In situ characterization of Ti-peroxy gel during formation on titanium surfaces in hydrogen peroxide containing solutions

Three possible functions of Ti-peroxy gel are: reduction of the inflammatory response through the reduction of hydrogen peroxide and other reactive oxygen species; creation of a favorable surface for calcium phosphate nucleation; and as a transitional layer between the compliant surrounding tissue and the stiff titanium. Traditional surface characterization techniques operate in high vacuum environments that alter the actual sample–solution interface. Our studies used techniques that allowed samples to remain in solution and be observed over time. Atomic force microscopy (AFM) force–distance curves, electrochemical impedance spectroscopy (EIS), and Raman spectroscopy were each used in situ to define kinetic and mechanical properties of Ti-peroxy gel as it formed over time on titanium during exposure to hydrogen peroxide. Our studies enabled us to monitor real-time changes in the native oxide layer on titanium in hydrogen peroxide containing solution, including the formation of a Ti-peroxy gel layer above the native oxide. Peaks attributed to Ti-peroxy gel were seen to emerge over the course of several hours using in situ Raman spectroscopy. Force–distance curves suggest a layer that thickens with time on the titanium sample surface. EIS data showed that changes in the surface layers could be monitored in solution over time.     

纳米有机涂层在3.5%NaCl溶液中的电化学阻抗谱研究

纳米有机涂层防腐蚀性能良好,但目前有关其对金属防护的具体过程的研究却不多。将涂装纳米有机涂层的16MnR钢试样浸泡在3.5%的NaCl溶液中,采用电化学阻抗谱法(EIS)研究纳米有机涂层在试验周期360d不同测试时间的作用效果,分析各时段纳米有机涂层在NaCl溶液中对金属的防腐蚀情况。结果表明,纳米有机涂层体系对金属基体具有很好的保护性,其对金属的保护过程可以分为4个阶段:腐蚀介质渗入有机涂层阶段,腐蚀介质渗透到富锌涂层阶段,腐蚀产物形成阻挡层阶段,腐蚀产物填补孔隙阶段。     

Decarboxylation of oxidized single-wall carbon nanotubes

A classical protocol widely used in organic chemistry of aromatic and polyaromatic molecules has been successfully applied in this work for the decarboxylation of oxidized single-wall carbon nanotube (SWNT) to rend C-H SWNT derivatives. SWNT produced by arc discharge method have been oxidized during a purification process using strongly oxidant agents, such as hydrogen peroxide and nitric acid. The decarboxylation of oxidized SWNT has been conduced with copper(I) oxide in a 50:50 solution of N-methylpyrrolidone and quinoline. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and acid-base potentiometric titration analyses were carried out to characterize quali and quantitatively the changes in the chemical environment on the SWNT surface in each step of the purification and the decarboxylation process. Those techniques showed the appearance of mainly carboxylic and phenolic groups after the purification process and the disappearance of the carboxylic groups after the decarboxylation reaction. Fourier transform infrared spectroscopy analysis indicated also the formation of aliphatic and aromatic C-H groups. X-ray photoelectron spectroscopy and potentiometric titration results determined an efficiency higher than 90% for our decarboxylation procedure. The purity and structural quality of the SWNT sample used in the decarboxylation process were evaluated by thermogravimetry and Raman spectroscopy. Thermogravimetric analysis identified a purified sample with approximately 80 wt% of SWNT, in fractions distributed in highly structured SWNTs (25 wt%), with distribution in composition, length and structural quality (35 wt%) and with very defective and short tubes (25 wt%). The damages on the purified SWNT walls were characterized by the Raman scattering analysis.     

Corrosion behavior of Ti–Al–N/Ti–Al duplex coating on AZ31 magnesium alloy in NaCl aqueous solution

In this study, Ti–Al–N/Ti–Al duplex coating was deposited on AZ31 magnesium alloy by magnetron sputtering with a Ti/Al composite target. Scanning electron microscopy and Auger electron spectroscopy were applied to investigate the morphology and elemental concentration of the obtained coating, respectively. The top layer was Ti–Al–N film with a Ti:Al:O:N ratio of 0.32:0.84:0.08:1, and the bottom layer was Ti–Al film with a Ti:O:Al ratio of 1.94:0.12:1. Each layer of this coating presented a developed columnar structure. The polarization test and immersion test were used to investigate corrosion behavior of the coated sample in 3.5 wt.% NaCl aqueous solution. The results showed that this duplex coating could protect the substrate effectively in NaCl aqueous solution. Nevertheless, several through-thickness micropores in the coating finally induced the failure of the coated AZ31 in the immersion test.     

