Influence of Differently Structured Aluminium–Polypropylene Interfaces on Adhesion

Polar groups were introduced on polypropylene surfaces for increasing the surface energy and the peel strength to evaporated aluminium layers. Three kinds of plasma processes were used for introducing such functional groups to polyolefin surfaces: low-pressure radio-frequency (RF) O₂ plasma exposure, atmospheric-pressure dielectric-barrier discharge (DBD) treatment in air, and the deposition of allylamine plasma polymer. The amino groups of the allylamine plasma polymer were also used as anchoring points for chemical introduction of covalently bonded spacer molecules equipped with reactive endgroups. Thus, silanol endgroups of a covalently bonded spacer were able to interact with the evaporated metal layer. The Al–PP composites achieved a maximal peel strength of 470 N/m by exposing the polymer to the lowpressure O₂ plasma and 500 N/m on exposure to the atmospheric DBD plasma. After allylamine plasma polymerization and grafting of spacers, the peel strength was usually higher than 1500 N/m and the composites could not be peeled.     

Effect of grafting of acrylic acid onto PET film surfaces by UV irradiation on the adhesion of PSAs

To improve the peel strength between a pressure-sensitive adhesive (PSA) and its substrate, grafting of acrylic acid (AA) onto the surface of poly(ethylene terephthalate) (PET) film was carried out. After AA was coated onto the surface of PET films using a spin coater, the coated PET films were irradiated by UV. To investigate the surface chemistry and topography of the PET-g-AA films, the grafted surface of the PET films was characterized by FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS) and scanning probe microscopy (SPM). From these investigations, the effects of grafting of AA at the surface of PET by UV irradiation were discussed. In addition, to determine the effect of grafting on the adhesion between PSA polymer and PET-g-AA films, peel strength was measured after the PSA/PET-g-AA system was cured at various temperatures. As the esterification between PSA polymer and PET-g-AA films occurred in the interfacial region, the peel strength of the PSA/PET-g-AA system generally increased with increasing curing temperature.     

Plasma-induced adhesion improvement of cotton/polypropylene-laminated fabrics

In this study, improvement in the adhesion strength of plasma-pretreated and laminated cotton/polypropylene (PP) fabrics using acrylic-based adhesive was investigated. Low-temperature, low-pressure oxygen plasma was utilized for surface modification of cotton/PP-laminated fabrics. Water absorption time was measured on plasma-treated cotton fabrics at different plasma power and treatment time conditions. The plasma conditions providing the fastest liquid absorption on the surface were selected and applied during plasma pretreatments. Surface wettability increased with increasing plasma power and plasma exposure time. Plasma-induced surface morphology changes were observed via Scanning Electron Microscope (SEM) images. X-ray Photoelectron Spectroscopy (XPS) analysis showed that oxygen content on the surface increased with plasma treatment, which contributed to the surface polarity and hydrophilicity. Peel bond strength results of untreated and plasma-treated samples were analyzed to determine the effect of plasma pretreatment process. Adhesion strength values of laminated samples, before washing and after 40 wash cycles, were determined by peel bond strength tests. Before washing, adhesion strength of plasma pre-treated, laminated samples was 28–60% higher than that of untreated laminated fabrics. After 40 wash cycles, adhesion strength of plasma pre-treated and laminated samples was about 40–69% higher than the untreated laminated fabrics. Peel bond strength values decreased with the increased number of wash cycles. Plasma pretreatment enhanced both the adhesion strength and washing resistance of laminated samples.     

Effects of surface modification by oxygen plasma on peel adhesion of pressure‐sensitive adhesive tapes

Surfaces of poly(isobutylene) (PIB) and poly(butylacrylate) (PBA) pressure‐sensitive adhesive tapes were treated by oxygen plasma, and effects of surface modification on their adhesive behavior were investigated from the viewpoint of peel adhesion. The peel adhesion between PIB and PBA pressure‐sensitive adhesive tapes and stainless steel has been improved by the oxygen plasma treatment. The surface‐modification layer was formed on PIB and PBA pressure‐sensitive adhesive surfaces by the oxygen plasma treatment. The oxygen plasma treatment led to the formation of functional groups such as various carbonyl groups. The treated layer was restricted to the topmost layer (50–300 nm) from the surface. The GPC curves of the oxygen plasma‐treated PBA adhesive were less changed. Although a degradation product of 1–3% was formed in the process of the oxygen plasma treatment of the PIB adhesive. There are differences in the oxygen plasma treatment between the PIB and PBA adhesives. A close relationship was recognized between the amount of carbonyl groups and peel adhesion. Therefore, the carbonyl groups formed on the PIB and PBA adhesive surfaces may be a main factor to improve the peel adhesion between the PIB and PBA adhesive and stainless steel. The peel adhesion could be controlled by changing the carbonyl concentration on the PIB and PBA adhesive surfaces. We speculate that the carbonyl groups on the PIB and PBA adhesive surface might provide an interaction with a stainless steel surface. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1392–1401, 2000     

