Adhesion and Surface Analysis

In the last 25 years, surface sensitive analytical techniques have made a major contribution to our understanding of adhesion phenomena and problems. There are several areas where these techniques have provided important information including the identification of failure modes, the chemistry of a substrate before and after pretreatments, the stability of surfaces and interfaces, the identification of surface contaminants, the interaction across an interface and the nature of interphases. X-ray photoelectron spectroscopy (XPS or ESCA), Auger electron spectroscopy (AES) and static secondary ion mass spectrometry (SSIMS) have proved to be especially useful. Many examples of the usefulness of these techniques are given.     

Adhesion Promotion by Silanes: A Study of their Interfacial Chemistry in a Model Polystyrene Coating by XPS and SIMS

Adhesion of a polystyrene coating to solvent cleaned steel is increased two-fold by addition of 0.5% wt/wt of aminosilane (A1120). A study has been carried out on the coating-substrate interfacial chemistry to gain an understanding of the mechanism of adhesion promotion. It is shown that in peel experiments the coating fails adhesively between the polystyrene and an adsorbed layer of aminosilane on the steel surface. The improvement in adhesion results from displacement by the silane of the 1.4 nm thick layer of residual carbonaceous contamination on the steel surface. It is proposed that this leads to a stronger substrate-coating interaction either through improved intermolecular contact between the segregated silane and the polymer or through secondary bonding between the amine groups of the silane and the polarisable aromatic rings of the polystyrene.     

Adhesion Promotion by Silanes: A Study of their Interfacial Chemistry in a Model Polystyrene Coating by XPS and SIMS

Adhesion of a polystyrene coating to solvent cleaned steel is increased two-fold by addition of 0.5% wt/wt of aminosilane (A1120). A study has been carried out on the coating-substrate interfacial chemistry to gain an understanding of the mechanism of adhesion promotion. It is shown that in peel experiments the coating fails adhesively between the polystyrene and an adsorbed layer of aminosilane on the steel surface. The improvement in adhesion results from displacement by the silane of the 1.4 nm thick layer of residual carbonaceous contamination on the steel surface. It is proposed that this leads to a stronger substrate-coating interaction either through improved intermolecular contact between the segregated silane and the polymer or through secondary bonding between the amine groups of the silane and the polarisable aromatic rings of the polystyrene.     

Surface segregation in blends containing poly(dimethylsiloxane)-polystyrene block copolymers

The surface composition of polystyrene blends containing poly(dimethylsiloxane)-polystyrene block copolymers have been analyzed using X-ray photoelectron spectroscopy (XPS), contact angle measurements, and time-of-flight secondary ion mass spectrometry (TOFSIMS). The three techniques showed the surface of the blend samples to be identical to pure poly(dimethylsiloxane) homopolymer, despite the fact that the systems each contained only a 2% bulk concentration of siloxane. The high surface sensitivity of TOFSIMS—which probes the samples to depths of a few angstroms—indicates an enrichment of-Si(CH₃)₃ groups at the surface. These are the terminal groups of the PDMS part of the block. Their enrichment at the surface of the samples is presumably due to their low surface energy, in addition to the tendency for end groups to be at the surface due to free volume considerations.Presented at the XXVIth Silicon Symposium, Indiana University-Purdue University at Indianapolis, March 26–27, 1993.     

Degradation of Interfacial Chemistry of Epoxy/Silane/Aluminium Interfaces as a Result of Aqueous Attack

The degradation of a thin layer of adhesive on a grit-blasted aluminium substrate, as a result of aqueous attack, was investigated and compared with the behavior of the adhesive on a grit-blasted aluminium substrate treated with γ-glycidoxypropyl trimethoxy silane (GPS). The degradation study was achieved by examining aluminium coupons treated with adhesive that had been immersed in water at 25°C and an elevated temperature (50°C) for various treatment times ranging between 10 min and 1 day. All samples were characterized using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). XPS and ToF-SIMS data indicated that the adhesive layer on both types of substrate was readily displaced by water. This is shown to be a two-stage process with bond rupture being identified by ToF-SIMS analysis and the displacement of the organic phase occurring at a later stage, as indicated by the XPS analysis, which showed a reduction in surface carbon concentration. When the substrates were directly in contact with water, a hydration process occurred and hydrated oxide species were formed on the surfaces. The results indicated that the hydration process was a postfailure event.     

