Microstructure: Surface and cross-sectional studies of hydroxyapatite formation on the surface of white Portland cement paste in vitro

The formation of hydroxyapatite was investigated at the surface and at the cross-section of white Portland cement paste samples before and after immersion in simulated body fluid. Scanning electron microscope images showed that hydroxyapatite were found at the surface of white Portland cement after immersion in simulated body fluid. Hydroxyapatite grains of mostly ≈1 μm size with some grain size of ≈2-3 μm were seen after 4 days immersion period. More estabilshed hydroxyapatite grain size of ≈3 μm grains were observed at longer period of immersion at 7 and 10 days. The cross-section of the samples was investigated using line scanning technique and was used to determine the hydroxyapatite layer. A strong spectrum of phosphorus is detected up to 6-8 μm depth for samples after 4, 7 and 10 days immersion in simulated body fluid when compared to weak spectrum detected before immersion. The increase in the phosphorus spectrum corresponds to the hydroxyapatite formation on the surface of the samples after the samples were placed in simulated body fluid.     

Surface modification of polypropylene and compatibilization of interfaces in incompatible blends of polypropylene with polystyrene by plasma of CO2

The effect of surface modification of polypropylene (PP) film is induced by CO₂ plasma in this study. The change in chemical structures on the surface of PP film is characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR). The polarity of modified surface of PP film is investigated by contact angle method. The compatibilization of interfaces between polypropylene and polystyrene phases in incompatible blends is studied by the treatment of plasma of CO₂. Transition layer thickness is measured by small angle light scattering (SALS).     

Fabrication of hydroxyapatite and TiO2 nanorods on microarc-oxidized titanium surface using hydrothermal treatment

AC-type microarc oxidation (MAO) and hydrothermal treatment techniques were used to enhance the bioactivity of commercially pure titanium (CP-Ti). The porous TiO₂ layer fabricated by the MAO treatment had a dominant anatase structure and contained Ca and P ions. The MAO-treated specimens were treated hydrothermally to form HAp crystallites on the titanium oxide layer in an alkaline aqueous solution (OH-solution) or phosphorous-containing alkaline solution (POH-solution). A small number of micro-sized hydroxyapatite (HAp) crystallites and a thin layer composed of nano-sized HAps were formed on the Ti-MAO-OH group treated hydrothermally in an OH-solution, whereas a large number of micro-sized HAp crystallites and dense anatase TiO₂ nanorods were formed on the Ti-MAO-POH group treated hydrothermally in a POH-solution. The layer of bone-like apatite that formed on the surface of the POH-treated sample after soaking in a modified simulated body fluid was thicker than that on the OH-treated samples.     

Composite SiO2/TiO2 and amine polymer/TiO2 nanoparticles produced using plasma-enhanced chemical vapor deposition

Plasma-enhanced chemical vapor deposition was used to conformally coat commercial TiO₂ nanoparticles to create nanocomposite materials. Hexamethyldisiloxane (HMDSO)/O₂ plasmas were used to deposit SiO₂ or SiO_xC_yH_z films, depending on the oxidant concentration; and hexylamine (HexAm) plasmas were used to deposit amorphous amine-containing polymeric films on the TiO₂ nanoparticles. The composite materials were analyzed using Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). These analyses reveal film composition on the nanoparticles was virtually identical to that deposited on flat substrates and that the films deposit a conformal coating on the nanoparticles. The performance of the nanocomposite materials was evaluated using UV-vis spectroscopy to determine the dispersion characteristics of both SiO_x and HexAm coated TiO₂ materials. Notably, the coated materials stay suspended longer in distilled water than the uncoated materials for all deposited films.     

