Surface modification of polyimide by combining swelling and TiO2 photocatalytic treatments for adhesion improvement of electroless Cu

In order to enhance the adhesion strength between the PI film and the electroless copper film, a combination of swelling and TiO₂ photocatalytic treatments was used to modify polyimide (PI) film. The effects of the swelling solution composition and TiO₂ photocatalytic condition on the surface performance were investigated. After the optimal swelling and photocatalytic treatment, the surface contact angle of the PI film decreased from 85 to 28.7°, and the surface average roughness of the PI film only increased from 1.3 to 13.6?nm, indicating no obvious change for the surface topography of PI film after the photocatalytic treatment. However, the adhesion strength between electroless copper film and the PI film reached to 0.6?KN·m^?1. The FT-IR spectra and XPS analyses indicated that –COOH group was formed on the PI surface after the treatment, and the surface hydrophilicity was improved, which improved the adhesion strength between the PI film and the electroless copper film.     

Study of an environment-friendly surface pretreatment of ABS-polycarbonate surface for adhesion improvement

In this paper, an environmentally friendly etching system containing MnO₂–H₃PO₄–H₂SO₄ colloid was used to investigate surface etching for ABS- polycarbonate (PC/ABS) as a replacement for conventional chromic acid etching solutions. In order to obtain a good etching performance, a swelling system, containing tetramethylammonium hydroxide (TMAH), and 1-Methyl-2-pyrrolidinone (NMP), was used to investigate the surface swelling for PC/ABS resin. Then the effects of H₂SO₄ concentration, and etching time on the surface topographies and surface contact angle were investigated. After the optimal swelling and etching treatment, the surface contact angle of PC/ABS resin decreased from 95.7° to 28.3°, and the adhesion strength between electroless copper film and PC/ABS resin reached to 1.04 KN m⁻¹. The FT-IR spectra and XPS analyses indicated that hydroxyl and carboxyl groups formed on the PC/ABS surface as a result of the swelling and etching treatment, which improved the adhesion strength between PC/ABS substrate and elctroless copper film.     

The effect of TiO2 morphology on the surface modification of poly (ethylene terephthalate) for electroless plating

In this study, a surface modification of the poly (ethylene terephthalate) (PET) film using TiO₂ photocatalytic treatment was investigated. In order to enhance the adhesion strength between the PET film and the electroless copper film, the effects of TiO₂ crystal forms, TiO₂ particle sizes, and TiO₂ content, as well as treatment condition, upon the surface contact angle, surface characterization, and adhesion strength were investigated. Anatase TiO₂ with a particle size of 5 nm had a high catalytic activity and dispersibility in aqueous solution. After the optimal photocatalytic treatment, the surface contact angle of the PET film decreased from 84.4° to 19.8°, and the surface roughness of the PET film increased from 36 to 117 nm. The adhesion strength between the PET film and the electroless copper film reached 0.89?KN?m^?1. X-ray photoelectron spectroscopy analyses indicated the carbonyl group was formed on the PET surface after photocatalytic treatment, and the surface hydrophilicity was improved. Consequently, TiO₂ photocatalytic treatment is an environmentally friendly and effective method for the surface modification of the PET film.     

Adhesion Improvement of ABS Resin to Electroless Copper by H2SO4–MnO2 Colloid with Ultrasound-Assisted Treatment

The adhesion strength between electroless copper and acrylonitrile-butadiene-styrene (ABS) resin can be improved significantly by an environmentally friendly etching system containing H₂SO₄–MnO₂ colloid as a replacement for conventional chromic acid etching solutions. In this paper, the effects of the H₂SO₄ concentration and ultrasound-assisted treatment (UAT) on the surface roughness and adhesion strength were investigated. When the H₂SO₄ concentration was 11.8～12.7 M, good etching was obtained. With UAT, many uniform cavities formed on the ABS surface with the average surface roughness (R _a) and maximum roughness (R _max) of ABS substrates decreasing from 386 and 397 nm to 278 and 285 nm, respectively, which were much lower than that etched by CrO₃–H₂SO₄ colloid (420 and 510 nm, respectively). The average adhesion strength increased from 1.29 to 1.39 kN/m, which was close to that obtained with chromic acid etching treatment (1.42 kN/m). The surface contact angle measurement indicated that the density of the polar groups on the ABS surface increased with increasing time of UAT. The results indicated that surface etching with UAT not only improved the uniformity of cavities, but also enhanced the oxidation rate of ABS resin, which in turn resulted in greater adhesion strength and a lower surface roughness.     