Effect of crystallization and interface formation mechanism on mechanical properties of film‐insert injection‐molded poly(propylene) (PP) film/PP substrate

A previous study has shown that the adhesion between the film and substrate of film‐insert injection‐molded poly(propylene) (PP) film/PP substrate was evident with the increases in barrel temperature and injection holding pressure. In this second part of the research work, the crystallinity at the interfacial region (i.e., region between the film and the injected substrate) was extensively studied using FTIR imaging, polarized light microscopy, and DSC in an attempt to determine the level of influence that crystallinity has on the interface and bulk mechanical properties. Consequently, a more thorough and clearer picture of the influence of the inserted film on the interfacial crystallinity and subsequently the substrate mechanical properties, such as peel strength and impact strength, has been revealed. The initial proposition that crystallinity could enhance film–substrate interfacial bonding has been confirmed, judging from the higher peel strength with increasing crystallinity at the interfacial region. Nevertheless, the change in crystallinity was not only confined to the interfacial region. With the film acting as heat‐transfer inhibitor between the injected resin and the mold wall, the total crystal structure of the substrate was substantially altered, which subsequently affected the bulk mechanical properties. The lower impact strength of film‐insert injection‐molded samples compared to that of samples without film inserts provided evidence of how the film could impart inferior properties to the substrate. The difference in cooling rate between the substrate and film might also cause other defects such as warpage and/or residual stress build‐up within the product. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 294–301, 2005     

Plasma surface modification of polyimide for improving adhesion to electroless copper coatings

The influences of oxygen plasma treatment of polyimide (PI) films on the adhesion of electroless copper coatings as well as on the chemical composition of the film surface and the PI surface morphology were investigated. The plasma operating parameters were 1800 W forward power with O₂ flowing at a rate of 300 cm³/min at a pressure of 200 mTorr. The peel strength increased with decreasing plasma treatment temperature. However, extension of the treatment time at higher temperatures had a positive effect on adhesion. A correlation between the enhancement in peel strength and the content of oxygen-containing groups at the PI surface (investigated using XPS) was observed. A change in the morphology as a result of plasma etching was also observed, in the formation of pits in the film surface. The pits ranged from 3 to 6 μm in depth and the diameter varied from 10 to 200 μm. Comparison of the data obtained after plasma treatment with the results of chemical etching in alkaline solutions of permanganate showed approximately the same adhesion increase (to 0.6 kN/m) in both cases. However, chemical etching did not affect the surface morphology and increased the oxygen content at the PI surface less than the plasma treatment.     

Atomic force microscopy analysis of cellulose triacetate surface modified in low temperature argon plasma and its adhesion behavior

The surface of cellulose triacetate (CTA) film was modified with gaseous plasma of several discharge power in the presence of Argon (Ar) gas at 0.5 torr pressure. After gas plasma etching, the surface structure of the films is analyzed by atomic force microscopy (AFM) and measured with peel strength. Furthermore, the wetting properties of the CTA film treated with Ar plasma are studied by contact angle measurement. Peel strength after plasma treatment was increased with increasing plasma treatment time. However, treatments of plasma greater than 7 min did not find an additional increase in peel strength, similarly to roughness and morphological changes of AFM. The water contact angle decreased for an initial treatment time due to the improved wettability of the film, but showed an increasing trend for a higher treatment time (7 min). These results show that Ar plasma treatment is a convenient tool for improving the adhesive properties of CTA film. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3963–3971, 2006     

Long Term Effects of Air Dielectric Barrier Discharge Treatment on the Surface Properties of Ethylene Vinyl Acetate (EVA)

This paper discusses the long term effects of dielectric barrier discharge (DBD) treatment on the surface properties of ethylene vinyl acetate (EVA) film. The EVA surface was characterised using contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and 180° peel tests. EVA subjected to two different treatment times was compared to as-received and solvent cleaned film. The long term stability of the surface modification induced by the DBD treatment was studied over a period of 466 days. On initial application of DBD treatment to the EVA surface an increased wettability was observed, evident from a decreased water contact angle, improved peel strength when bonded, and an increased level of carbon–oxygen moieties measured using XPS. However, over the storage period of 466 days the material reverted to almost its original state with the contact angle being only ～3° lower than that of as-received EVA compared to a difference ～25° directly after treatment. AFM measurements showed that the treatment had a slight smoothing effect on the surface topography.     