Surface modification of activated carbons for CO2 capture

The reduction of anthropogenic CO₂ emissions to address the consequences of climate change is a matter of concern for all developed countries. In the short term, one of the most viable options for reducing carbon emissions is to capture and store CO₂ at large stationary sources. Adsorption with solid sorbents is one of the most promising options. In this work, two series of materials were prepared from two commercial activated carbons, C and R, by heat treatment with gaseous ammonia at temperatures in the 200-800 °C range. The aim was to improve the selectivity and capacity of the sorbents to capture CO₂, by introducing basic nitrogen-functionalities into the carbons. The sorbents were characterised in terms of texture and chemical composition. Their surface chemistry was studied through temperature-programmed desorption tests and X-ray photoelectron spectroscopy. The capture performance of the carbons was evaluated by using a thermogravimetric analyser to record mass uptakes by the samples when exposed to a CO₂ atmosphere.     

Surface modification of the titanium implant using TEA CO2 laser pulses in controllable gas atmospheres - Comparative study

Interaction of a TEA CO₂ laser, operating at 10.6 μm wavelength and pulse duration of 100 ns (FWHM), with a titanium implant in various gas atmospheres was studied. The Ti implant surface modification was typically studied at the moderate laser beam energy density/fluence of 28 J/cm² in the surrounding of air, N₂, O₂ or He. The energy absorbed from the TEA CO₂ laser beam is partially converted to thermal energy, which generates a series of effects, such as melting, vaporization of the molten material, shock waves, etc. The following titanium implant surface changes and phenomena were observed, depending on the gas used: (i) creation of cone-like surface structures in the atmospheres of air, N₂ and O₂, and dominant micro-holes/pores in He ambient; (ii) hydrodynamic features, most prominent in air; (iii) formation of titanium nitride and titanium oxide layers, and (iv) occurrence of plasma in front of the implant. It can be concluded from this study that the reported laser fluence and gas ambiences can effectively be applied for enhancing the titanium implant roughness and creation of titanium oxides and nitrides on the strictly localized surface area. The appearance of plasma in front of the implants indicates relatively high temperatures created above the surface. This offers a sterilizing effect, facilitating contaminant-free conditions.     

Ti+(CO2)2Ar和Ti+(CO2)n(n=3-7)络合物离子的红外光解离光谱 (cited: 1)

利用脉冲激光溅射-超声分子束载带方法制备了气相Ti⁺(CO₂)₂Ar和Ti⁺(CO₂)_n(n=3-7)络合物离子．采用红外光解离光谱研究了这些选定的质量离子的振动光谱． 对于每一种络合物离子, 在CO伸缩振动频率范围都观察到了振动峰,表明这些离子具有插入的OTi⁺CO(CO₂)_n-1结构． 对于n≦5的OTi⁺CO(CO₂)_n-1离子,其CO振动和CO₂的反对称伸缩振动频率都比自由的CO和CO₂的频率要高,表明CO和CO₂配体与中心金属离子之间主要是静电相互作用．实验结果还表明TiO⁺可以直接络合五个配体(1个CO和4个CO₂分子)．对于n=2络合物体系,除了插入的OTi⁺CO(CO₂)结构以外,还观察到了具有弯曲结构的OCO-Ti⁺-OCO异构体的存在     

Interactions of D2O with CO and CO2 molecules at cryogenic temperatures

On the basis of the matrix effect of secondary-ion mass spectrometry (SIMS), the intermolecular interactions between D₂O and hydrophobic molecules have been investigated at temperature of 15 K. The D⁺ yield is found to be enhanced markedly relative to the D₃O⁺ yield when the D₂O molecule forms a complex with the CO or CO₂ molecules on the surface. The CO molecules are incorporated in the inner pores of amorphous solid water and then cover the outermost surface facing to the vacuum, which is followed by the 3D-island growth on it. A similar result is obtained for the adsorption of the CO₂ molecule but the filling of the inner pores is not complete due to the lower mobility of the CO₂ molecule. The D₂O film grows on the CO₂ layer, but a pure D₂O film is hardly formed on the CO layer due to the occurrence of intermixing.     