Adhesion improvement of electroless copper to PC substrate by a low environmental pollution MnO2–H3PO4–H2SO4–H2O system

A low environmental pollution etching system, MnO₂–H₂SO₄–H₃PO₄–H₂O colloid, was used to investigate surface etching performance of polycarbonate (PC) as a replacement for the chromic acid etching solution. The effects of H₂SO₄ concentrations, H₃PO₄ concentrations and etching times upon the surface topography, surface chemistry and surface roughness were studied. With the appropriate etching treatment, the surface average roughness (R_a) of PC substrates increased from 3 to 177 nm, and the adhesion strength between the electroless copper and PC substrate also reached 1.10 KN m⁻¹. After the etching treatment, the PC surface became hydrophilic and the surface contact angle decreased from 95.2° to 24.8°. The intensity of C–O groups increased and the new functional groups (–COOH) formed on the PC surface with the etching treatment, which improved the adhesion strength between PC substrate and elctroless copper film.     

A study of the environmentally friendly polycarbonate surface etching system containing H2SO4–MnO2 colloid

In this paper, an environmentally friendly etching system containing H₂SO₄–MnO₂ colloid was used to investigate surface etching for polycarbonate (PC). The effects of swelling condition, H₂SO₄ concentrations and etching times on surface topography and surface roughness were studied. With the etching treatment, the surface average roughness (R _a) of PC substrates increased from 3 to 76?nm and the adhesion strength between the electroless copper and PC substrate reached 1.08 KN/m. Surface chemistry of PC substrates was investigated by the contact angle measurement and X-ray photoelectron spectroscopy spectra (XPS). After the etching treatment, PC surface became hydrophilic and the contact angle decreased from 95.2 to 39.6^o. XPS analyses indicate that hydroxyl and carboxyl groups are formed on the PC surface as a result of the etching treatment, which improve the adhesion strength between PC substrate and electroless copper film.     

Surface modification of ABS with Cr6+ free etching process in the electroless plating

ABS resin is widely used after the plating process. The traditional ABS resin surface etching process uses a chromic acid system, which is a great threat to environmental protection. This paper examines a new environment-friendly measure in the etching system, which is composed of HNO₃, H₂SO₄, and NiSO₄. With this system, the solution will be etching at 60?°C for 20?minutes on an ABS resin surface and causing the surface roughness of the ABS resin to become larger, and an increase of hydrophilicity. It is observed that the root mean square (RMS) of the surface roughness of the ABS resin increased from 3.21?nm to 27.5?nm after etching, and the surface contact angle of ABS resin decreased from 88.04° to 65.29°. After the etching process, the surface of ABS can be electroless plated successfully and the bonding force of coating and resin can reach 2.09 MPa. The FT-IR spectra and XPS analyses showed that hydroxyl and nitro groups on the ABS surface are as a result of etching treatment, which improves the bonding strength between ABS substrate and electroless copper plating. This new etching system can be a substitute for the traditional chromic acid system in the industry, which will greatly reduce the pollution caused by the traditional process.     

Study on the pretreatment method of glass-epoxy resin in the presence of TiO2 sol prepared by hydrothermal method

In the present study, the pretreatment of glass-epoxy resin using photoreaction of TiO₂ sol prepared by hydrothermal method was investigated. The surface properties for the pretreated substrate were examined, and the change of contact angle was measured to confirm the hydrophile property caused by the photocatalytic reaction. After the pretreatment, the surface was oxidized with showing no changes in its morphology. However, the surface roughness at nano-scale order increased with the photocatalytic reaction time. When UV light was irradiated for 60 min in TiO₂ sol, the adhesion strength of electroless-plated Cu film was most excellent in other test conditions.     

