Surface modification of a biomedical polyethylene terephthalate (PET) by air plasma

In this work, low-pressure air plasma has been used to improve polyethylene terephthalate (PET) surface properties for technical applications. Surface free energy values have been estimated using contact angle value for different exposure times and different test liquids. Surface composition and morphology of the films were analyzed by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Surface topography changes related with the etching mechanism have been followed by weight loss study. The results show a considerable improvement in surface wettability and the surface free energy values even for short exposure times in the different discharge areas (discharge area, afterglow area and remote area), as observed by a remarkable decrease in contact angle values. Change of chemical composition made the polymer surfaces to be highly hydrophilic, which mainly depends on the increase in oxygen-containing groups. In addition to, the surface activation and AFM analyses show obvious changes in surface topography as a consequence of the plasma-etching mechanism.     

Asymmetric surface modification of poly(ethylene terephthalate) film by CF4 plasma immersion

Poly(ethylene terephthalate) (PET) films were treated with CF₄ plasma immersion. The samples were processed at different RF powers and treatment time. The surface modification of PET films was evaluated by water contact angle (CA), X-ray photoelectron spectroscopy (XPS) and atomic force microscope (AFM). Decrease in contact angle of both sides of PET films was observed under mild treatment conditions. However, as raising treatment power and/or time, the change in contact angle between the two sides of PET films was different. The relatively hydrophobic and hydrophilic surfaces were being in situ formed on the two sides of PET films, respectively. And the extreme values of water contact angle reached 108.63 and 7.56°, respectively. XPS analyses revealed that there was a substantial incorporation of fluorine and/or oxygen atoms in both side surfaces. The relative chemical composition of the C (ls) spectra's showed the incorporation of non-polar fluorine-based functionalities (i.e. CFCF_n, CF₂ or CF₃ groups) and polar oxygen-based functionalities (i.e. COOH or OH groups) in the surfaces. Correlation between the plasma parameters and the surface modification of PET films is also discussed.     

Interfacial bonding characteristic of nanoclay/polymer composites

Using a small amount of nanoclay (montmorillonite (MMT)) can significantly enhance the thermal and mechanical properties of polymer-based composites. Therefore, an in depth understanding of the bonding characteristic between the nanoclay and its surrounding matrix is essential. In this study, Fourier Transform Infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were conducted to analyze the chemical composition between epoxy matrix and nanocomposite. These experiments revealed that a chemical bonding at an interface between the matrix and nanoclay of the composites did exist. Thus, such bonding can enhance the mechanical and thermal properties of resultant polymer composites as reported in many literatures.     

Near surface composition of some alloys by X-ray photoelectron spectroscopy

Chemical compositions of the alloys of CuNi (Cu_0.10Ni_0.90, Cu_0.30Ni_0.70, Cu_0.70Ni_0.30) and BiSb (Bi_0.80Sb_0.20, Bi_0.64Sb_0.34, Bi_0.55Sb_0.45) are determined by X-ray photoelectron spectroscopy. The stoichiometries are determined and are compared with the bulk compositions. Possible sources of systematic errors contributing to the results are discussed. Errors arising out of preferential etching in these alloys have been investigated. It has been inferred from such studies that the preferential etching does not enrich the surface composition with a particular component for the two systems reported here. Quantitative results of CuNi system indicate that the surface regions of the Cu_0.70Ni_0.30 alloy is Cu-rich, although no such evidence is observed in case of BiSb system.     

The effect of working pressure on the chemical bond structure and hydrophobic properties of PET surface treated by N ion beams bombardment

Polyethylene terephthalate (PET) surface was bombarded by N ion beams at room temperature. Varying the working pressure of the ion beams, PET surfaces with different composition and properties were obtained. Characterization by X-ray photoelectron spectrometry showed that only on film surface, ester bonds, especially C-O bonds, were broken and N element chemical bonded with C. The influence depth was less than 5 nm because of the lower ion energy (about 10³ eV). Contact angle results revealed that with increasing the working pressure of ion beams, the contact angle of PET surface to pure water increased from 51° to 130°. With these results, one conclusion could be deduced that the hydrophilic and hydrophobic properties of PET surface could be influenced by N atom chemical bond with C, which in turn is controlled by the working pressure of N ion beams.     