Adhesion Properties and Structure of Ion-Beam Modified Polyimide Films

Polyimide (PI) surface modification was carried out by an ion beam treatment to improve the adhesion between the polyimide film and copper. The PI film surface was treated with an ion-beam source at ion doses ranging from 1.96 × 10¹³ to 2.38 × 10¹³ ions/cm² using a mixture of nitrogen (N₂) and hydrogen (H₂). Contact angle measurement, atomic force microscopy and X-ray photoelectron spectroscopy, respectively revealed an increase in the surface roughness, a decrease in contact angle, and the formation of oxygen complexes and functional groups on the treated PI surfaces. Adhesion between the copper and PI film treated with the beam was superior to that of the untreated PI film. The 90° peel test revealed the highest peel strength of 7.8 N/cm.     

Adhesion of vacuum-deposited thin cobalt metal film to poly(ethylene terephthalate) pretreated with RF plasma

Specific polar groups were introduced on a poly(ethylene terephthalate) (PET) film surface by radio-frequency (RF) plasma treatment. These polar groups were analyzed quantitatively by ESCA, and their effect on the adhesion strength of vacuum-deposited thin cobalt metal film on the plasma-treated PET film surface was investigated. Hydroperoxide and hydroxyl groups introduced onto the PET film surface by RF plasma under an argon or oxygen atmosphere greatly increased the adhesion strength. In particular, oxygen plasma treatment at high RF power was most effective. A large number of amino groups were introduced by the ammonia plasma treatment, but they did not increase the adhesion strength.     

Plasma‐induced surface modification and adhesion enhancement of polypropylene surface

Unoriented (UPP) and biaxially oriented (BOPP) polypropylene films were treated under radio frequency plasma of air, nitrogen, oxygen, and ammonia. Surface modification of polypropylene films was investigated by using surface energy measurement and attenuated total reflection (ATR)‐FTIR spectroscopy. Surface energy of air and nitrogen plasma‐treated polypropylene film increased for shorter treatment time and then decreased and attained an equilibrium value. Such changes in surface energy were not observed for oxygen and ammonia plasma‐treated polypropylene film, which increased to an equilibrium value. ATR‐FTIR studies revealed characteristic differences in the absorption spectra for short‐duration and long‐duration treatments. From the relative intensity change in the C—H stretching vibration, the mechanism of surface chemical reaction could be inferred. Studies regarding the durability of surface modification due to plasma treatment were evaluated by investigating surface energy of samples aged for 2 months. Treated films subjected to peel strength measurement showed improvement in bondability for UPP and BOPP film by hydrophilic surface modification accompanied by surface crosslinking. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 925–936, 2002     

Plasma-induced hydrogel grafting of vinyl monomers on polypropylene

Polypropylene (PP) film was plasma-treated using a 13.56 MHz direct plasma with argon, nitrogen, and oxygen as the plasma-forming gases. The three gases induced very different changes on the PP film surface, which were studied using contact angle measurements. Because of its degrading and oxidative effect, oxygen plasma pretreatment was not used for the homogeneous grafting of acrylic acid and acrylamide. Nitrogen plasma treatment did not lead to the formation of stable peroxides on the film surface and did not undergo grafting reactions. This may be due to the types of radicals and functional groups created on the surface during the plasma treatment. Finally, argon plasma pretreatment was found to be the most effective for the grafting of vinyl monomers. The amount of grafted poly(acrylic acid) was shown to be proportional to the concentration of peroxides created by argon plasma treatment.     

