Preparation of hollow TiC nanoparticles by the two-stage refluxing method

The two-stage refluxing method was applied to prepare hollow TiC nanoparticles. In this method, after refluxing the hydrous TiO₂ and ethanol, the precipitate and n-dedocane were refluxed to obtain the refluxing-derived precursor. The precursor was heat-treated at 1300 °C for 1 h and hollow TiC nanoparticles could be achieved. It is found that the pore size of the hollow TiC nanoparticles ranges from 3 to 76 nm and the mean pore size is 26.776 nm. The formation of the hollow structure is due to that the mesoporous channels of the precursor confine the carbide's growth inside it. In comparison with commercial TiC nanocrystals, the hollow TiC nanoparticles have higher specific surface area and pore volume significantly.     

开放体系下碳热还原法制备碳氮化钛粉末的研究

在开放体系下,采用碳热还原氮化的方法制备出了碳氮化钛粉末.结合TG、DSC、XRD、SEM等分析测试手段对开放体系下TiO2的碳热还原氮化的反应过程,以及该过程中的物相演变进行了研究.结果表明,随着温度的升高,反应过程中的物相演变遵循TiO2(anatase)→TiO2(rutile)→Ti4O7→Ti3O5→Ti(N,O)→Ti(C,N,O)→Ti(C,N)的顺序;1355℃时,对应着中间氧化物Ti3O5向立方相Ti(C,N,O)的转变,该过程在整个反应进程中转化速度最快;当,m(Ti):m(C)=1:2.7,氮气流量为500ml/min,1600℃下保温3h的情况下,可获得晶粒大小为40.9nm的TiC0.704N0.296粉末.     

Preparation,characterization and photocatalytic activities of holmium-doped titanium dioxide nanoparticles

Holmium-doped TiO₂ nanoparticles with high photocatalytic activities were prepared by sol–gel method and characterized by X-ray diffraction, transmission electron microscopy, ultraviolet–visible diffuse reflectance spectroscopy, and surface area measurement by nitrogen adsorption in this study. Experimental results indicated holmium doping could increase the surface area of TiO₂ nanoparticles, and inhibit the growth of crystalline size and the anatase-to-rutile phase transformation. The results of photodegrading methyl orange showed holmium doping improved the photocatalytic activity of TiO₂, and the reasons could be attributed to the synergetic effects of large surface areas, small crystallite size, lattice distortion and more charge imbalance of holmium-doped TiO₂. In our experiment, the optimal doped amount was 0.3 mol.% for the maximum photocatalytic degradation ratio when holmium-doped TiO₂ was calcined at 500 °C, and the optimal calcined temperature was 600 °C when the doped amount was 0.5 mol.%.     

Preparation of black titanium monoxide nanoparticles and their potential in electromagnetic wave absorption

In this work, black titanium monoxide (TiO) nanoparticles were synthesized by hydrogen assisted magnesium thermal reduction method from nanotube titanic acid (NTA) and their electromagnetic properties were investigated. The black TiO nanoparticles exhibited the optimal reflection loss of −37.7 dB at a thin absorbance layer of 1.2 mm in thickness, which showing a promising candidate in electromagnetic wave absorbing (EA). To explore the mechanism of EA, TiO nanoparticles prepared from the other two initiators (commercial grade TiO and P25 titanium dioxide) was used as a comparison. The results show that the crystalline structure and microscopic defects, which arouse from the formation of TiO in the hydrogen assisted process, affect the electromagnetic performance of Ti-O binary system significantly in addition to their intrinsic effects. We hope this study help to open a new way for the designing of high-performance EA materials.     

Aerosol synthesis of titanium nitride nanoparticles by direct current arc discharge method

