Surface molecular characterisation of different epoxy resin composites subjected to UV accelerated degradation using XPS and ToF-SIMS

Epoxy resin composites reinforced with E-glass (E), 3D glass (3D) and carbon fibre (CF) were subjected to an intense UV and high temperature accelerated degradation environment. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to provide a molecular characterisation of the surface of the degraded composites. The response at the surface of the epoxy resin composites to oxidative degradation is influenced by the composite reinforcement type and characteristics. XPS results indicate that 3D resin composites exhibit more surface oxidation as a result of the accelerated degradation in comparison with E and CF composites. Principal components analysis (PCA) of the ToF-SIMS positive ion spectra showed that E and 3D resin composites suffered chain scission while CF composites suffered chain scission and cross-linking reactions as a result of the intense UV exposure. The extent of the surface oxidation, cross-linking/condensation reaction and loss of low molecular weight (lower than C₄H_x) aliphatic hydrocarbons may be indicated using PCA of both the ToF-SIMS positive and negative ion spectra. PCA also provides insight for proposing epoxy resin chain scission and oxidation reaction mechanisms.     

Surface molecular degradation of selected high performance polymer composites under low earth orbit environmental conditions

Carbon fibre (CF), carbon nanotube (CNT), nano-clay (NanoC), and 3D-glass (3DG) reinforced polymer composites were selected to undergo treatment with an accelerated Low Earth Orbit (LEO) simulated space environment. Surface degradation mechanisms of the selected polymer composites with different types of reinforcements are discussed. The extent of the oxidation reaction at the surface as a result of LEO exposure was linked to the increase in the intensity of the oxygen-containing ions, as revealed by time-of-flight secondary ion mass spectrometry (ToF-SIMS). X-ray photoelectron spectroscopy (XPS) indicated that an increasing duration of surface treatment correlates with increasing oxygen concentration and decreasing carbon concentration. The degraded CF composite showed the least amount of oxygen (15.6%) and nitrogen (2.5%) on the surface, likely indicating less surface degradation. Further, XPS high resolution region scans showed decreases in the overall carbon concentration accompanied increases in oxygen-containing carbon species C-O, CO and O-CO; functional groups which are attributed to the LEO treatment of the composite materials. All the sample surfaces were eroded upon exposure to LEO conditions with erosion mostly confined to encapsulating epoxy resin.     

Resistance of Nanoclay Reinforced Epoxy Composites to Hyperthermal Atomic Oxygen Attack

Due to outstanding mechanical properties, heat resistance, and relatively facile production, nanoclay reinforced epoxy composites (NCRE composites) have been suggested as candidate materials for use on external surfaces of spacecraft residing in the low Earth orbit (LEO) environment. The resistance of the NCRE composites to bombardment by atomic oxygen (AO), a dominant component of the LEO environment, has been investigated. Four types of samples were used in this study. They were pure epoxy (0 wt% nanoclay content), and NCRE composites with different loadings of nanoclay—1 wt%, 2 wt%, and 4 wt%. Etch depths decreased with increasing nanoclay content, and for the 4 wt% samples it ranged from 28% to 37% compared to that of pure epoxy. X-ray photoelectron spectroscopy (XPS) indicates that after AO bombardment, relative area of C-C/C-H peak decreased, while the area of the C-O, ketones peaks increased, and the oxidation degree of surfaces increased. New carbon-related component carbonates were detected on nanoclay containing composite surfaces. Scanning electron microscopy indicates that aggregates formed on nanoclay-containing surfaces after AO bombardment. The sizes and densities of aggregates increased with nanoclay content. The combined erosion depths, XPS and SEM results indicate that although all the studied surfaces got eroded and oxidized after AO bombardment, the nanoclay containing composites showed better AO resistance compared to pure epoxy, because the produced aggregates on surface potentially act as a physical “shield”, e ectively retarding parts of the surface from further AO etching.     

Influence of Vapor Phase Pretreatments of Epoxy Surfaces on the Nucleation of MOCVD Copper Thin Films

Vapor phase pretreatments of epoxy composite material reinforced with carbon fibers were carried out prior to the growth of Cu thin films by metal-organic chemical vapor deposition (MOCVD) using Cu (hfa)(COD) as copper precursor. These dry surface oxidation processes include H₂O/UV, O₂/UV and O₂/Plasma treatments. Oxygen plasma method is the most efficient to oxidize the surface and it has the greatest effect to improve the wettability of epoxy samples. As a consequence, the higher hydrophilicity of the plasma-modified epoxy surface induces a higher nucleation density in the Cu film. Furthermore, this treatment reduces drastically the induction period observed for the growth of the metal. Even though the O₂/UV pretreatment incorporates almost the same amount of oxygen in the epoxy surface than the plasma treatment, the functional groups are different, as revealed by XPS analyses, and the surface is less hydrophilic. Correlations between oxidation, wettability and nucleation density of the Cu films are discussed.     

