Study of siloxane additives migration to the surface of polyester-(melamine)-polyurethane coatings: Aging effects after ethanol cleaning

This study determines the influences of siloxane flow agents’ migration on the outermost surface composition of clearcoats, before and after ethanol cleaning. This evaluation is undertaken to improve adhesion of pressure-sensitive adhesives (PSAs) on automotive paint systems. Most of the siloxane flow agents segregate from the bulk to the clearcoat outermost surface during curing. These additives can cover until 50% of the surface area but X-ray photoelectron spectroscopy (XPS) and time of flight-secondary ion mass spectrometry (ToF-SIMS) analyses indicate that they can be removed by ethanol cleaning. Composition of the cleaned clearcoats surfaces are similar as the composition of clearcoat formulated without siloxane additives: the polyester-(melamine)-polyurethane network is more detected than before cleaning. However, outermost surface analyses show that several aging weeks increase the siloxane additives segregation. This post-cleaning migration modifies the clearcoat surface composition and cancels the chemical modifications due to the ethanol cleaning. XPS analyses show that silicon concentrations after cleaning and aging are inversely proportional to the initial silicon concentrations measured after curing. It highlights that aging has to be controlled to improve adhesion of PSAs on clearcoats. A second ethanol cleaning on aged clearcoats is not effective to remove these new siloxane additives. Their formulation should be different from the flow agents and it could modify their solubility in ethanol. This result could also indicate that these new siloxane additives are not located on the last molecular layer of surface and they would not be soluble in ethanol.     

The interfacial interaction between isocyanate and stainless steel

The interfacial interactions between methylene diphenyl di-isocyanate (MDI) and polymeric MDI (PMDI) with 316L stainless steel have been studied in order to understand the adhesion properties of polyurethane based adhesives (containing free isocyanate groups) on metal surfaces. A thin (<5 nm) layer of MDI and PMDI was deposited on the surface of clean 316L stainless steel and then analysed by X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (ToF-SIMS). By using density functional theory (DFT) methods for the interpretation of XPS data, the presence of specific interactions between the adsorbate and the substrate was established. The reaction between isocyanate and metal hydroxyl groups with the formation of urethane-like bonding with the metal was observed. The formation of hydrogen bonds between the isocyanate nitrogen and the hydroxyl groups and the formation of a nitrogen-metal double bond, as a consequence of the cycloaddition reaction between isocyanate and metal oxide, are also proposed.     

Friction and Wear Reduction Mechanism of Polyalkylene Glycol-Based Engine Oils

Polyalkylene glycols (PAG) have been explored as a possible base stock for engine oil formulation. The friction, wear, and load-carrying capacity of five different PAG chemistries were evaluated either as a base stock or as formulated oils in pure sliding and sliding-rolling conditions using various laboratory bench test rigs operating under boundary and mixed lubrication regimes. The results were compared against GF-5 SAE 5W-20 and a mineral-based oil. The wear surfaces were also characterized using various surface-sensitive techniques for analysis of tribofilms to understand the mechanism of friction reduction. The results indicated that PAG oils show lower friction/traction coefficients and improved load-carrying capability, depending on the formulation, than those of the GF-5 SAE 5W-20 and mineral-based oil. The adsorption of PAG molecules on the surface appeared to be responsible for the lower friction characteristics.     