水热法合成N-乙酰-L-半胱氨酸稳定的Cd_xZn_（1-x）Se合金量子点

采用了N-乙酰-L-半胱氨酸为稳定剂,通过水热法制备了荧光发射峰可调、粒径均匀且结晶性能良好的ZnxCd1-xSe合金量子点,并采用紫外-可见光吸收光谱（UV-Vis）、荧光光谱（PL）、X射线衍射（XRD）、高分辨透射电镜（HRTEM）等对其结构和性能进行了表征。重点研究了Cd2＋/Zn2＋比值、初始溶液pH值、水热反应温度和时间等实验条件对ZnxCd1-xSe量子点荧光性能的影响。研究表明所制备的量子点荧光量子产率高（35%）,荧光发射谱半峰宽窄（FWHM〈50nm）,有望作为生物荧光标记物。     

Monolayer polystyrene micro-spheres array master derived by spin-coating method for UV nanoimprint

Polystyrene micro-spheres aqueous suspensions were obtained by an emulsifier-free polymerization method. Fourier transform infrared spectroscopy and laser particle size distribution were used to characterize the colloidal solutions. Results indicate that the polystyrene micro-spheres colloidal solution has a good dispersion and the micro-spheres have a uniform size and smooth surface. The as-prepared polystyrene micro-spheres colloidal solution was spun onto glass substrates and then the coated sample was heated at 70 degrees C for 1 h to form close-packed monolayer polystyrene microspheres arrays, which are used as a master. Scanning electron microscopy was used to observe the morphological properties of the polystyrene micro-spheres array. A relative good result can be easily obtained by a spinning speed of 2000 rpm for 30 second, when the solution concentration is around 10 wt.%. Furthermore, the polydimethylsiloxane soft mold was replicated from the-fabricated polystyrene micro-spheres array master and was then imprinted onto the photosensitive hybrid film under UV-irradiation and thus the micro-lens arrays built in the photosensitive hybrid sol-gel film were obtained.     

Development and characterization of sol‐gel composite coatings on aluminum alloys for corrosion protection

For several years, Cr^IV compounds were used as effective and inexpensive corrosion inhibitors. Studies showed that these materials were toxic and carcinogenic. This has led to extensive research to develop alternative inhibitors. Organo‐silicate hybrid coatings appeared as an effective technique for forming protective layers on different metal alloys. A silane film was obtained by dip coating of the sample in sol solution prepared from the hydrolysis of 3‐glycidoxypropyltrimethoxysilane (GPTM), tetraethylorthosilicate (TEOS) with acid as catalyst and water as solvent instead of VOC (volatile organic compound). The sol solution was aged at ambient temperature to to enhance the effectiveness of the solution for the hydrolysis process. The sample was cured at 150 °C to ensure cross‐linking of the film. The experiments have shown that heat treatment leads to increased density and corrosion resistance of the films. Organic and inorganic inhibitors were added in different concentrations to improve the protection and self‐healing properties of the coating even after long‐time immersion in corrosive solution. The protection performance of the film was evaluated by electrochemical impedance spectroscopy (EIS) in 0.5 M NaCl solution (pH value 7). The surface morphologies of the treated samples were investigated using SEM.     

Synthesis and characterization of iron-substituted hydroxyapatite via a simple ion-exchange procedure

Hydroxyapatite (HA), the main inorganic component of natural bones, is widely studied as a biomaterial due to its excellent biocompatibility and osteoinductivity. The crystal structure of HA lends itself to a wide variety of substitutions and ion doping, which allows for tailoring of material properties. In this study, iron-doped HA was synthesized via a simple ion-exchange procedure and characterized thoroughly for crystal structure and phase purity using X-ray diffraction, energy-dispersive X-ray spectroscopy, inductively coupled plasma atomic emission spectroscopy, and Fourier transform infrared spectroscopy. Magnetic properties were studied using vibrating sample magnetometer and superconducting quantum interference device analysis. Ion-exchange was attempted using both ferric and ferrous chloride iron solutions, but a substitution was only achieved using ferric chloride solution. The results showed that after iron substitution the powder retained characteristic apatite crystal structure and functional groups, but the iron-doped samples displayed paramagnetic properties, as opposed to the diamagnetism of pure HA. The effect of soaking time on iron content was also examined, and collectively X-ray diffraction and inductively coupled plasma atomic emission spectroscopy results suggested that an increase in soaking time led to an increase in iron content in the sample powder. Iron-substituted HA nanoparticles, a biomaterial with magnetic properties, could be a promising biomaterial to be used in a variety of biomedical fields, including magnetic imaging, drug delivery, or hyperthermia-based cancer treatments.     