Enhanced photocatalytic activity of highly transparent superhydrophilic doped TiO2 thin films for improving the self-cleaning property of solar panel covers

Undoped and metal doped nanocrystalline TiO₂ transparent thin films were synthesized on glass substrates via sol-gel/dip-coating method. TiO₂ thin film coatings can be applied to the surfaces of solar panels to impart self-cleaning properties to them. The structural and optical properties of few nanometer-thick films were characterized by XRD, SEM, CA, AFM, XPS, and UV–Vis spectrophotometry techniques. The stoichiometric TiO₂ films crystallized in anatase phase, with a particle size of ～100 nm, which were uniformly distributed on the surface. The prepared films with a roughness of ～1–5 nm, increased the hydrophilicity of the glass surface. Reducing the amount of Ti precursor (X) favored the improvement of film quality. To improve the photocatalytic activity of the TiO₂ thin film, it was doped with Ni, Cd, Mo, Bi and Sr metal ions. The effect of metal doping on the photocatalytic activity of the films was investigated using the degradation process of methylene blue (MB) dye as the model contaminant. Among the prepared coatings, the Sr–TiO₂ film showed the highest efficiency for MB degradation. It increased the dye degradation efficiency of the films under both UV and Vis lights. The kinetic investigations also showed that the degradation of MB by TiO₂ and M ? TiO₂ films obeyed the pseudo-first order kinetics.     

Effects of titania content and plasma treatment on the interfacial adhesion mechanism of nano titania-hybridized polyimide and copper system

Nano-titania (TiO₂) incorporated into polyimide (PI) matrix can significantly enhance the adhesion strength for PI/TiO₂ hybrid film and copper system. Surface modifications by various plasma treatments (Ar, Ar/N₂ and Ar/O₂) were also applied in this study to improve the adhesion strength. The Ar/N₂ plasma treatment is regarded as the more effective way in promoting the adhesion strength. The maximum adhesion value of 9.53 N/cm was obtained for the PI/TiO₂-1 wt% hybrid film with Ar/N₂ plasma treatment. It is enhanced about 10 times as large as pristine PI. Furthermore, by Ar/O₂ plasma treatment, a weak boundary of copper oxide was formed at the interlayer between PI/TiO₂ hybrid film and copper which decreases the adhesion strength. The effects of plasma treatment and content of nanosized TiO₂ on the adhesion strength between PI/TiO₂ hybrid film and copper system were studied. Atomic force microscope and contact angle analyses were used to measure the changes in surface morphology and surface energy as a result of plasma treatment. Besides, the interfacial states of peeled-off polymer side and copper side were investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Based on the result of XPS spectra, the peeled-off failure mode between PI/TiO₂ hybrid film and copper was proposed in this study.     

Photocatalytic hydrogen production from methanol aqueous solution under visible-light using Cu/S–TiO2 prepared by electroless plating method

Cu was loaded on the S-doped TiO₂ by electroless plating method. The prepared Cu/S–TiO₂ exhibited high photocatalytic activity for hydrogen generation, and the yield is up to 7.5 mmol h^− 1 g^− 1cat in methanol solution. Their physical structure and chemical properties were characterized by UV–Vis, XRD, XPS and EXAFS. The copper species were CuO and Cu₂O, and the sample showed excellent visible light absorption ability. Comparing with the sample prepared by chemical reducing method, the electroless plated copper on S–TiO₂ was highly dispersed, which could facilitate photo-generated charges capture, transfer and separation.     