The adsorption of an epoxy acrylate resin on aluminium alloy conversion coatings

A thermodynamic study of the adsorption of an epoxy acrylate resin used for UV-cured coatings on two different anticorrosion pretreatments on aluminium alloys relevant to aerospace industry has been undertaken. Aluminium alloy Al2219 specimens, treated with an inorganic chromate based conversion coating (Alodine 1200S) and an organic titanium based conversion coating (Nabutan STI/310), were immersed in solutions of different concentrations of the resin and adsorption isotherms were determined by assessing the uptake of the adsorbate, as a function of solution concentration, by time-of-flight secondary ion mass spectrometry (ToF-SIMS). The results show different behaviour for the two substrates, which can be attributed to the organic component of the titanium based coating. In the case of the inorganic conversion coating a clear plateau is achieved at relatively low concentrations and at a lower level of adsorption than for the hybrid coating. The data for both the coatings conform well to the Langmuir model, the organic coating, as well as showing a higher level of adsorption of the resin, also presents oscillatory behaviour at low concentration, which is shown to be complementary to the behaviour of the reactive diluent included with the epoxy acrylate to aid processing. A discussion of this competitive adsorption of the epoxy resin and the diluent on the different substrates is presented, based on considerations of the chemistry of the systems under investigation.     

焊球阵列封装(BGA)中吸水性测量概述

塑料焊球阵列封装(PBGA)对爆米花裂纹的抵抗力较小,一旦因焊接产生的高温使水汽迅速地扩展,就会发生此种现象。在粘片胶处发生爆米花现象,因此,必须研究在粘片胶附近发生的吸水性和解吸现象。本文主要讨论BGA中爆米花裂纹产生的机理,特别是对吸水性分布情况的探讨。用重水进行模拟分析,因为重水与水的吸收性比较接近。采用飞行时间次级离子质谱分析法(TOF-SIMS)来测量重水吸收性分布。弄清BGA封装主要是通过模塑包封部分的上部吸收水分的,由基板吸收的水分是少量的。因BGA基板具有叠层结构,水分不能首先透过基板。应优化BGA封装系统的设计,使其不易产生爆米花裂纹。     

The distribution of lithium intercalated in V2O5 thin films studied by XPS and ToF-SIMS

The distribution of lithium in V₂O₅/V lower oxide duplex thin films prepared by thermal oxidation of V metal was analysed by XPS and ToF-SIMS after intercalation at 2.8 V versus Li/Li⁺ and de-intercalation at 3.8 V following cycling between 3.8 and 2.8 V in 1 M LiClO₄-PC. XPS analysis of the intercalated thin film evidenced a partial reduction (43 at.% V⁴⁺) of the V₂O₅ surface, the modification of its electronic structure and the presence of Li, consistent with the formation of the δ-Li_xV₂O₅ (0.9 ≤ x ≤ 1) phase. The Li in-depth distribution measured by ToF-SIMS shows a maximum in the outer layer of V₂O₅, but Li is also found at the oxide film/metal substrate interface indicating its diffusion across the inner layer of V lower oxides. The analyses performed after de-intercalation on the samples cycled 12, 120 and 300 times reveal the effect of aging on the trapping of lithium. A significant reduction (17-22 at.% V⁴⁺) of the V₂O₅ surface was measured after 300 cycles. The Li in-depth distribution shows a maximum at the interface between the outer layer of V₂O₅ and the inner layer of lower oxides. Aging favours the accumulation of lithium at this interface with a resulting enlarged distribution enriching the sub-surface of the outer layer of V₂O₅ and the inner layer of lower oxides after 300 cycles. Lithium is also found, but in smaller quantities, at the oxide film/metal substrate interface. Measurements performed in the non-electrochemically treated surface areas of the de-intercalated samples revealed the same type of modifications, evidencing the diffusion of lithium along the interfaces where it is trapped.     

Failure mechanism of thin Al2O3 coatings grown by atomic layer deposition for corrosion protection of carbon steel