Oxidation of H2/CO2 mixtures and effect of hydrogen initial concentration on the combustion of CH4 and CH4/CO2 mixtures: Experiments and modeling

An experimental investigation of the oxidation of hydrogen diluted by nitrogen in presence of CO₂ was performed in a fused silica jet-stirred reactor (JSR) over the temperature range 800-1050 K, from fuel-lean to fuel-rich conditions and at atmospheric pressure. The mean residence time was kept constant in the experiments: 120 ms at 1 atm and 250 ms at 10 atm. The effect of variable initial concentrations of hydrogen on the combustion of methane and methane/carbon dioxide mixtures diluted by nitrogen was also experimentally studied. Concentration profiles for O₂, H₂, H₂O, CO, CO₂, CH₂O, CH₄, C₂H₆, C₂H₄, and C₂H₂ were measured by sonic probe sampling followed by chemical analyses (FT-IR, gas chromatography). A detailed chemical kinetic modeling of the present experiments and of the literature data (flame speed and ignition delays) was performed using a recently proposed kinetic scheme showing good agreement between the data and this modeling, and providing further validation of the kinetic model (128 species and 924 reversible reactions). Sensitivity and reaction paths analyses were used to delineate the important reactions influencing the kinetic of oxidation of the fuels in absence and in presence of additives (CO₂ and H₂). The kinetic reaction scheme proposed helps understanding the inhibiting effect of CO₂ on the oxidation of hydrogen and methane and should be useful for gas turbine modeling.     

使用金属掺杂SnO2(110)作为表面催化剂的电催化CO2还原反应：通过调控Sn:O原子比例来控制产物

电催化CO₂还原反应可以产生HCOOH和CO,目前该反应是将可再生电力转化为化学能存储在燃料中的最有前景的方法之一. SnO₂作为将CO₂转换为HCOOH和CO的良好催化剂,其反应发生的晶面可以是不同的. 其中(110)面的SnO₂非常稳定,易于合成. 通过改变SnO₂(110)的Sn:O原子比例,得到了两种典型的SnO₂薄膜：完全氧化型(符合化学计量)和部分还原型. 本文研究了不同金属(Fe、Co、Ni、Cu、Ru、Rh、Pd、Ag、Os、Ir、Pt和Au)掺杂的SnO₂(110),发现在CO₂还原反应中这些材料的催化活性和选择性是不同的. 所有这些变化都可以通过调控(110)表面中Sn:O原子的比例来控制. 结果表明,化学计量型和部分还原型Cu/Ag掺杂的SnO₂(110)对CO₂还原反应具有不同的选择性. 具体而言,化学计量型的Cu/Ag掺杂的SnO₂(110)倾向于产生CO(g),而部分还原型的表面倾向于产生HCOOH(g). 此外,本文还考虑了CO₂还原的竞争析氢反应. 其中Ru、Rh、Pd、Os、Ir和Pt掺杂的SnO₂(110)催化剂对析氢反应具有较高的活性,其他催化剂对CO₂还原反应具有良好的催化作用.     

Deposition of titanium nitride and hydroxyapatite-based biocompatible composite by reactive plasma spraying

Titanium nitride is a bioceramic material successfully used for covering medical implants due to the high hardness meaning good wear resistance. Hydroxyapatite is a bioactive ceramic that contributes to the restoration of bone tissue, which together with titanium nitride may contribute to obtaining a superior composite in terms of mechanical and bone tissue interaction matters.The paper presents the experimental results in obtaining composite layers of titanium nitride and hydroxyapatite by reactive plasma spraying in ambient atmosphere. X-ray diffraction analysis shows that in both cases of powders mixtures used (10% HA + 90% Ti; 25% HA + 75% Ti), hydroxyapatite decomposition occurred; in variant 1 the decomposition is higher compared with the second variant. Microstructure of the deposited layers was investigated using scanning electron microscope, the surfaces presenting a lamellar morphology without defects such as cracks or microcracks. Surface roughness values obtained vary as function of the spraying distance, presenting higher values at lower thermal spraying distances.     