A New Surface Etching Method Using MnO2/H2SO4 Colloid for Adhesion Improvement of Epoxy Polymer

Abstract

A new surface etching method using MnO₂/H₂SO₄ as the etchant to improve the adhesion between an epoxy polymer surface and a metallic layer, was studied. The effects of bath temperature, etching time and H₂SO₄ concentration on the surface topography and chemical properties were investigated. After the etching treatment of the MnO₂–H₂SO₄ colloid, not only did the surface roughness increase remarkably, but also the surface of epoxy became hydrophilic and the contact angle of the epoxy surface was also decreased from 93.5° to about 8.0°. The X-ray photoelectron spectroscopy analysis indicated that as a result of the etching treatment, hydroxyl, carbonyl and carboxylic acid groups formed on the epoxy surface. The adhesion strength was markedly enhanced with the appropriate etching treatment, which was attributed to the improvement of the surface roughness and the increased hydrophilicity.     

Surface Modification of a Photo-Definable Epoxy Resin with Polydopamine to Improve Adhesion with Electroless Deposited Copper

Abstract

This paper describes the influence of polydopamine surface modifications on the adhesion strength of electroless deposited copper on roughened epoxy resin substrates. The surfaces are characterized with XPS and ToF-S-SIMS. Next, a thorough investigation of the copper–epoxy interface is performed using SEM. Both the polydopamine modification and the variation of the electroless plating bath temperature lead to new insights into the different contributions of chemical and physical adhesion to the overall adhesion strength.     

Effect of sputtering parameters on the self-cleaning properties of amorphous titanium dioxide thin films

The aim of this work was to assess the effect of the direct current magnetron sputtering parameters on the photocatalytic activity and photoinduced wettability of amorphous TiO₂ films. TiO₂ films were deposited on glass using the direct current magnetron sputtering technique, without heating, at different total working pressures. Qualitative analysis using in situ X-ray photoelectron spectroscopy confirmed the TiO₂ stoichiometry of the deposited films. Surface structure was studied as a function of working pressure using scanning electron microscopy. The hydrophilicity of the TiO₂ surfaces was investigated macroscopically using measurements of the water contact angle. A threshold working pressure was observed, with a strong dependence on the film thickness. A super hydrophilic surface was observed after less than 1 h of UV irradiation. The photocatalytic activity of the films was evaluated under UV light through the degradation of methylene blue (\(\lambda_{\hbox{max} } \approx 660\;{\text{nm}}\)). The effect of UV irradiation on the photocatalytic activity was rapid, strong, and dependent on film thickness and total working pressure. Fifty percent of organic compounds were photodegraded by films with a thickness of 60 nm deposited at 10 mTorr.     

Photocatalytic Cancer (HeLa) Cell-Killing Enhanced with Cu–TiO2 Nanocomposite

The metallic Cu nanoparticles have been successfully deposited on the heterogeneous TiO₂ surface by the borohydride reduction of copper nitrate in water/CH₃CN mixture under Ar atmosphere. The catalytic activity of the Cu–TiO₂ nanocomposite was evaluated by the application to a photocatalytic cancer cell-killing under UV–visible light irradiation. Based on the obtained results, a plausible mechanism was proposed.     

Self-cleaning performance of sol–gel-derived TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> double-layer thin films

The self-cleaning properties of the TiO₂/SiO₂ double-layer films prepared by sol–gel method were investigated. Thin films were prepared by spin coating onto glass and then thermally treated at different temperatures, and characterized using X-ray diffraction, atomic force microscopy, field emission scanning electron microscopy, and UV–visible spectroscopy. The cross-sectional structure of the films was observed by FESEM. The surface roughness of the films was characterized by AFM. The root mean square surface roughness of the thin films was below 2 nm, which should enhance their optical transparency. The photo-induced hydrophilicity of the films was evaluated by water contact angle measurement in air. The photocatalytic activity of the films was studied by the photocatalytic degradation of methylene blue under UV light irradiations. The TiO₂/SiO₂ double-layer thin films are plausibly applicable to developing self-cleaning materials in various applications such as windows, solar panels, cement, and paints.     