Si衬底上生长的MnSi薄膜和MnSi1．7纳米线的STM和XPS分析

本文采用分子束外延方法制备出MnSi薄膜和MnSi1．7纳米线,利用扫描隧道显微镜进行观察,采用X射线光电子能谱仪系统地分析了MnSi薄膜和MnSi1．7纳米线的Mn2p和Si2p．结果表明厚度为-0．9nm的MnSi薄膜表面为／3×／3重构,MnSi1．7纳米线长50ff--1500nm,宽16—18nm,高-3nm．MnSi薄膜的Mn2p1／2和Mn2p3／2峰位与MnSil．7纳米线相同,均分别为649．7eV和638．7ev结合能在640-645eV和-653．8eV处的锰氧化合物的Mn2ps／2和Mn2p1／2峰证明在短暂暴露于空气中后MnSi薄膜和MnSi1．7纳米线表面有氧化层形成．相对于纯si的si2p谱,两种锰硅化合物的Si2p谱向低结合能方向发生了位移,表明随着锰硅化合物的形成Si的化学环境发生了变化．     

Formation of Ti and TiN ultra-thin films on Si by ion beam sputter deposition

Ultra-thin titanium and titanium nitride films on silicon substrate were obtained by ion beam sputtering of titanium target in vacuum and nitrogen atmosphere, using argon ions with energy of 5 keV and 15 μA target current. Elemental composition and chemical state of obtained films were investigated by X-ray photoelectron spectroscopy with using Mg-Kα X-ray radiation (photon energy 1253.6 eV). It was shown that it is possible to form both ultra-thin titanium films (sputtering in vacuum) and ultra-thin titanium nitride films (sputtering in nitrogen atmosphere) in the same temperature conditions. Photoelectron spectra of samples surface, obtained in different steps of films synthesis, detailed spectra of photoelectron emission from Si 2p, Ti 2p, N 1s core levels and also X-ray photoelectron spectra of Auger electrons emission are presented.     

Gas barrier properties of titanium oxynitride films deposited on polyethylene terephthalate substrates by reactive magnetron sputtering

Titanium oxynitride (TiN_xO_y) films were deposited on polyethylene terephthalate (PET) substrates by means of a reactive radio frequency (RF) magnetron sputtering system in which the power density and substrate bias were the varied parameters. Experimental results show that the deposited TiN_xO_y films exhibited an amorphous or a columnar structure with fine crystalline dependent on power density. The deposition rate increases significantly in conjunction as the power density increases from 2 W/cm² to 7 W/cm². The maximum deposition rate occurs, as the substrate bias is −40 V at a certain power densities chosen in this study. The film's roughness slightly decreases with increasing substrate bias. The TiN_xO_y films deposited at power densities above 4 W/cm² show a steady Ti:N:O ratio of about 1:1:0.8. The water vapor and oxygen transmission rates of the TiN_xO_y films reach values as low as 0.98 g/m²-day-atm and 0.60 cm³/m²-day-atm which are about 6 and 47 times lower than those of the uncoated PET substrate, respectively. These transmission rates are comparable to those of DLC, carbon-based and Al₂O₃ barrier films. Therefore, TiN_xO_y films are potential candidates to be used as a gas permeation barrier for PET substrate.     

XPS and bioactivity study of the bisphosphonate pamidronate adsorbed onto plasma sprayed hydroxyapatite coatings

This paper reports the use of X-ray photoelectron spectroscopy (XPS) to investigate bisphosphonate (BP) adsorption onto plasma sprayed hydroxyapatite (HA) coatings commonly used for orthopaedic implants. BPs exhibit high binding affinity for the calcium present in HA and hence can be adsorbed onto HA-coated implants to exploit their beneficial properties for improved bone growth at the implant interface. A rigorous XPS analysis of pamidronate, a commonly used nitrogenous BP, adsorbed onto plasma sprayed HA-coated cobalt-chromium substrates has been carried out, aimed at: (a) confirming the adsorption of this BP onto HA; (b) studying the BP diffusion profile in the HA coating by employing the technique of XPS depth profiling; (c) confirming the bioactivity of the adsorbed BP. XPS spectra of plasma sprayed HA-coated discs exposed to a 10 mM aqueous BP solution (pamidronate) for periods of 1, 2 and 24 h showed nitrogen and phosphorous photoelectron signals corresponding to the BP, confirming its adsorption onto the HA substrate. XPS depth profiling of the 2 h BP-exposed HA discs showed penetration of the BP into the HA matrix to depths of at least 260 nm. The bioactivity of the adsorbed BP was confirmed by the observed inhibition of osteoclast (bone resorbing) cell activity. In comparison to the HA sample, the HA sample with adsorbed BP exhibited a 25-fold decrease in primary osteoclast cells.     