XPS- and AES-investigations of electron and ion beam induced effects on SK16 glass surfaces

Summary Electron beam induced effects in the near surface region of SK16 glass samples (44% SiO₂, 25% B₂O₃, 28% BaO, 3% other) have been studied using Auger electron spectroscopy (AES) with 3 keV primary electrons at different current densities (4.7 mAcm^–2–75 mAcm^–2). It was found that the SiO₂ and B₂O₃ constituents dissociate during electron bombardment to form binding structures which are characteristic for elemental Si and B, respectively. To investigate the influence of the ion beam irradiation on the binding structure, the glass samples were bombarded with Ar⁺ ions of different kinetic energies (0.5 keV–5 keV), followed by XPS analysis. In comparison to the XPS signal of a virgin SK16 surface from a sample fractured in situ under UHV conditions, the FWHM of the photoelectron peaks were found to increase with the bombarding ion energy. Subsequent Auger spectra revealed that the ion bombardment also caused a dissociation of the SiO₂ and B₂O₃ components. Depending on the ion energy, a constant ratio between elemental and oxidized binding form is obtained.     

原位XPS技术研究碳化铀的表面氧化

采用X射线光电子能谱(XPS)原位分析研究了298 K时烧结UC的清洁表面在O₂气氛中的初始氧化过程. UC试样清洁表面通过氩离子束长时间溅射获取. 初始反应各阶段U4f, O1s和C1s芯能级谱的变化显示样品表面的氧化产物为UO₂和自由碳. 当O₂饱和吸附后, UC表面氧化膜的增长呈抛物线型, 氧透过氧化膜的扩散为UC进一步氧化的速率控制步骤. 定量分析表明, 反应过程中U, C原子均未出现明显的表面偏析.     

ToF-SIMS analysis of poly(l-lysine)-graft-poly(2-methyl-2-oxazoline) ultrathin adlayers

Understanding of the interfacial chemistry of ultrathin polymeric adlayers is fundamentally important in the context of establishing quantitative design rules for the fabrication of nonfouling surfaces in various applications such as biomaterials and medical devices. In this study, seven poly(l-lysine)-graft-poly(2-methyl-2-oxazoline) (PLL–PMOXA) copolymers with grafting density (number of PMOXA chains per lysine residue) 0.09, 0.14, 0.19, 0.33, 0.43, 0.56, and 0.77, respectively, were synthesized and characterized by means of nuclear magnetic resonance spectroscopy (NMR). The copolymers were then adsorbed on Nb₂O₅ surfaces. Optical waveguide lightmode spectroscopy method was used to monitor the surface adsorption in situ of these copolymers and provide information on adlayer masses that were then converted into PLL and PMOXA surface densities. To investigate the relationship between copolymer bulk architecture (as shown by NMR data) and surface coverage as well as surface architecture, time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis was performed. Furthermore, ToF-SIMS method combined with principal component analysis (PCA) was used to verify the protein resistant properties of PLL–PMOXA adlayers, by thorough characterization before and after adlayer exposure to human serum. ToF-SIMS analysis revealed that the chemical composition as well as the architecture of the different PLL–PMOXA adlayers indeed reflects the copolymer bulk composition. ToF-SIMS results also indicated a heterogeneous surface coverage of PLL–PMOXA adlayers with high grafting densities higher than 0.33. In the case of protein resistant surface, PCA results showed clear differences between protein resistant and nonprotein-resistant surfaces. Therefore, ToF-SIMS results combined with PCA confirmed that the PLL–PMOXA adlayer with brush architecture resists protein adsorption. However, low increases of some amino acid signals in ToF-SIMS spectra were detected after the adlayer has been exposed to human serum.