Arc discharge synthesis has industrial relevance due to its low cost and scale-up potential. The production of titanium nitride nanoparticles was achieved by direct current arc discharge in an atmospheric-pressured ambient composed of N₂ and Ar. We systematically investigated the effect of the synthesis parameters, including quench gas velocity, quench gas composition, and applied arc current, on the particle quality, yield, and size. It is found that increasing quench gas velocity enables to produce particles with a primary size of 10–15 nm, while titanium nitride particles of 20–50 nm are produced at low quench gas velocity based on scanning electron microscope (SEM) analysis. X-ray diffraction (XRD) results indicated that titanium nitride particles produced at various nitrogen compositions are almost stoichiometric, while the crystallite size increases almost 20 nm when increasing nitrogen contents in the quench gas. Quench gas composition also has a significant impact on the arc voltage as well as particle production rate. When increasing the nitrogen concentration from 20% to 100%, the production rate can be enhanced by a factor of three. Besides, raising the applied arc current from 12 A to 50 A leads to a yield enhancement of factor 10. According to the Brunauer-Emmett-Teller (BET) measurement, the increase of applied arc current has a limited impact on primary particle size. The enhancement in particle production rate is mainly reflected by the larger agglomerate sizes and agglomerate number concentration. Additionally, based on experimental observations and previous studies, a mechanism is presented to explain the growth of deposits on the cathode tip.     

Synthesis of nano-TiC powder using titanium gel precursor and carbon particles

The paper presents a novel process for synthesis of nano-size titanium carbide by reaction between titanium bearing precursor gel and nano carbon particles derived from soot at different temperatures in the range of 1300-1580 °C for 2 h under argon cover. The HRTEM studies of TiC powder synthesized by heating at 1580 °C show the presence of cube shaped particles (~ 60-140 nm) and hollow rods (diameter ~ 30-185 nm). The average particle size of crystallites, calculated by Scherer equation is observed to be ~ 35 nm while the surface area-density measurements indicate it to be ~ 113 nm. The surface area decreases with increase in reaction temperature.     

A new process for titanium aluminides production from TiO2

This paper describes a new process for producing titanium aluminides, in particular TiAl, from TiO2 raw material. On the basis of obtained results, the non-completed reaction of TiO2 with Al and Ca in a special reaction vessel results in the production of granulates of titanium aluminides especially Ti3Al and other Ti- Al phases as the metallic product and Ca12Al14O33 as the non-metallic product. By adding KClO4 in the mixture, a nearly completed reaction can be carried out. The products of this reaction are titanium aluminide particularly TiAl as the metallic part and CaAl4O7 （grossite） as the non-metallic slag part. Both product and slag are produced in a separated form. This process, called KRH-method is described in this article. The scanning electron microscopic microstructure of metallic part of the product shows different phases： the matrix phase is TiAI, where the needle form precipitation is TiAl2 and the plate form precipitation includes TiAI and Ti3Al phases. The microstructure of the remelted metallic part indicates dendritic phase with a lamellar structure comprising of TiAl and Ti3Al phases. The interdendritic phase of TiAI is also seen.     

Synthesis of titanium dioxide nanoparticles by reactive DC magnetron sputtering

Nanometer-sized titanium dioxide (TiO₂) particles were prepared on carbon substrates by reactive direct-current magnetron sputtering. By performing measurements with high resolution electron microscopes, the mean nanoparticle diameter and the coverage fraction of the substrate by the nanoparticles (NPs) were measured at 19 nm and 30%, respectively. Moreover, electron diffraction analysis showed that the TiO₂ NPs' crystalline structure on the carbon substrate was a mixture of anatase and rutile. Finally, we provided information on the TiO₂ initial growth stage: crystalline NPs were formed after deposition of amorphous nanoparticles on the substrate and heating.     

Preparing low-oxygen titanium powder by calcium reductant from titanium hydride

In a previous study, we prepared a low-oxygen titanium powder from titanium scrap through Hydrogenation-Dehydrogenation and deoxidation in a solid-state (DOSS) process with calcium. In this study, an advanced deoxidation in a solid-state process applied titanium hydride as a raw material is proposed to shorten the time of the previous DOSS process. Compared to the previous DOSS process, the total process time was shortened, and the same oxygen reduction rate was obtained. In addition, it was confirmed that the low-oxygen titanium powder prepared this by advanced DOSS process has a superior oxidation resistance than the titanium powder obtained by the previous study.     

Preparation and characterization of APTES films on modification titanium by SAMs

In this study, the titanium plates, which were modified by NaOH alkali solution, were associated with 3-Aminopropyltriethoxysilane (APTES) films using self-assembled monolayers (SAMs). The surfaces of titanium before and after modification were characterized by scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and attenuated total refraction-Fourier transform infrared spectroscopy (ATR-FTIR). After bonding the APTES films on the modification titanium, the new peaks located around 1095 cm⁻¹ attributes to siloxane groups indicating that silane agent had been grafted onto the surface of the modification titanium substrate by SAMs. Following the deposition of APTES films on titanium, significant change were seen in the amounts of oxygen, silicon and carbon present on the titanium surface, which were consistent with the anticipated reaction steps.     