A study of the formation and oxidation of PtSi by SR-PES

In the paper we present the results on the formation of platinum silicide (PtSi) by means of synchrotron radiation photoelectron spectroscopy (SR-PES) and show the effect of a Pt/Si sample exposure to both a low and high-pressure oxygen atmosphere at the end of an annealing process. We have carried out a detailed analysis of high resolution photoelectron spectra of the Pt 4f and Si 2p peaks which were taken during the sample annealing at specific temperatures. In addition to the generally known Pt₂Si and PtSi phases we have recognized an additional intermediate phase during the formation of Pt₂Si and attributed it to the Pt₃Si phase. We have proved that silicon diffuses towards the sample surface. The results of a low-pressure oxygen experiment have shown that oxygen binds only to surface silicon, however, in the case of a PtSi sample prepared externally in the ON Semiconductor labs under nitrogen/oxygen atmosphere oxygen binds not only to surface silicon but also takes over Si atoms out of the PtSi phase which results in the formation of a SiO₂ layer on almost pure platinum.     

Construction of self-assembled monolayer terminated with N-heterocyclic carbene-rhodium(I) complex moiety

Functionalization of self-assembled monolayer (SAM) of alkanethiolate with metal containing unit is one of the versatile methods to obtain functional surfaces such as heterogeneous catalysts. However, organic molecules that strongly bind to transition metals at SAM terminal are limited. Recently N-heterocyclic carbenes (NHCs) such as cyclic diaminocarbenes have emerged as strongly σ-donating ligands forming a robust bond with broad spectrum of transition metals. In the present study, for the purpose of establishment of a new robust basement for heterogeneous metal catalysts, a SAM of the alkanethiolate terminated with NHC-rhodium(I) complex moiety was prepared by utilizing a newly designed disulfide molecule bearing NHC-metal complex terminals. X-ray photoelectron spectroscopy (XPS) analysis and angle resolved XPS measurement revealed successful formation of the Rh-complex-terminated SAM on a gold substrate. Infrared reflection absorption spectroscopy (IRRAS) analysis suggested that the linker methylene chains connecting the rhodium complex moiety and the gold surface are in a loosely packed structure. This unique chemical species, NHC, would be a promising candidate as a basement for the construction of functional surface.     

XPS study of SnTe(1 0 0) oxidation by molecular oxygen

The interaction between the (1 0 0) surface of SnTe single crystal and molecular oxygen was studied by means of X-ray photoelectron spectroscopy (XPS). Analysis of the obtained spectra shows that the mechanism of surface oxidation does not change in the range of oxygen exposure 10⁸-10¹³ L. During the oxidation an additional component shifted 1.1 eV towards higher binding energies appears in the Sn 3d spectra. The Te 3d_5/2 spectra fitting reveals two additional components with binding energies close to Te⁰ and Te⁺⁴. The dependence of the additional components fraction in both Sn 3d and Te 3d_5/2 spectra on the oxygen exposure is semi-logarithmic. On the base of the experimental data two possible mechanisms are proposed.     