Electronic referencing techniques for quantitative NMR: pitfalls and how to avoid them using amplitude-corrected referencing through signal injection

NMR spectroscopy can be a superior analytical technique for quantification of compounds dissolved in solution. Traditionally a chemical reference standard of known concentration is added to the sample. The concentration of the solute can then be determined by comparing the signal integrals. However, it can be inconvenient or impossible to use internal references. Electronic referencing was developed to circumvent problems with internal standards and has been used successfully in well-controlled situations. However, it is not always possible or convenient to have samples where the dielectric sample properties do not change from one to the next. We propose a modification of the old electronic referencing technique that takes into account the electronic changes between dissimilar samples. We have called this new technique Amplitude-corrected Referencing Through Signal Injection or ARTSI.     

Near-infrared spectroscopy for cocrystal screening. A comparative study with Raman spectroscopy

Near-infrared (NIR) spectroscopy is a well-established technique for solid-state analysis, providing fast, noninvasive measurements. The use of NIR spectroscopy for polymorph screening and the associated advantages have recently been demonstrated. The objective of this work was to evaluate the analytical potential of NIR spectroscopy for cocrystal screening using Raman spectroscopy as a comparative method. Indomethacin was used as the parent molecule, while saccharin and l-aspartic acid were chosen as guest molecules. Molar ratios of 1:1 for each system were subjected to two types of preparative methods. In the case of saccharin, liquid-assisted cogrinding as well as cocrystallization from solution resulted in a stable 1:1 cocrystalline phase termed IND-SAC cocrystal. For l-aspartic acid, the solution-based method resulted in a polymorphic transition of indomethacin into the metastable alpha form retained in a physical mixture with the guest molecule, while liquid-assisted cogrinding did not induce any changes in the crystal lattice. The good chemical peak selectivity of Raman spectroscopy allowed a straightforward interpretation of sample data by analyzing peak positions and comparing to those of pure references. In addition, Raman spectroscopy provided additional information on the crystal structure of the IND-SAC cocrystal. The broad spectral line shapes of NIR spectra make visual interpretation of the spectra difficult, and consequently, multivariate modeling by principal component analysis (PCA) was applied. Successful use of NIR/PCA was possible only through the inclusion of a set of reference mixtures of parent and guest molecules representing possible solid-state outcomes from the cocrystal screening. The practical hurdle related to the need for reference mixtures seems to restrict the applicability of NIR spectroscopy in cocrystal screening.     

pH值对X90管线钢在模拟酸性土壤溶液中腐蚀行为的影响

目前,对X90等第三代管线钢在土壤中的腐蚀研究较少。采用动电位极化曲线、交流阻抗谱和腐蚀失重等研究了不同pH值下,X90管线钢在模拟酸性土壤溶液中的腐蚀行为。结果表明:pH值的变化不影响X90钢的阴阳极反应机理;当pH≤4时,交流阻抗谱低频区出现感抗弧,此过程存在吸附或点蚀形核,当pH≥4时,交流阻抗谱出现Warburg扩散阻抗,传质扩散为反应主要控制步骤;随着溶液pH值降低,腐蚀电流密度增大,溶液中总铁含量增加,试样表面腐蚀程度加剧,均表明X90管线钢的腐蚀速率增大。     

Thermal Diffusivity Determination of Protoporphyrin IX Solution Mixed with Gold Metallic Nanoparticles

Nanoparticles appear to be ideally suited for applications in targeted thermal effects in medical therapies and photothermally activated drug delivery; all depend critically on the thermal transport between the nanoparticles and the surrounding liquid. In this work thermal lens spectroscopy (TLS) was used to determine the thermal diffusivity of protoporphyrin IX (PpIX) solutions mixed with gold metallic nanoparticles. PpIX disodium salt (DS) was used in a HCl solution at 25%. Fluids containing gold (Au) nanoparticles at different concentrations were prepared and added to the PpIX solutions. For each solution, UV–Vis spectroscopy was used to obtain the optical absorption spectrum, and transmission electron microscopy (TEM) was used to obtain the gold nanoparticle size. From the TLS signal intensity, it was possible to determine the characteristic time constant of the transient thermal by fitting the theoretical expression to the experimental data. From this characteristic time, the thermal diffusivity was obtained for each solution. The results show that the thermal diffusivity of PpIX mixed with gold nanoparticles increases with an increase of the nanoparticle metallic concentration.     