Surface modification of calcium fluoro and hydroxyapatite by 1-octylphosphonic dichloride

The reactivity of the surface of calcium hydroxyapatite (CaHAp) and fluorapatite (CaFAp) was tested and compared by grafting the 1-octylphosphonic dichloride (C₈H₁₇OPCl₂) using a molar ratio x = 2 or 4, x = n(organic)/n(apatite). Successful synthesis was confirmed by different characterisation techniques such as X-ray powder diffraction patterns, IR spectroscopy, MAS-NMR (¹H and ³¹P) and chemical analysis.The difference between their specific surface area (SSA: 57.46 for HAp and 12.09 m²/g for FAp), the percentage of carbon measured after treatment with (C₈H₁₇OPCl₂) and the intensities of IR bands attributed to the grafted moiety suggests that the surface of hydroxyapatite is more reactive than that of fluorapatite.The ³¹P CP-MAS-NMR spectra of treated fluorapatite show a significant change in isotropic signal due to the protonation and deprotonation of superficial phosphate group. This can be explained by the difference in the nature of inorganic material.     

Comparison of CH4/H2 and C2H6/H2 inductively coupled plasma etching of ZnO

CH₄/H₂-based discharges are attractive for dry etching of single crystal ZnO because of their non-corrosive nature. We show that substitution of C₂H₆ for CH₄ increases the ZnO etch rate by approximately a factor of 2 both with and without any inert gas additive. The C₂H₆/H₂/Ar mixture provides a strong enhancement over pure Ar sputtering, in sharp contrast to the case of CH₄/H₂/Ar. The threshold ion energy for initiating etching is 42.4 eV for C₂H₆/H₂/Ar and 59.8 eV for CH₄/H₂/Ar. The etched surface morphologies were smooth, independent of the chemistry and the Zn/O ratio in the near-surface region was unchanged within experimental error after etching with both chemistries. The plasma etching improved the band-edge photoluminescence intensity and suppressed the deep level emission from the bulk ZnO under our conditions, due possibly to removal of surface contamination layer.     

Spectroscopic studies of CO2 trapped in rare gas matrices

Low temperature (5 K) high resolution (0.15 and 0.03 cm⁻¹) absorption spectra of ¹³CO₂ have been recorded in neon, argon, krypton, and xenon matrices, in the ν₃ and ν₂ regions. Diffusion experiments have been performed in krypton and xenon in order to identify vibrational traps which could be responsible for the decrease and shortening of the emission observed after laser excitation: high-frequency structures in the ν₃ region are assigned to dimers and a doubling of the monomer line is due to a site effect. In neon, only a double substitutional site, with a splitting of the degenerate ν₂ vibration, is observed. In argon, as previously reported, a single and a double site are characterized. In krypton and xenon, where ν₂ is not split, only single sites would be predicted. As one of them exhibits a ν₃ line highly sensitive to temperature, we expect a large coupling with the lattice and a fast vibrational relaxation. This site is very likely the vibrational trap we are looking for.     

Mathematical modeling of CO2 TEA laser

Five and six-temperature models for the CO₂–N₂–He system are used to describe the process of the dynamic emission in the TEA CO₂ laser. All physical constants and relaxation rates related to these models are examined to estimate the output pulse parameters as a function of the input parameters. The two pumping processes implemented; empirical function and differential equation show a good agreement with the experimental data.     

Effect of surface roughness of TiO2 films on short-circuit current density of photoelectrochemical cell of ITO/TiO2/PVC-LiClO4/graphite

This paper reports the effect of surface topography of titanium dioxide films on short-circuit current density of photoelectrochemical solar cell of ITO/TiO₂/PVC-LiCLO₄/graphite. The films were deposited onto ITO-covered glass substrate by screen-printing technique. The films were tempered at 300 °C, 350 °C, 400 °C, 450 °C and 500 °C for 30 min to burn out the organic parts and to achieve the films with porous structure. The surface roughness of the films were studied using scanning electron microscope (SEM). Current–voltage relationship of the devices were characterized in dark at room temperature and under illumination of 100 mW cm⁻² light from tungsten halogen lamp at 50 °C. The device utilising the TiO₂ film annealed at 400 °C produces the highest short-circuit current density and open-circuit voltage as it posses the smoothest surface topography with the electrolyte. The short-circuit current density and open-circuit voltage of the devices increase with the decreasing grain size of the TiO₂ films. The short-circuit current density and open-circuit voltage are 0.6 μA/cm² and 109 mV respectively.     