XPS investigation on Upilex-S polyimide ablated by pulse TEA CO2 laser

Laser ablation of Upilex-S polyimide films 80 μm thick was performed in air using a pulse TEA CO₂ laser with wavelength 9.3 μm. A halo surrounding the hole was observed, which is covered with sub-micro particles. Pieces of ablation products protrude from the ablated surface, leading to considerable roughness of the ablated area. Chemical and structural changes of Upilex-S polyimide film surface irradiated by the pulse TEA CO₂ laser in air were analyzed by X-ray photoelectron spectroscopy (XPS). Relative C content in the ablated area was found to be higher, whilst both O and N contents were lower than in the untreated area. This means that TEA CO₂ laser ablation released both the O and N atoms. Also, the peak areas corresponding with carbonyl group (C=O) in the imide system were reduced much more and a new component at 287.0 eV assigned to the amide structure (N---C=O) was detected after laser ablation. These suggest that the pyrolysis of the Upilex-S polyimide was the decomposition of the imide ring between the nitrogen/aromatic carbon atom and carbonyl carbon atom. In addition, another new component arising from >C=O groups was also detected for higher fluence (7.83 J/cm²), and its peak areas is very small. This result indicates that the slight oxidation may take place with higher fluence during laser ablation in air. Based on above-mentioned experimental results, a possible thermally-induced decomposition path of Upilex-S polyimide ablated by TEA CO₂ laser is presented.     

Uniformity analysis of dielectric barrier discharge (DBD) processed polyethylene terephthalate (PET) surface

A dielectric barrier discharge (DBD) plasma, operating in air at atmospheric pressure, has been used to induce changes in the surface properties of polyethylene terephthalate (PET) films. The effects that the key DBD operating parameters: discharge power, processing speed, processing duration, and electrode configurations, have on producing wettability changes in the PET surface region have been investigated. The approach taken involves the application of an Taguchi experimental design and robust analysis methodology. The various data sets obtained from these analyses have been used to studies the effect of the operating parameters on the surface uniformity and efficiency of the said treatment.In general, the results obtained indicate that DBD plasma processing is an effective method for the controlled surface modification of PET. Relatively short exposures to the atmospheric pressure discharge produces significant wettability changes at the polymer film surface, as indicted by pronounced reductions in the water contact angle measured. It was observed that the wettability of the resultant surface shows no significant differences in respect to orientation parallel (L-direction) or perpendicular (T-direction) to the electrode long axis. However, there was significant differences between the data obtained from these two orientations. Analysis of the role of each of the operating parameters concerned shows that they have a selective effectiveness with respect to resultant surface modification in terms of uniformity of modification and wettability. The number of treatment cycles and the electrode configuration used were found to have the most significant effects on the homogeneity of the resultant PET surface changes in L- and T-orientation, respectively. On the other hand, the applied power showed no significant role in this regard. The number of treatment cycles was found to be the dominant factor (at significance level of 0.05) in respect of water contact angle changes at the processed PET surface in both orientations. The driven metal electrodes (stainless steel or aluminium) were apparently superior to the driven dielectric electrode (ceramic or quartz) configurations. The grounded electrode in each case was a silicon rubber-covered aluminium plate (see later). The nature and scale of the surface changes that originate from the various processing conditions employed have been considered so as to determine the optimum treatment conditions in respect of processing outcomes, properties and any orientation dependence. Thus, it was revealed that higher processing speeds and longer processing durations are key for uniformity along the electrode axial orientation, while lower processing speeds and short exposure durations are key considerations, in the corresponding perpendicular orientation. In general, longer processing durations (low processing speeds and a high number of treatment cycles) and higher plasma powers induced greater changes in the surface wettability of the PET, as demonstrated by the observed water contact angles. This behaviour is taken to indicate that different combinations of DBD operating parameters and electrodes produce discharge conditions that can result in different plasma chemical processes in respect of uniformity, treatment efficiency and orientation dependence.     

XPS depth-profile of the suboxide distribution at the native oxide/Ta interface

A X-ray photoelectron spectroscopy (XPS) depth-profile study of the naturally formed native oxide on polycrystalline Ta sample is probed by observing the core level spectra, valence band spectra and workfunction changes. The present paper addresses the issue of the presence of different Ta suboxides along the depth of the oxide layer. Core level spectra, valence band and workfunction measurements all manifest the transformation of insulating Ta₂O₅ to metallic Ta with a graded distribution of Ta sub-oxides. Effect of ion-beam irradiation and variation in the synthesis method in determining the profile is discussed. By using different ion-beam energies, it has been shown that the ion-beam induced effects are negligible in the study. Differences in the valence states reported in literature with the present study are attributed to the variations in the growth methods.     