Degradation of Interfacial Chemistry of Epoxy/Silane/Aluminium Interfaces as a Result of Aqueous Attack

The degradation of a thin layer of adhesive on a grit-blasted aluminium substrate, as a result of aqueous attack, was investigated and compared with the behavior of the adhesive on a grit-blasted aluminium substrate treated with γ-glycidoxypropyl trimethoxy silane (GPS). The degradation study was achieved by examining aluminium coupons treated with adhesive that had been immersed in water at 25°C and an elevated temperature (50°C) for various treatment times ranging between 10 min and 1 day. All samples were characterized using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). XPS and ToF-SIMS data indicated that the adhesive layer on both types of substrate was readily displaced by water. This is shown to be a two-stage process with bond rupture being identified by ToF-SIMS analysis and the displacement of the organic phase occurring at a later stage, as indicated by the XPS analysis, which showed a reduction in surface carbon concentration. When the substrates were directly in contact with water, a hydration process occurred and hydrated oxide species were formed on the surfaces. The results indicated that the hydration process was a postfailure event.     

New developments in polymer surface analysis

Surface and interface characterization of polymeric materials has not enjoyed the multi-technique approach which typifies other types of materials. X-ray photoelectron spectroscopy (XPS) has dominated, despite several major disadvantages. New approaches are discussed which either improve XPS (particularly derivatization techniques) or utilize ‘static’ secondary ion mass spectrometry (SIMS) to overcome these limitations, with examples of their application in materials problem solving.     

Film Structure and Adhesion

Paint films although attached to a substrate on one side only may be subjected to stresses, comparable to those in structural adhesives. These stresses result from shrinkage during film formation and subsequent ageing, mechanical strains, relative thermal movements of film and substrate and from osmotic pressure due to soluble material under or within the film. The adhesive strength required to prevent detachment varies from very little for weak, highly porous coatings to 10,000 lb/in² for tough coatings of high elastic modulus. Generally, adhesive strength both to the substrate and between coats in a paint system must exceed cohesive strength, under the conditions when failure is likely to develop. Dispersion and other forces, such as hydrogen bridging, between coatings and clean metal substrates should suffice to ensure adhesion but most practical surfaces carry contaminants, which interfere with wetting and intimacy of contact. Solvents and other low molecular weight components may also provide a weak interfacial layer, at least for a period after application. Modification of polymer structure to improve contaminant displacement and to increase polymer/substrate interaction forces, for example by the introduction of polar substituent or end groups will be discussed and potentialities of adhesion-promoting surface treatments reviewed.     

A Study on Hydrophobic Surface Coatings with Abrasion Resistance Property

The aim of this study is to synthesize a hydrophobic surface coating with abrasion-resistant inorganic-organic hybrid materials. First, the copolymer of poly (MMA-co-MPTS)-colloid silica was synthesized by using the free radical polymerization of the methyl methacrylate (MMA) with γ-methacrylate propyltriethoxysilane (γ-MPTS). Next, the copolymer was hydrolyzed with tetraethoxylsilane (TEOS), fluoroalkylsilane (FAS), and colloid silica in the weak acid condition by a sol-gel process to obtain the surface coatings of hybrid material of poly (MMA-co-MPTS)-colloid silica. Finally, the effects of the colloid silica content on the optical properties, abrasion resistance, and morphology of the hybrid surface coatings were discussed in this study.     

Identification of inductive behavior for polyaniline via electrochemical impedance spectroscopy

Polyaniline (PANI) film electrodeposited in HCl medium using cyclic voltammetry (CV) with an upper potential limit of 0.90 V, exhibited an inductive behavior. PANI films deposited with different conditions were subjected to various applied potentials and the impedance characteristics were recorded through electrochemical impedance spectroscopy (EIS). The impedance results clearly reveal the existence of inductive behavior to PANI. Inductive behavior was observed for PANI films deposited with conditions which favor benzoquinone/hydroquinone (BQ/HQ) formation and further evidenced by X-ray photoelectron spectroscopy (XPS). A comparative analysis of the EIS and XPS results of PANI films prepared under similar conditions with the upper potential limits of 0.75 and 0.90 V, respectively, clearly documented that the presence of BQ/HQ, the degradation product of PANI, formed during the electrochemical polymerization at the upper potential limits causes inductive behavior to PANI.     