The antioxygen radiation properties of the nanocomposite film consisted of hydrogenated amorphous carbon (a-C:H) and MoS2

MoS₂/a-C:H multilayer film and MoS₂/a-C:H composite film exhibit excellent tribological properties in vacuum, which can be used as the potential space lubricant. The radiation-protective properties of these two films in atomic oxygen (AO) are evaluated. The influences of AO radiation on structure, morphology, and tribological properties of the films were investigated. The results show that AO radiation mainly causes oxidation and increases sp² C content in both of the films. Furthermore, the MoS₂ sublayer on the surface of the multilayer film is oxidized heavily, whereas both the MoS₂ and the a-C:H matrix on the surface were oxidized in the composite film. As a result of this, the multilayer film exhibits high friction coefficient and short sliding lifetime in vacuum after AO radiation. Compared with that, the composite film exhibits lower friction and longer sliding time more than 3600 seconds in vacuum, which illustrates it has a good AO radiation protection. This indicates that MoS₂/a-C:H composite film is more likely to be used as a potential space lubricant.     

Effect of surface chemistry on the adsorption of basic dyes on carbon aerogels

This paper focuses on how the surface chemical groups of carbon aerogels (CAs) affect their adsorption properties of basic dyes. First of all, the surface structures of CAs were tailored by controlling carbonization temperatures and oxidation treatments including HNO₃ oxidation, H₂O₂ oxidation and hot air oxidation. The pore structures of samples were investigated by N₂ adsorption–desorption analysis. In addition, their surface chemistries were characterized by Boehm titration, elemental analysis and XPS analysis. Subsequently, the adsorption capacities of the typical basic dyes on them were determined by UV Spectroscopy. The results show that the surface chemistry of CAs plays a key role in dye adsorption performance. HNO₃ oxidation can produce much acidic groups on the surface of sample, such as carboxyl, lactone and phenolic groups, resulting in an increase in the adsorption amounts of basic dyes.     

Investigation of degradation mechanisms in mechanical properties of polyimide films exposed to a low earth orbit environment

The degradation of the mechanical properties of polyimide films was evaluated by means of tensile tests after exposure to a low earth orbit (LEO) environment. Polyimide films irradiated with atomic oxygen (AO), ultraviolet (UV) light, and electron beam (EB) rays using ground simulation facilities were also evaluated similarly and compared. In these experiments tensile stress (7.0 MPa or less) was applied to the samples in order to assess its effects on mechanical properties. The mechanical properties of the flight samples decreased concomitantly with increased exposure duration. The fracture surfaces exhibited characteristic radiated patterns initiating from the exposed surfaces which showed a rough texture. In the AO-irradiated samples the mechanical properties degraded and the surface texture developed as the AO fluence increased; similar fracture surfaces appeared in the flight samples. In contrast, UV and EB irradiation had little impact on mechanical properties. Based on these results, the eroded surfaces by AO irradiation served as the starting points of the rupture, resulting in degradation of mechanical properties of polyimide films exposed to a LEO environment. The tensile stress states induced no difference in evaluations.     

A Novel Inorganic-Organic Composite Constructed from Cobalt（Ⅱ）-Monosubstituted Polyoxometalates and Poly（amidoamine）-NH2 DendrimersA Novel Inorganic-Organic Composite Constructed from Cobalt（Ⅱ）-Monosubstituted Polyoxometalates and Poly（amidoamine）-NH2 Dendrimers

An inorganic-organic composite was prepared by poly（amidoamine） （PAMAM） dendrimer reacting with cobalt（Ⅱ）-monosubstituted polyoxometalates Na5Co^Ⅱ（H2O）PW11O39 （PW11CO） in an aqueous solution. The hybrid composite PW11Co/PAMAM was characterized by FT-IR, UV-Vis diffuse reflectance spectra （DR-UV-Vis）, XPS, XRD and TG/DTA, indicating that the PWI iCo was chemically anchored to PAMAM. The morphologies of the title composite were characterized by scanning electron microscopy （SEM） and transmission electron microscopy （TEM）. The catalytic activity was evaluated by oxidation of isobutyraldehyde （IBA） to isobutyric acid （IBAc） in MeCN under mild conditions （20 ℃, ambient pressure）, showing that the title compound is a more effective and recoverable catalyst than corresponding PW11Co.     

Effects of atomic oxygen irradiation on structural and tribological properties of polyimide/Al2O3 composites

To understand the effects of atomic oxygen (AO) irradiation on the structural and tribological behaviors of polymer composites, polyimide/Al₂O₃ composites were irradiated with AO in a ground‐based simulation facility. The structural changes were characterized by X‐ray photoelectron spectroscopy and attenuated total‐reflection FTIR, whereas the tribological changes were evaluated by friction and wear tests as well as scanning electron microscopy analysis of the worn surfaces. It was found that AO irradiation induced the oxidation and degradation of polyimide molecular chains, which increased the O concentration and decreased the C concentration in the composite surfaces. The destruction action of AO changed the surface chemical structure and morphology of the samples. Friction and wear tests indicated that AO irradiation decreased the friction coefficient but increased the wear rate of both pure and Al₂O₃ filled polyimides. In terms of the tribological properties, appropriate content of Al₂O₃ might be favorable for the improvement of tribological properties in AO environment. Copyright © 2011 John Wiley & Sons, Ltd.     