Studying the corrosion resistance and hydrolytic degradation of an epoxy coating containing ZnO nanoparticles

Epoxy nanocomposites containing different contents of Nano-ZnO particles were prepared. The nanocomposites were exposed to 3.5 wt% NaCl solution up to 60 days. Mechanical properties of the nanocomposites (before and after exposure to NaCl solution) were studied by dynamic mechanical thermal analysis (DMTA) and nano-indentation techniques. Fourier transform infrared spectroscopy (FTIR) was utilized to investigate hydrolytic degradation of coatings. Corrosion resistance of the composites was studied by an electrochemical impedance spectroscopy (EIS). Results showed that blank sample was severely deteriorated after exposure to corrosive electrolyte. Corrosion resistance of the epoxy coating was significantly improved using nanoparticles. The cross-linking density and indentation hardness of the blank sample were significantly decreased after exposure to corrosive electrolyte. Results showed that nanoparticles could significantly improve coating resistance against hydrolytic degradation. Results revealed that decrease in cross-linking density and indentation hardness of the epoxy coatings containing 3.5 and 5 wt% nanoparticles were not significant. Decrease in adhesion loss was also obtained using nanoparticles.     

Synthesis of CdS nanoparticles based on DNA network templates

CdS nanoparticles have been successfully synthesized by using DNA networks as templates. The synthesis was carried out by first dropping a mixture of cadmium acetate and DNA on a mica surface for the formation of the DNA network template and then transferring the sample into a heated thiourea solution. The Cd(2+) reacted with thiourea at high temperature and formed CdS nanoparticles on the DNA network template. UV-vis spectroscopy, photoluminescence, x-ray diffraction and atomic force microscopy (AFM) were used to characterize the CdS nanoparticles in detail. AFM results showed that the resulted CdS nanoparticles were directly aligned on the DNA network templates and that the synthesis and assembly of CdS nanoparticles was realized in one step. CdS nanoparticles fabricated with this method were smaller than those directly synthesized in a thiourea solution and were uniformly aligned on the DNA networks. By adjusting the density of the DNA networks and the concentration of Cd(2+), the size and density of the CdS nanoparticles could be effectively controlled and CdS nanoparticles could grow along the DNA chains into nanowires. The possible growth mechanism has also been discussed in detail.     

Electropolishing of NiTi for Improving Biocompatibility

A modified electrolyte （CH3COOH-HClO4-A-B） for electropolishing （EP） of NiTi was presented for improving the corrosion resistance and biocompatibility of the alloy. Using the proposed parameters, a homogeneous and uniform surface was obtained. Atomic force microscopy （AFM） revealed that the surface roughness （Ra） for EP sample （23.21 nm） was close to mechanical polishing （MP） sample （19.36 nm）. Analysis by X-ray photoelectron spectroscopy （XPS） showed that Ti/Ni ratio increased from 3.1 for MP sample to 27.6 for EP sample. Measurements using potentiodynamic polarization in Hanks＇ solution showed that no pitting occurred for EP sample even though the applied potential increased up to 1500 mV （vs SCE）, while the MP sample was broken down at 650 mV. The present study indicates that electropolishing NiTi with this modified electrolyte contributes to the improved biocompatibility of NiTi.     

含H2S的NaCl溶液中溶解氧对PH13-8Mo钢腐蚀性能的影响

为研究新型马氏体沉淀硬化不锈钢PH13-8Mo在含饱和H_2S的NaCl溶液中的腐蚀行为,利用极化曲线、电化学阻抗谱等电化学测试和浸泡实验相结合的方法,通过扫描电子显微镜(SEM)和X射线光电子能谱分析技术(XPS),观察了该高强钢在含H_2S的除氧和不除氧的NaCl溶液中的腐蚀形貌,并对其腐蚀产物的成分进行了分析.结果表明:在除氧的NaCl溶液中,阳极极化曲线的形状发生了明显的变化,电化学阻抗谱的容抗弧的幅值也较未除氧的溶液中变小;在除氧的NaCl溶液中浸泡7 d后,由于H_2S水解后的S~(2-)或HS~-离子侵入到钝化膜的内部,并与钝化膜或金属基体发生反应,使得试样表面发生全面腐蚀,腐蚀产物主要为Fe、Cr、Ni、Mo的氧化物和硫化物;而在未除氧的NaCl溶液中浸泡后,试样表面仅发生局部腐蚀.     