The Effect of Conditioning on Adhesion to Human Dentin

The effect of conditioning dentin was investigated using ethyleneglycol bis(aminoethylether) tetraacetic acid (EGTA) and three proprietary agents containing ethylenediamine tetraacetic acid (EDTA), maleic acid and dipentaerythritol pentaacrylate phsophoric acid ester (PENTA). Ground dentin was treated with EGTA or one of the three proprietary agents. After adhering composite resin to treated surfaces, the shear bond strength (SBS) was determined with and without thermal stress. Scanning electron and atomic force microscopies were used to assess morphological effects of each of the agents, while low resolution X-ray photoelectron spectroscopy (XPS) was employed to evaluate elemental changes due to treatment. Mean bond strength was greatest for the PENTA-conditioned surfaces. EDTA and maleic acid demineralized the dentin surface while the agent containing PENTA produced an adherent surface film. The XPS survey showed a reduction in Ca and an increase in N for agents containing EGTA, EDTA and maleic acid, while a simultaneous reduction in both these species was observed for PENTA. EGTA did not improve adhesion for systems which were based on smear layer removal and substrate demineralization. For the PENTA-based system, which relied on the development of a molecular overlayer, EGTA degraded bond strength.     

The Effect of Conditioning on Adhesion to Human Dentin

The effect of conditioning dentin was investigated using ethyleneglycol bis(aminoethylether) tetraacetic acid (EGTA) and three proprietary agents containing ethylenediamine tetraacetic acid (EDTA), maleic acid and dipentaerythritol pentaacrylate phsophoric acid ester (PENTA). Ground dentin was treated with EGTA or one of the three proprietary agents. After adhering composite resin to treated surfaces, the shear bond strength (SBS) was determined with and without thermal stress. Scanning electron and atomic force microscopies were used to assess morphological effects of each of the agents, while low resolution X-ray photoelectron spectroscopy (XPS) was employed to evaluate elemental changes due to treatment. Mean bond strength was greatest for the PENTA-conditioned surfaces. EDTA and maleic acid demineralized the dentin surface while the agent containing PENTA produced an adherent surface film. The XPS survey showed a reduction in Ca and an increase in N for agents containing EGTA, EDTA and maleic acid, while a simultaneous reduction in both these species was observed for PENTA. EGTA did not improve adhesion for systems which were based on smear layer removal and substrate demineralization. For the PENTA-based system, which relied on the development of a molecular overlayer, EGTA degraded bond strength.     

Comparative protective abilities of organothiols SAM coatings applied to copper dissolution in aqueous environments

Self-assembled monolayers (SAMs) obtained by adsorption of n-organothiols molecules have been formed onto polycrystalline copper surfaces in order to build up barrier films protecting copper from oxidation. In this context, formation of n-dodecanethiol (DT), (3-mercaptopropyl)trimethoxysilane (MPTS) and 11-perfluorobutylundecanethiol (F₄H₁₁) monolayers has been elaborated on copper and evaluated by X-ray photoelectron spectroscopy while polarization and cyclic voltammetry curves were used to compare the inhibition efficiency of the three organic coatings. Furthermore, atomic absorption spectrometry measurements were carried out in domestic water and in NaCl 0.5 M solutions in order to evaluate and quantify the dissolution of copper electrodes before and after protection. Results showed evidences that, among the three organic compounds assessed, F₄H₁₁ is the most suitable candidate to slow down the copper oxidation process.     

Metal–support interactions on rhodium model catalysts

Metal–support interactions on supported rhodium catalysts were studied by using specially prepared Rh/TiO₂/Mo model systems. For their characterization and the analysis of modifications due to various heat treatments several surface analytical methods were applied: low-energy ion scattering, X-ray photoemission spectroscopy and thermal desorption spectroscopy. Heating in ultrahigh vacuum to 670 K leads to Rh agglomeration followed (above 720 K) by encapsulation including the formation of reduced titanium oxide species. These morphological and chemisorption changes are reversible upon reoxidation and low-temperature reduction and thus exhibit the characteristic features of strong metal–support interactions. For the effective mechanism a reaction is suggested that involves oxygen chemisorption on the Rh clusters and partial reduction of the surrounding support oxide.     