Step-wise decomposition process of azobenzene self-assembled monolayers

The step-wise decomposition of 4-(12-(dodecyldithio)dodecyloxy)azobenzene (AzoC24) in self-assembled monolayer (SAMs) on Au(1 1 1) was observed by thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS) under the ultra-high vacuum (UHV) condition. This decomposition process only occurred after the formation of the SAM.The TD spectra clearly showed two steps of thermal decomposition of the azobenzene moiety. At approximately 450 K, fragments of m/e = 77 and 105 were clearly observed. These fragments were decomposed species obtained by the breakage of the C-N bonds of the azobenzene moiety. At about 490 K, other fragment of m/e = 93 assigned to the phenoxy ion was detected. In order to examine the decomposition process, we measured the S 2p and N 1s XPS of the SAM at various temperatures. The results suggest that diazonium moiety is the first to be decomposed and the remaining structure is desorbed together with breakage of C-O bond between the phenoxy moiety and alkyl chain with increasing temperature.     

Synthesis of SiC/graphene nanosheet composites by helicon wave plasma

We report an approach to the rapid, one-step, preparation of a variety of wide-bandgap silicon carbide/graphene nanosheet(Si C/GNSs) composites by using a high-density helicon wave plasma(HWP) source. The microstructure and morphology of the Si C/GNSs are characterized by using scanning electron microscopy(SEM), Raman spectroscopy, x-ray diffraction(XRD), x-ray photoelectron spectroscopy(XPS), and fluorescence(PL). The nucleation mechanism and the growth model are discussed. The existence of Si C and graphene structure are confirmed by XRD and Raman spectra.The electron excitation temperature is calculated by the intensity ratio method of optical emission spectroscopy. The main peak in the PL test is observed at 420 nm, with a corresponding bandgap of 2.95 e V that indicates the potential for broad application in blue light emission and ultraviolet light emission, field electron emission, and display devices.     

Surface oxidation behavior of MgNd alloys

The oxidation kinetics of MgNd alloys oxidized in pure O₂ at high temperatures has been investigated. The results revealed two stages of the reaction: A fast initial oxidation was followed by a slow oxide growth with a parabolic kinetics. For MgNd alloys (Nd = 25 wt.%), the oxidation rate increased with the enhancement of the oxidation temperature. A sudden ignition was found for this alloys oxidized at 873 K up to about 80 min. Moreover, the increase of the Nd content would harm the oxidation resistance of the MgNd alloys. By Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis, it was found that a triplex structure of oxide film formed. The outer layer was composed of MgO, Nd₂O₃ and Nd(OH)₃, the middle layer mainly consisted of MgO and Nd₂O₃, and the inner layer was the transitional layer made of MgO, Nd₂O₃ and the content of the substrate. The protective oxidation was associated with the formation of the dense Nd₂O₃/MgO layer during isothermal oxidation process. The oxidation mechanisms for the formation of oxide film are discussed.     

Changes in surface stress, morphology and chemical composition of silica and silicon nitride surfaces during the etching by gaseous HF acid

HF acid attack of SiO₂ and Si₃N₄ substrates is analyzed to improve the sensitivity of a sensor based on microcantilever. Ex situ analysis of the etching using XPS, SIMS and AFM show significant changes in the anisotropy and the rate of the etching of the oxides on SiO₂ and Si₃N₄ surface. Those differences influence the kinetic evolution of the plastic bending deflection of the cantilever coated with SiO₂ and Si₃N₄ layer, respectively. The linear dependence between the HF concentration and the Si₃N₄ cantilever bending corresponds to a deep attack of the layer whereas the non-linear behavior observed for SiO₂ layer can be explained by a combination of deep and lateral etching. The cantilever bending is discussed in terms of free surface energy, layer thickness and grain size.     

低速高电荷态重离子辐照的GaN晶体表面X射线光电子能谱研究

利用低速高电荷态Xeq+和Pbq+离子对在蓝宝石衬底上生长的GaN晶体膜样品进行辐照,并利用X射线光电子能谱(XPS)对样品表面化学组成和元素化合态进行了分析.结果表明,高电荷态离子对样品表面有显著的刻蚀作用;经高电荷态离子辐照的GaN样品表面氮元素贫乏而镓元素富集;随着入射离子剂量和所携带电荷数的增大,Ga—Ga键相对含量增大;辐照后,GaN样品中Ga—Ga键对应的Ga3d5/2电子的束缚能偏小,晶格损伤使内层轨道电子束缚能向低端方向偏移.