The rate of gasification by CO2 of chars from waste

Three chars and an activated carbon were gasified by reaction with CO₂ in a fluidised bed of sand, at 800–1050 °C. The chars were produced from (i) dried sewage sludge, (ii) car tyres, and (iii) a bituminous coal. For the conditions used, the rate of CO₂ + C → 2CO was largely determined by chemical kinetics; there was a small effect from mass transfer for the most reactive char, derived from sewage sludge. The rate of CO formation, r, differed greatly for these chars, but was well described by:

The reactivity of a char depends on: (i) its pore structure, (ii) catalytic activity of the associated ash, and (iii) the activity of the char’s carbon. The sewage sludge char was the most reactive, on the basis of either BET area or mass by 2 orders of magnitude. The activated carbon had the lowest reactivity per unit BET surface area, indicating that the area in its micropores is comparatively unreactive.     

Dynamical analysis of acousto-optically Q-switched CO2 laser

A compacted size high power CO₂ laser has been developed using an acousto-optically (AO) Q-switch. Performance characteristics have been investigated as a function of output mirror transmittance. The theory of six-temperature model for CO₂ lasers has firstly been utilized to analyze the dynamical process in the AO Q-switched CO₂ laser. This theory perfectly explains the behavior of energy transfer between different molecules in laser gain medium, and describes the shape of pulse laser. The calculated pulse waveforms are in good agreement with the experimental result. Both the experimental and theoretical results present that the optimal value of output mirror transmittance is 39%. Under this condition, the measured peak power is 4750 W and pulsed width is 160 ns, which is consistent with the calculations. Six-temperature model is a perfect theory for CO₂ laser kinetics, which will lay a theoretical foundation for the laser optimum design.     

Absorption spectra of CO2 and CO2 near 1.05 μm

The absolute line intensities of the Fermi triad 2003i-00001 (i = 1, 2, 3) of ¹²C¹⁶O₂ and ¹³C¹⁶O₂ isotopic species of carbon dioxide were retrieved from Fourier-transform spectra recorded at Doppler limited resolution in the region 9200-9700 cm⁻¹. The accuracy of the line intensity determination is estimated to be better than 15% for most lines. The vibrational transition dipole moments squared and Herman-Wallis coefficients have been determined. The global fittings of the observed line intensities within the framework of the effective operators method have been performed. The fitting results reproduce the data within experimental uncertainty.     

A combined experimental and theoretical analysis of Fe-implanted TiO2 modified by metal plasma ion implantation

Photocatalyst titanium dioxide (TiO₂) thin films were prepared using sol-gel process. To improve the photosensitivity of TiO₂ at visible light, transition metal of Fe was implanted into TiO₂ matrix at 20 keV using the metal plasma ion implantation process. The primary phase of the Fe-implanted TiO₂ films is anatase, but X-ray diffraction revealed a slight shift of diffraction peaks toward higher angles due to the substitutional doping of iron. The additional band gap energy levels were created due to the formation of the impurity levels (Fe-O) verified by X-ray photoelectron spectroscopy, which resulted in a shift of the absorption edge toward a longer wavelength in the absorption spectra. The optical band gap energy of TiO₂ films was reduced from 3.22 to 2.87 eV with an increase of Fe ion dosages from 0 to 1 × 10¹⁶ ions/cm². The band gap was determined by the Tauc plots. The photocatalysis efficiency of Fe-implanted TiO₂ was assessed using the degradation of methylene blue under ultraviolet and visible light irradiation. The calculated density of states for substitutional Fe-implanted TiO₂ was investigated using the first-principle calculations based on the density functional theory. A combined experimental and theoretical Fe-implanted TiO₂ film was formed, consistent with the experimentally observed photocatalysis efficiency of Fe-implanted TiO₂ in the visible region.