Changes in the Peeled Surfaces of Copper Thin Films Deposited on Polyimide Substrates After Heat Treatment

Peel strength between a copper (Cu) thin film and a polyimide (pyromellitic dianhydride-oxydianiline, or PMDA-ODA) substrate is reduced by heat treatment at 150°C in air. In this work, we investigated the peel strength, the morphology of the interface between Cu films and polyimide substrates using optical microscopy and electron microscopy, and chemical change of the interface using Auger electron spectroscopy (AES) and micro X-ray photoelectron spectroscopy (XPS). The analysis showed that CuO “lumps” were present on the peeled surface of PMDA-ODA after heat treatment at 150°C in air. The peeled surfaces of other polyimide substrates were also analyzed: biphenyl dianhydride-para phenylene diamine (BPDA-PDA) and biphenyl dianhydride-oxydianiline (BPDA-ODA). CuO lumps were present on the peeled surface of BPDA-ODA after the heat treatment, but not that of BPDA-PDA. Compared with the adhesion strength for the Cu thin film, the adhesion strength was high for the Cu/PMDA-ODA and Cu/BPDA-ODA laminates, but the adhesion strength was very low for the Cu/BPDA-PDA laminate. This low strength is the reason that CuO lumps were not detected on the peeled surface of the BPDA-PDA substrate. These CuO lumps were related to the adhesion degradation of the Cu/polyimide laminates after the heat treatment.     

Surface modification of thermotropic poly(oxybenzoate‐co‐oxynaphthoate) copolyester by remote oxygen plasma for copper metalization

Poly(oxybenzoate‐co‐oxynaphthoate) (POCO) film surfaces were modified with remote oxygen plasma, and the effects of the modification on the adhesion between the copper layer and POCO were investigated. The remote‐oxygen‐plasma treatment led to a noticeable decrease in the contact angle, which was mainly due to the C? O functional groups on the surface. The modification of the POCO surface by remote oxygen plasma was effective in improving the adhesion with copper metal. The peel strength for the copper metal/POCO system was enhanced from 10 to 127.5 mN/5 mm by the surface modification. The failure mode of the copper metal/POCO system was an interface layer between the oxidized micro‐POCO fibril surface and the copper metal layer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2400–2408, 2003     

Melt grafting of maleic anhydride onto polypropylene with 1‐decene as a second monomer

The influence of 1‐decene as the second monomer on the melt‐grafting behavior of maleic anhydride (MAH) onto polypropylene (PP) was studied with differential scanning calorimetry and Fourier transform infrared spectroscopy. We found that the value of the grafting degree increased from 0.68% for pure MAH‐g‐PP to 1.43% for the system with a 1‐decene/MAH molar ratio of 0.3, whereas the maximum value with styrene (St) as the second monomer was 0.98% under an St/MAH molar ratio of 1.0. Compared with the contribution of St/MAH‐g‐PP to the peeling strength between the PP and polyamide (PA) layer for a PP/PA laminated film, the introduction of 1‐decene/MAH‐g‐PP increased the peeling strength from 180 g/15 mm to 250 g/15 mm. 1‐Decene inhibited the chain scission behavior of PP. 1‐Decene reacted with MAH to form a 1‐decene/MAH copolymer or the Alder‐ene reaction product before the two monomers grafted onto PP. The grafting of the reactive product onto PP greatly improved the grafting degree of MAH. What is more, because of the similar chemical structures of 1‐decene and PP, the affinity of 1‐decene with PP was higher than that of St. Compared with St, the introduction of less 1‐decene led to a higher grafting degree and higher peeling strength. Therefore, we concluded that 1‐decene was more effective for improving the grafting degree of MAH onto PP. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of environment and heat treatment on an oxygen plasma-treated polyimide surface and its adhesion to a chromium overcoat

—The effects of oxygen plasma treatment time, duration of storage, and heat treatment on the surface chemistry of and Cr adhesion to Dupont RC5878 and Kapton polyimides were investigated using X-ray photoelectron spectroscopy (XPS), and contact angle and peel strength measurements. The XPS results indicate that the initial stage of plasma treatment involves oxygen adsorption with insignificant modification of the surface chemistry. After 5 s of plasma treatment the surface chemistry is modified, as suggested by the changes in the carbonyl and partially oxidized carbon functional groups' contributions to the C(1s) line shape. These modifications resulted in an increase in the peel strength and a decrease in the contact angle of water. Over the first month of storage, the intensity of the carbonyl functional group peak decreased, while the contact angle increased and reached a steady-state value of 30° after 20 days of storage. These changes are mainly attributed to moisture absorption. Importantly, the metal adhesion to polyimide remained fairly constant over the storage period. The aged plasma-treated surface experienced loss of moisture when baked at 150°C for less than 5 min. This was followed by an increase of the partially oxidized carbon at the expense of the plasma-induced carbon-oxygen bonds at higher baking temperatures or longer times.     

