free process than the pristine FPI surfaces, and the FPI surfaces modified by Ar plasma pretreatment alone. T‐peel adhesion strengths above 9 N/cm were achieved for the electrolessly deposited copper on both VIDz‐g‐FPI surfaces (the Cu/VIDz‐g‐FPI assemblies) and 4VP‐g‐FPI surfaces (the Cu/4VP‐g‐FPI assemblies). These adhesion strength values were much higher than those obtained for assemblies involving electrolessly deposited copper on pristine or on Ar plasma pretreated FPI films. The high adhesion strength of the Cu/VIDz‐g‐FPI and Cu/4VP‐g‐FPI assemblies was attributed to the synergistic effect of spatial interactions of the grafted VIDz or 4VP polymer chains with the copper atoms, and the fact that the VIDz or 4VP polymer chains were covalently tethered on the FPI surfaces. XPS results also revealed that the Cu/VIDz‐g‐FPI and Cu/4VP‐g‐FPI assemblies delaminated by cohesive failure inside the FPI films.