Photocatalytic thin films of TiO2 formed by a sol-gel process using titanium tetraisopropoxide as the precursor

Thin TiO₂ films were prepared with the dip-coating technique by using sols deriving from titanium tetraisopropoxide. TiO₂ films were formed on glass substrates previously covered by a SiO₂ layer obtained from a tetraethylortosilicate sol. The films, after a thermal treatment at 673 K, mainly consisted of TiO₂ anatase. The samples were characterised by X-ray diffraction, UV-Vis spectroscopy, scanning electron microscopy and atomic force microscopy. The photoactivity of the various films was tested by using as probe reaction the photo-oxidation of 2-propanol in gas-solid regime. The photoreactivity results indicated that the TiO₂ films were efficient for degrading 2-propanol under UV illumination, propanone being the only compound detected as intermediate product. Films prepared by using Degussa P25 appeared to be more photoactive, but the coating was easily detached by wiping.     

Characterization of titanium dioxide atomic layer growth from titanium ethoxide and water

Atomic layer growth of titanium dioxide from titanium ethoxide and water was studied. Real-time quartz crystal microbalance measurements revealed that adsorption of titanium ethoxide is a self-limited process at substrate temperatures 100–250°C. A relatively small amount of precursor ligands was released during titanium ethoxide adsorption while most of them was exchanged during the following water pulse. At temperatures 100–150°C, incomplete reaction between surface intermediates and water hindered the film growth. Nevertheless, the deposition rate reached 0.06 nm per cycle at optimized precursor doses. At substrate temperatures above 250°C, the thermal decomposition of titanium ethoxide markedly influenced the growth process. The growth rate increased with the reactor temperature and titanium ethoxide pulse time but it insignificantly depended on the titanium ethoxide pressure. Therefore reproducible deposition of thin films with uniform thickness was still possible at substrate temperatures up to 350°C. The films grown at 100–150°C were amorphous while those grown at 180°C and higher substrate temperature, contained polycrystalline anatase. The refractive index of polycrystalline films reached 2.5 at the wavelength 580 nm.     

Failure of titanium condenser tube

Failure investigation was carried out on a titanium condenser tube that suffered from a large size perforation. The environment at the shell side is hydrocarbon with low pressure steam, while it is seawater at the tube side. The tube was totally plugged with alkaline scale, consisting of calcium carbonate and calcium sulfate. The investigation revealed that in the initial stages of fouling, the titanium tube suffered from erosion–corrosion damage due to the presence of turbulent flow conditions and suspended solids. On the other hand, when the tube became totally fouled, overheating occurred, leading to growth of the oxide film on the internal tube surface. However, the titanium oxide film cracked due to the pressure exerted by the growing scale inside the tube, leading to thin lip rupture.     

Preparation of graphite fibres from a modified PAN precursor

Graphite fibres were developed from polyacrylonitrile (PAN) fibres modified with potassium permanganate. To our knowledge, this is the first time that the effect of modification on the physical properties, microstructure, elemental composition, electrical resistivity, and mechanical properties of fibres has been examined during the graphitization process. The graphite fibres developed from modified PAN fibres had a higher density, a greater stacking size,L _c, and a higher preferred orientation than those developed from unmodified PAN fibres. The graphite fibres also showed an improvement of 20%–40% in electrical resistivity and modulus.     

New doxorubicin nanoparticles engineered from calcium-crosslinked carbomer and a microemulsion precursor

Abstract

The purpose of this study was to investigate a new polymeric system and production process in which self-assembled doxorubicin-loaded nanoparticles were synthetized by using a water-in-oil microemulsion as a template and calcium ions as cross-linkers. The manufacturing process combined cross-linking of carbomer within a W/O microemulsion followed by a phase-separation technique to avoid using organic solvents for extraction. To assess the sustained release behavior of doxorubicin from the nanoparticles, we have developed a new simple method based on the permeability coefficient of a synthetic membrane mounted on Franz diffusion cell system. Franz cells were preferred over the commonly used dialysis tubing because they provide adequate measures of the diffusion area as well as the volumes of the media in both sides of the membrane. The lower permeability values obtained for nanoparticles have shown that the release is a limiting step of the diffusion process, while the calculated straight lines may imply that the apparent release rate of the nanoparticle ensembles is close to a zero-order kinetics. The new drug release method for the evaluation of nano-carriers, utilizing a simple linear model to determine the permeability coefficient, has been proposed for perfect sink and non-sink conditions.     