Effects of V and Zn codoping on the microstructures and photocatalytic activities of nanocrystalline TiO2 films

To enhance the photocatalytic activity of TiO₂, V and Zn co-doped TiO₂ films were synthesized by the sol–gel method. The experimental results indicated that the films were composed of round-like nano-particles or aggregates. V and Zn codoping could not only obviously increase the specific surface area of TiO₂ but also result in the narrowed band gap of TiO₂ sample. The photocatalytic activities of the TiO₂ films were evaluated by the photocatalytic decomposition of organic dyes in aqueous solution. Compared with un-doped TiO₂ film or single doped TiO₂ film, V and Zn co-doped TiO₂ film exhibited excellent photocatalytic activities under both UV light and visible light. The improvement mechanism by V and Zn codoping was also discussed.     

Template-assisted hydrothermal synthesis and photocatalytic activity of novel TiO2 hollow nanostructures

TiO₂ hollow nanostructures were successfully synthesized by a controlled hydrothermal precipitation reaction using Resorcinol–Formaldehyde resin spheres as templates in aqueous solution, and then removal of the RF resins spheres by calcination in air at 450 °C for 4 h. The obtained TiO₂ hollow spheres were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N₂ adsorption–desorption analysis, and UV–visible diffuse reflectance spectroscopy. The photocatalytic activity of the as-prepared samples was evaluated by photocatalytic decolorization of rhodamine B aqueous solution at ambient temperature under UV illumination. The results indicated TiO₂ hollow nanostructures exhibit the excellent photocatalytic activity probably due to the unique hollow micro-architectures.     

Investigation of inter‐relationship between tensile behavior and photocatalytic activity of an acrylic‐based composite upon UVA exposure

The aim of this work is to produce a photocatalytic pseudo‐paint for benzene removal from air and find the role of TiO₂ nanoparticles, TiO₂ pigment, and CaCO₃ extender on photocatalytic performance of this paint along with their role on stress–strain behavior after ultraviolet (UV) exposure. For this purpose, TiO₂ nanoparticles were dispersed into an indoor paint resin (i.e., copolymer acrylic–styrene). The impact of main components of the paint on photocatalytic oxidation (PCO) rate of benzene was studied. It was found that dispersion of nanoparticles had the most dramatic effect on photo activity of nanocomposite. TiO₂ pigment generally increased PCO rate and also made the paint more stable under tensile stress. CaCO₃ may increase and/or decrease PCO of benzene, whether there is pigment in the formulation or not. However, it does not generally contribute to making the formulation resistant to UV exposure. Nanoparticles bring PCO and mechanical strength into the paint, but fail to strengthen the composite against UV deterioration. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44447.     

Visible light photocatalytic activity of TiO2/heat‐treated PVC film

BACKGROUND: Semiconductor TiO₂ has been investigated extensively due to its chemical stability, nontoxicity and inexpensiveness. However, the wide band gap of anatase TiO₂ (about 3.2 eV) only allows it to absorb UV light. TiO₂ nanoparticles modified by conditional conjugated polymers show excellent photocatalytic activity under visible light. However, these conjugated polymers are not only expensive, but also difficult to process. Polyvinyl chloride (PVC) was heat‐treated at high temperature to remove HCl and a C?C conjugated chain structure was obtained. When TiO₂ nanoparticles were dispersed into the conjugated polymer film derived from PVC, this composites film exhibited high visible light photocatalytic activity. RESULTS: The photocatalytic activity of TiO₂/heat‐treated PVC (HTPVC) film was investigated by degrading Rhodamine B (RhB) under visible light irradiation. The photodegradation of RhB follows apparent first‐order kinetics. The rate constants of RhB photodegradation in the presence of the TiO₂/HTPVC films with different mass content of TiO₂ are 16–56 and 4–14 times that obtained in the presence of the pure HTPVC and TiO₂/polymethyl methacrylate (PMMA) composite film, respectively. The TiO₂/HTPVC film showed excellent photocatalytic activity and stability after 10 cycles under visible light irradiation. CONCLUSION: TiO₂/HTPVC film exhibits high visible light photocatalytic activity and stability. Copyright © 2012 Society of Chemical Industry