Combined analysis by electrochemical impedance spectroscopy (EIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and field emission scanning electron microscopy (FESEM) of the corrosion protection provided to carbon steel by thin (50 nm) Al₂O₃ coatings grown by atomic layer deposition (ALD) and its failure mechanism is reported. In spite of excellent sealing properties, the results show an average dissolution rate of the alumina coating of ∼7 nm h⁻¹ in neutral 0.2 M NaCl and increasing porosity of the remaining layers with increasing immersion time. Alumina dissolution is triggered by the penetration of the solution via cracks/pinholes through the coating to the substrate surface where oxygen reduction takes place, raising the pH. At defective substrate surface sites of high aspect ratio and concentrated residual mechanical stress (along scratches) presumably exposing a higher steel surface fraction, localized dissolution of the coating is promoted by a more facile access of the solution to the substrate surface enhancing oxygen reduction. De-adhesion of the coating is also promoted in these sites by the ingress of the anodic dissolution trenching the steel surface. Localized corrosion of the alloy (i.e. pitting) is triggered prior to complete dissolution of the alumina film on the elsewhere still coated surface matrix.     

Mixed reactions: Glass durability and the mixed-alkali effect

Multiple-component oxide silicate glasses possess a complex network backbone, which results in manifolded composition property relationships. The relation between the chemical composition and durability of silicate glasses is not linear, however, this relation has always been considered somewhat relevant. Several contradicting observations on the mixed-alkali effect and its relation with their chemical alteration have been reported. Here, laboratory results and historical evidence show that the often good state of preservation of aged mixed modifier glasses is in good agreement with the influence of a mixed-modifier cation effect (MMCE) such as had been observed for other mobility- and bulk-related properties. This concordance supports the proposals made through this work concerning pore closure and lower diffusivity of mobile species under the MMCE.     

THE INFLUENCE OF PROCESS PARAMETERS ON THE INTERFACIAL CHEMISTRY OF γ-GPS ON ALUMINIUM: A REVIEW

Within the “International Collaborative Programme on Organosilane Adhesion Promoters” (ICOSAP), scientists from the U.S. and Europe contributed to the understanding of an organosilane primer process, based on an aqueous solution of γ-glycidoxypropyl trimethoxysilane (γ-GPS), used currently for aerospace repair purposes. Parameters such as temperature of cure, ageing time, and concentration of the aqueous solution have been investigated, and this work reviews the effect that each variable has on the process, and the resulting integrity of the GPS/aluminium interface. The aim of the work was to provide a more environmentally friendly replacement for pretreatments containing Cr(VI) that are currently used, such as chromic acid anodising and acid etching employed for the structural adhesive bonding of aluminium.

The formation of covalent interfacial bonding is shown to be a function of the hydrolysis and condensation of the silane molecules in solution as well as the type of solvent used. The curing temperature of the aqueous film on the aluminium is also shown to have an effect on the chemistry of the resulting primer film and its efficacy as an adhesion promoter. All these parameters must be optimised to obtain durability that matches that obtained by a phosphoric acid anodising pretreatment. This work reports on the various studies performed towards this aim carried out within the remit of the ICOSAP initiative, with a particular emphasis on the interfacial chemistry between γ-GPS and the aluminium substrate, and indicates the manner in which the results point the way towards a viable, environmentally friendly pretreatment for the adhesive bonding of aluminium for aerospaceapplications.     

The Interaction of γ-Glycidoxypropyltrimethoxysilane with Oxidised Aluminium Substrates: The Effect of Drying Temperature

The interaction of γ-glycidoxypropyltrimethoxysilane (GPS) with oxidised aluminium substrates has been investigated in terms of the effect of the drying, or curing, temperature. Samples treated with aqueous solutions of GPS at concentrations of 1,4 and 8% v/v were cured at 25, 50, 93 and 120°C. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to construct adsorption isotherms and determine the thicknesses of the various GPS coatings. A temperature effect induces subtle changes in the structure of the resulting films. The uptake of GPS is increasing with increasing concentration of GPS. The structure of the films changes at a threshold temperature between 50 to 93°C. XPS and ToF-SIMS data both indicate that the interaction of the GPS film on aluminium is different for low and high temperatures drying regimes. Using the Beer-Lambert equation, it was found that increasing the curing temperature leads to the variation of the thickness of silane films. This is interpreted in terms of changes in the crosslink density of the films and in their state of hydration and/or degradation.