Modification of Conductive Polymer for Polymeric Anodes of Flexible Organic Light-Emitting Diodes

A conductive polymer, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), was modified with dimethyl sulfoxide (DMSO) in solution state, together with sub-sequential thermal treatment of its spin-coated film. The electrical conductivity increased by more than three orders of magnitude improvement was achieved. The mechanism for the conductivity improvement was studied at nanoscale by particle size analysis, field emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS). Smaller particle size was observed, resulting in larger contact area and better electrical conductive connections. Connection of conductive PEDOT increased on the surface of the PEDOT:PSS particles, which promoted high conductivity. Flexible anodes based on the modified PEDOT:PSS were fabricated. Flexible organic light-emitting diodes (FOLED) based the polymeric anodes have a comparable performance to those on indium–tin–oxide (ITO) anodes.     

Catalytic performance for CO2 conversion to methanol of gallium-promoted copper-based catalysts: influence of metallic precursors

This study reports new gallium-promoted copper-based catalysts prepared by co-impregnation of methoxide–acetylacetonate (acac) precursors from methanolic solutions onto silica and zinc oxide supports. Catalyst performance in the CO₂ hydrogenation to methanol was investigated at 2 MPa and temperatures between 523 and 543 K. A high activity and selectivity for ZnO-supported catalysts was found, which also showed a high stability in terms of both activity and selectivity. The maximum value for the activity was 378 g MeOH/kg cat h at 543 K, with a selectivity of 88% towards methanol production. The high performance of these materials in the CO₂ hydrogenation is related to the presence of Ga₂O₃ promoter and highly dispersed Cu⁺ species on the surface, determined by XPS and Auger on used catalysts.     

Surface Molecular Mobility for Copolymers Having Both Hydrophobic and Hydrophilic Side Chains Via Dynamic Contact Angle Measurement

The reorganization of a surface structure in response to a change in environmental media was investigated for copolymers having both hydrophobic polydimethylsiloxane (PDMS) and hydrophilic methoxypoly-ethyleneglycol (MPEG) side chains via dynamic contact angle (DCA). These copolymers showed a large contact angle hysteresis and a dependency of the advancing and receding contact angle on dipping velocity (DV). Composition dependency of DCA for these copolymers is also discussed. In addition to this, adhesion tension relaxation, F(t), for MMA/MPEGMA/PDMSMA was determined. F(t) in the advancing process increased with elapsed time and decreased in the receding process. These phenomena were explained by the adsorption and reorientation of hydrophilic segments to the water/copolymer interface in water. In XPS analysis, more oxygen atoms were detected on the surfaces of MMA/MPEGMA after immersion in water than before. For MMA/MPEGMA/PDMSMA, the atomic ratio of Si to C increased with an increase in PDMSMA content.     

Surface Molecular Mobility for Copolymers Having Both Hydrophobic and Hydrophilic Side Chains Via Dynamic Contact Angle Measurement

The reorganization of a surface structure in response to a change in environmental media was investigated for copolymers having both hydrophobic polydimethylsiloxane (PDMS) and hydrophilic methoxypoly-ethyleneglycol (MPEG) side chains via dynamic contact angle (DCA). These copolymers showed a large contact angle hysteresis and a dependency of the advancing and receding contact angle on dipping velocity (DV). Composition dependency of DCA for these copolymers is also discussed. In addition to this, adhesion tension relaxation, F(t), for MMA/MPEGMA/PDMSMA was determined. F(t) in the advancing process increased with elapsed time and decreased in the receding process. These phenomena were explained by the adsorption and reorientation of hydrophilic segments to the water/copolymer interface in water. In XPS analysis, more oxygen atoms were detected on the surfaces of MMA/MPEGMA after immersion in water than before. For MMA/MPEGMA/PDMSMA, the atomic ratio of Si to C increased with an increase in PDMSMA content.     

Review of autoxidation and driers

This article is an overview of the chemistry and driers used in autoxidatively cured coatings and in particular alkyds. The drying process for alkyds and other unsaturated fatty acid materials is based on a series of chemical reactions known as autoxidation. The autoxidative process is usually catalyzed by metal salts known as driers. Numerous of investigations have elucidated the catalytic activity and reaction mechanism of the drying process. Spectroscopic techniques, especially mass spectrometry, have been used to study the autoxidation process and its products. Recent investigations on the oxidative drying of alkyd coating films are presented with a focus on both metal based and more environmental friendly means of catalysis.