Nanotome cluster bombardment to recover spatial chemistry after preparation of biological samples for SIMS imaging

A C₆₀⁺ cluster ion projectile is employed for sputter cleaning biological surfaces to reveal spatio-chemical information obscured by contamination overlayers. This protocol is used as a supplemental sample preparation method for time of flight secondary ion mass spectrometry (ToF-SIMS) imaging of frozen and freeze-dried biological materials. Following the removal of nanometers of material from the surface using sputter cleaning, a frozen-patterned cholesterol film and a freeze-dried tissue sample were analyzed using ToF-SIMS imaging. In both experiments, the chemical information was maintained after the sputter dose, due to the minimal chemical damage caused by C₆₀⁺ bombardment. The damage to the surface produced by freeze-drying the tissue sample was found to have a greater effect on the loss of cholesterol signal than the sputter-induced damage. In addition to maintaining the chemical information, sputtering is not found to alter the spatial distribution of molecules on the surface. This approach removes artifacts that might obscure the surface chemistry of the sample and are common to many biological sample preparation schemes for ToF-SIMS imaging.     

Surface treatment of 25‐μm Kapton film by ammonia for improvement of TiO2/SiO2 coating's adhesion

Due to a smooth hydrophobic surface of Kapton film, it is very difficult to coat an inorganic oxide coating on its surface. In this study, the surface of Kapton was treated by NH₃·H₂O and silicon coupling agent to improve the polymer surface wettability. Changes in surface hydrophilicity were studied by contact angle measurement. The samples were irradiated by atomic oxygen (AO) in a ground‐based simulation system. TiO₂/SiO₂ multi‐layer coatings were prepared on the surface of Kapton by sol–gel method to resist AO erosion. The optical transmittance and surface morphology of samples were investigated by UV–vis spectroscopy and scanning electronic microscope. The results indicated that the TiO₂/SiO₂ sol could easily form a uniform thin coating on the surface of pretreated Kapton. After AO exposure, the coatings became more compact, without peeling off. The AO erosion yield value of coated Kapton was sharply down, and the samples had good optical transparency. Copyright © 2017 John Wiley & Sons, Ltd.     

Photoinduced release of active proteins from TiO2 surfaces

The present work reports on enzyme attachment on and photoinduced release from TiO₂ surfaces. TiO₂ layers (amorphous and anatase) were modified with 3-aminopropyltriethoxysilane (APTES), followed by attachment of vitamin C and horseradish peroxidase (HRP). Using step by step XPS characterization and vis-spectroscopy we show that upon UV illumination the linker chain to the protein can be cut, releasing active HRP into the environment. The head silane group remains attached to the TiO₂ surface. The kinetics of this photoinduced release is significantly faster for the anatase form of TiO₂ compared with amorphous material. The results indicate that UV induced chain scission represents a very versatile tool for payload release from TiO₂ surfaces.     

Effects of S and Ta codoping on photocatalytic activity of rutile TiO<Subscript>2</Subscript>

In this study, pure titanium dioxide (TiO₂), Ta-doped TiO₂, S-doped TiO₂, and Ta-S-codoped rutile TiO₂ photocatalysts were prepared by a sol-gel method. To evaluate the properties of the synthesized samples, X-ray diffraction analysis (XRD) and X-ray photoelectron spectroscopy (XPS) were applied. XRD detection results showed that the samples contained rutile phase basically. Scanning electron microscope observation showed that the morphology of Ta-S-TiO₂ was nearly spherical. Transmission electron microscope investigation indicated that Ta-S-TiO₂ had a flower-shaped structure consisting of many nanorods. The measurement of Brunauer-Emmett-Teller (BET)-specific surface areas (S_BET) showed that tantalum and sulfur codoping can effectively increase the S_BET of TiO₂. XPS results indicated that Ta was in the form of Ta⁵⁺ in the TiO₂ structure. Finally, the photocatalytic activities of synthesized photocatalyst samples were measured for the degradation of methylene blue in ultraviolet and visible light irradiation. The results demonstrated that the Ta-S-codoped rutile TiO₂ photocatalyst had better photocatalytic performance than pure rutile TiO₂, Ta-doped rutile TiO₂ and S-doped rutile TiO₂ photocatalyst.