Mssbauer Effect in Ultrafine Particles with Fe-C Solid Solution, γ-Fe and Fe_3C Phases

Ultrafine particles prepared by evaporating pure Fe in CH4 atmosphere using arc-dischargeheating method, were found to consist of Fe-C solid solution, γ-Fe and Fe3C phases. EfFect of annealing temperature on phase transformation and hyperfine interactions has been investigated by Mossbauer spectroscopy, X-ray diffraction (XRD), differential thermal analysis and thermogravimetry (DTA-TG), transmission electron microscopy (TEM), oxygen determination and vibrating sample magnetometer (VSM) measurements. It was observed that phase transformation of γ-Fe to α-Fe occurs during annealing in vacuum. The mechanism causing the change of hyperfine interactions with annealing temperature differs for Fe-C solution and interstitial compounds. DifFerence of hyperfine interactions of Fe-C solid solution in the starting sample and its annealed samples is ascribed to the improvement of activation of interstitial carbon atoms. Stress-relieving in structure of annealed Fe3C particle can result in a weak influence on hyperfine interactions. Parameters fitted to the Mossbauer spectra show the existence of superparamagnetism in all the samples. Absorbed and combined oxygen on particle surface of the starting sample were determined.     

Spontaneous ring-like self-assembly of BaF2 nanoparticles

Self-assembly of BaF2 nanoparticles was described. BaF2 nanoparticles were prepared by microemulsion technology. The self-assembly of the particles is spontaneous without coating reagent on the surface or external force being applied during the procedure of sample preparation. XRD examination and ICP data showed the phase purity of the final product; FTIR spectroscopy confirmed that there was no organic species leaved in the product. By depositing one drop of colloid solution containing BaF2 particles on the TEM grid directly, we can get the ring-like self-assembly with larger particles dispersing peripherally to form a ring and smaller particles inside this ring forming circles.     

UV-radiation curing of simultaneous interpenetrating polymer network hydrogels for enhanced heavy metal ion removal

Simultaneous interpenetrating polymer network (IPN) hydrogels have been prepared by UV-initiated polymerization of a mixture of acrylamide (AM) and triethylene glycol divinyl ether (DVE-3). The consumption of each monomer upon UV-irradiation was monitored in situ by real-time infrared (RTIR) spectroscopy. The acrylamide monomer AM was shown to polymerize faster and more extensively than the vinyl ether monomer DVE-3, which was further consumed upon storage of the sample in the dark, due to the living character of the cationic polymerization. The IPN hydrogels were used to remove heavy metal ions from aqueous solution under the non-competitive condition. The effects of pH values of the feed solution and the DVE-3 content in the formulation on the adsorption capacity were investigated. The results indicated that the adsorption capacity of the IPN hydrogels increased with the pH values and DVE-3 content in the formulation. Furthermore, the synergistic complexation of metal ions with two polymer networks in the IPN was found in the adsorption studies. Adsorption kinetics and regeneration studies suggested that the IPN hydrogels could be used as fast-responsive and renewable sorbent materials in heavy metal removing processes.     

Laser-induced breakdown spectroscopy used to detect palladium and silver metal dispersed in bacterial cellulose membranes

The technique of laser-induced breakdown spectroscopy has been used for the first time to our knowledge for the identification of metals such as palladium and silver that were dispersed in bacterial cellulose membranes. These results for palladium-dispersed films have been correlated to a calibration curve obtained by use of atomic absorption spectroscopy and were found to be in good agreement. The experiments were conducted by use of wet and dry metal-doped membranes. The metal peaks obtained with a dry membrane are greater than five times higher in signal-to-background ratio than when metals are detected by a hydrated membrane. The advantage of this laser-based technique is that minimal sample handling and sample preparation are needed and measurements are completed in real time (a few seconds). Hence this technique can be used for the detection of metals in dry membranes that would be used in the construction of electrode assemblies.