Preparation, characterization and photocatalytic activities of holmium-doped titanium dioxide nanoparticles

The objective of the proposed work was focused to provide promising solid-phase materials that combine relatively inexpensive and high removal capacity of some radionuclides from low-level radioactive liquid waste (LLRLW). Four various zeolite minerals including natural clinoptilolite (NaNCl), natural chabazite (NaNCh), natural mordenite (NaNM) and synthetic mordenite (NaSM) were investigated. The effective key parameters on the sorption behavior of cesium (Cs-134) were investigated using batch equilibrium technique with respect to the waste solution pH, contacting time, potassium ion concentration, waste solution volume/sorbent weight ratio and Cs ion concentration. The obtained results revealed that natural chabazite (NaNCh) has the higher distribution coefficients and capacity towards Cs ion rather than the other investigated zeolite materials. Furthermore, novel impregnated zeolite material (ISM) was prepared by loading Calix [4] arene bis(-2,3 naphtho-crown-6) onto synthetic mordenite to combine the high removal uptake of the mordenite with the high selectivity of Calix [4] arene towards Cs radionuclide. Comparing the obtained results for both NaSM and the impregnated synthetic mordenite (ISM-25), it could be observed that the impregnation process leads to high improvement in the distribution coefficients of Cs⁺ ion (from 0.52 to 27.63 L/g). The final objective in all cases was aimed at determining feasible and economically reliable solution to the management of LLRLW specifically for the problems related to the low decontamination factor and the effective recovery of monovalent cesium ion.     

Effect of film thickness and the presence of surface fluorine on the structure of a thin barrier film deposited from tetrakis-(dimethylamino)-titanium onto a Si(100)-2 × 1 substrate

The structure of a thin film deposited using tetrakis-(dimethylamino)-titanium (Ti(N(CH₃)₂)₄) as a precursor onto a Si(100)-2 × 1 substrate at ultra-high-vacuum conditions was investigated as a function of film thickness for the films of 20 and 145 nm in the presence of surface copper and fluorine produced by in situ dosing of a common copper deposition precursor, (hexafluoroacetylacetonate)Cu(vinyltrimethylsilane), (hfac)Cu(VTMS), and a hydrogenated form of the hfac ligand, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, hfacH. A combination of surface, depth-profiling, and microscopy analytical techniques suggests that the structure of the titanium carbonitride film depends profoundly on its thickness. While the composition of the film was relatively constant throughout its whole thickness, the nanometer-scale structure changed from amorphous at the top of a 145-nm-thick film, to having a significant amount of small (∼ 5 nm) crystallites closer to the TiCN/Si interface. These studies also confirmed the absence of microfractures in the film prepared by this approach. The ex situ depth profiling investigation suggested that if (hfac)Cu(VTMS) is deposited on a TiCN-precovered silicon substrate and briefly annealed to 800 K, the film acts as a diffusion barrier for copper, while surface fluorine penetrates the film rather easily, resulting in fluorine that is distributed uniformly throughout the film.     

The effect of different methods to add nitrogen to titanium alloys on the properties of titanium nitride clad layers

In this investigation, titanium nitride (TiN) reinforcements are synthesized in situ on the surface of Ti–6Al–4V substrates with gas tungsten arc welding (GTAW) process by different methods to add nitrogen, nitrogen gas or TiN powder, to titanium alloys. The results showed that if nitrogen gas was added to titanium alloys, the TiN phase would be formed. But if TiN powder was added to titanium alloys, TiN + TiN_x dual phases would be presented. The results of the dry sliding wear test revealed that the wear performance of the Ti–6Al–4V alloy specimen coated with TiN or TiN + TiN_x clad layers were much better than that of the pure Ti–6Al–4V alloy specimen. Furthermore, the evolution of the microstructure during cooling was elucidated and the relationship among the wear behavior of the clad layer, microstructures, and microhardness was determined.