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Effects of pure TiO₂, Ta-TiO₂, S-TiO₂, and Ta-S-TiO₂ on degradation of MB under visible light irradiation (a) and ultraviolet (UV) irradiation (b) were studied. Ta-S-TiO₂ exhibited a good photocatalytic performance under UV and visible light irradiation.

     

石墨烯氢氧化钴复合催化剂的一步合成及其对酸性橙的催化降解

用一步合成自组装法制备出了氢氧化钴与还原氧化石墨烯（Co（OH）₂/rGO）的复合催化剂,并将其用于水中染料的催化降解实验. 通过X射线衍射（XRD）,激光拉曼（Raman）光谱,透射电镜（TEM）,X射线能量色散谱（EDS）以及X射线光电子能谱（XPS）等一系列分析手段对催化剂的结构形貌进行了详细的表征,表征结果证实氢氧化钴很好地附着在还原石墨烯的表面. 最后初步考察了催化剂催化单过硫酸钾（PMS）降解酸性橙（AO7）的性能. 结果表明,催化剂显示出了高效的催化性能,酸性橙的色度可在12 min内完全去除,总有机碳（TOC）实验也表明染料降解的同时也可获得较高的矿化度. 循环稳定性实验表明在进行到第三次实验时,催化剂仍能保持高的催化活性,将酸性橙在16 min内降解完毕.     

An XPS and STM Study of Oxidized Platinum Particles Formed by the Interaction between Pt/HOPG with NO<Subscript>2</Subscript>

X-ray photoelectron spectroscopy (XPS) (with AlK_α and AgL_α radiations) and scanning tunneling microscopy (STM) were used to study the interaction of two model samples prepared by vacuum evaporation of platinum on highly oriented pyrolytic graphite (HOPG) with NO₂ at room temperature. According to STM data, platinum evaporation on the graphite surface produced particles of a flattened shape. In the Pt/HOPGS1 sample with a lower concentration of platinum, the average diameter of particles d and the height-to-diameter ratio h/d were 2.8 nm and 0.29, respectively. In the Pt/HOPG-S2 sample with a higher concentration of platinum, the average values of d and h/d were 5.1 nm and 0.32. When the samples interacted with NO₂ (P ≈ 3 × 10^–6 mbar), the particles of metallic platinum completely converted to the particles of PtO_2· Upon oxidation, the shape of larger platinum particles in the Pt/HOPG-S2 sample did not change, although for the dispersed particles in the Pt/HOPG-S1 samples under these conditions, the h/d ratio increases. The reduction of oxide to metal particles on heating the Pt/HOPG-S1 sample in vacuum at 460°С is accompanied by an increase in the size of particles. Their shape became more round compared to the initial one. It was found that X-ray radiation affects the state of platinum in the oxidized sample by reducing the surface layer of PtO₂ to PtO.     

ToF-SIMS analysis of surface-anchored organometallic clusters

ToF-SIMS analysis of the organometallic cluster Os₃(μ-H)(CO)₁₀(μ-SCH₂CH₂SH) chemically attached onto a silver or gold surface, and of the cluster fragment Os₃(μ-H)(CO)₁₀(μ-OSi) on a silica surface, allows for identification of the surface organometallic species, and also gives information on its reactivity.     

Surface reactions of molecular and atomic oxygen with carbon phosphide films

The surface reactions of atomic and molecular oxygen with carbon phosphide films have been studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Carbon phosphide films were produced by ion implantation of trimethylphosphine into polyethylene. Atmospheric oxidation of carbon phosphide films was dominated by phosphorus oxidation and generated a carbon-containing phosphate surface film. This oxidized surface layer acted as an effective diffusion barrier, limiting the depth of phosphorus oxidation within the carbon phosphide film to < 3 nm. The effect of atomic oxygen (AO) exposure on this oxidized carbon phosphide layer was subsequently probed in situ using XPS. Initially AO exposure resulted in a loss of carbon atoms from the surface, but increased the surface concentration of phosphorus atoms as well as the degree of phosphorus oxidation. For more prolonged AO exposures, a highly oxidized phosphate surface layer formed that appeared to be inert toward further AO-mediated erosion. By utilizing phosphorus-containing hydrocarbon thin films, the phosphorus oxides produced during exposure to AO were found to desorb at temperatures >500 K under vacuum conditions. Results from this study suggest that carbon phosphide films can be used as AO-resistant surface coatings on polymers.