Surface modification of low‐density polyethylene (LDPE) film and improvement of adhesion between evaporated copper metal film and LDPE

To improve the interfacial adhesion between evaporated copper film and low‐density polyethylene (LDPE) film, the surface of LDPE films was modified by treating with chromic acid [K₂Cr₂O₇/H₂O/H₂SO₄ (4.4/7.1/88.5)]/oxygen plasma. Chromic‐acid‐etched LDPE was exposed to oxygen plasma to achieve a higher content of polar groups on the LDPE surface. We investigated the effect of the treatment time of chromic acid in the range of 1–60 min at 70°C and oxygen plasma in the range of 30–90 sec on the extent of polar groups created on the LDPE. We also investigated the surface topography of and water contact angle on the LDPE film surface, mechanical properties of the LDPE film, and adhesion strength of the evaporated copper metal film to the LDPE film surface. IR and electron spectroscopy for chemical analysis revealed the introduction of polar groups on the modified LDPE film surface, which exhibited an improved contact angle and copper/LDPE adhesion. The number of polar groups and the surface roughness increased with increasing treatment time of chromic acid/plasma. Water contact angle significantly decreased with increasing treatment time of chromic acid/plasma. Combination treatment of oxygen plasma with chromic acid drastically decreased the contact angle. When the treatment times of chromic acid and oxygen plasma were greater than 10 min and 30 sec, respectively, the contact angle was below 20°. With an increasing treatment time of chromic acid, the tensile strength of the LDPE film decreased, and the film color changed after about 10 min and then became blackened after 30 min. With the scratch test, the adhesion between copper and LDPE was found to increase with an increasing treatment time of chromic acid/oxygen plasma. From these results, we found that the optimum treatment times with chromic acid and oxygen plasma were near 30 min and 30 sec, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1677–1690, 2001     

Improvement of adhesion of PET fibers to rubber by argon-oxygen plasma treatment

Polyethylene terephthalate fibers cords were modified with argon, oxygen, and successive argon/oxygen cold plasmas as a function of treatment time. Plasma treated cords were coated with resorcinol formaldehyde latex, then tested as rubber reinforcing materials. The peel strength was discussed with respect to the polar component of the surface energy and the etching of the fibers. An increased adhesion of ∼ 280% was obtained with 30 min argon plasma followed by 30 min oxygen plasma, at 75 W power and 40 Pa pressure without altering the traction strength of the fibers cords. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2321–2330, 1998     

Effect of DC glow discharge treatment on the surface energy and surface resistivity of thin film of polypropylene

A change in the surface energy and surface resistivity of a thin film of polypropylene (PP) of thickness 100 μm was investigated, using direct current (DC) glow discharge. The thin film of the PP was treated for various discharge powers and treatment time and the modification in the surface energy and the surface resistivity was observed. To investigate the modification in the surface energy after DC glow discharge treatment, contact angle of two test liquids formamide and de‐ionized water over the surface of PP film was measured. By measuring the contact angle the change in surface energy and its two polar and dispersive components have been measured. It was observed that at a given power level of DC glow discharge surface energy and its polar component increases with increase of the treatment time, attains a maximum value, and then becomes almost constant. Correspondingly, with increase in surface energy, a decrease in surface resistivity was observed. Also, a change in surface morphology was observed by atomic force microscopy and by FT‐IR spectra generation of polar groups at the surface of PP film. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 767–772, 2007     

Toughening vinyl ester networks with polypropylene meso-fibers: Interface modification and composite properties

Polymer-polymer composites comprised of vinyl ester matrices (VE) and polypropylene (PP) fiber meshes were fabricated and tested in this investigation. Results indicated that PP fibers greatly enhanced fracture toughness; however, strength of the VE was significantly reduced as voids were observed at the interface of the PP and VE. A two-step surface modification, oxygen plasma treatment followed by grafting vinyltrimethoxysilane (VTMS), was conducted on PP fibers in an effort to improve interfacial strength. Interfacial discontinuities of composites were improved after surface modification of PP. The oxygen plasma treatment added hydrophilic functional groups but caused surface roughness. Surface treatment of PP slightly increased fracture toughness of the PP-VE composite by enhancing energy absorption capacity at the interface. However, mechanical strength and modulus did not significantly increase for the composite using VTMS grafted PP fibers due to the weak fiber material. Small PP fibers with higher strength may attain the expected improvement in mechanical properties after surface treatment.