Synthesis of glass ceramics from kaolin and dolomite mixture

Cordierite-and anorthite-based binary glass ceramics of the CaO-MgO-Al₂O₃-SiO₂ (CMAS) system were synthesized by mixing local and abundant raw minerals (kaolin and doloma by mass ratio of 82/18). A kinetics study reveals that the activation energy of crystallization (Ea) calculated by the methods of Kissinger and Marotta are 438 kJ·mol-1 and 459 kJ·mol-1, respectively. The Avrami parameter (n) is estimated to be approximately equal to 1, corresponding to the surface crystallization mechanism. X-ray diffraction (XRD) analysis shows that the anorthite and cordierite crystals are precipitated from the parent glass as major phases. Anorthite crystals first form at 850℃, whereas the μ-cordierite phase appears after heat treatment at 950℃. Thereafter, the cordierite allotropically transforms to α-cordierite at 1000℃. Complete densification is achieved at 950℃; however, the density slightly decreases at higher temperatures, reaching a stable value of 2.63 kg·m-3 between 1000℃ and 1100℃. The highest Vickers hardness of 6 GPa is also obtained at 950℃. However, a substantial decrease in hardness is recorded at 1000℃; at higher sintering temperatures, it slightly increases with increasing temperature as the α-cordierite crystallizes.     

Specific structural features of LnZrOx (Ln: La, Sm) mixed oxides prepared by different methods

LnZrOx(Ln: La, Sm) mixed oxides of Ln: Zr = 1 were prepared by different methods(complex polymerized method, sorption of cations on starch from aqueous salt solution and conventional co-precipitation with additional redispersion of precipitate by ultra sound) and calcined at 700–1300 °C. Their specific structural features and changes were studied and discussed. Various characterization methods were used such as X-ray diffraction,Electron microscopy, Fourier-transform infrared and Raman spectroscopy, UV–Vis spectroscopy, X-Ray absorption fine structure and X-ray photoelectron spectroscopy.The formation of pyrochlore structure occurred at 1100–1300 °C from fluorite-like pseudocubic phase ZrO_2 regardless the method of preparation. This phase had a block-like structure consisting of ZrO_2 nanocrystals stabilized by Ln cations and residual anions such as hydroxyls and carbonates. The desorption of such anions with heating already started at 900 °C and lead to local changes of Zr cations coordination to octahedral and to the formation of pyrochlore nanodomains inclusions within fluorite-like phase. The increased cation mobility and further elimination of anions caused by further heating was accompanied by the formation of bulk pyrochlore phase at 1100–1300 °C. Even after calcination at 1300 °C the local microheterogeneity as well as defects were identified at domains boundaries or sintered microstructure. These specific features of the formed pyrochlores depend on the method of preparation.     

In situ observations of austenite grain growth in Fe-C-Mn-Si super bainitic steel

In situ observations of austenite grain growth in Fe-C-Mn-Si super bainitic steel were conducted on a high-temperature laser scanning confocal microscope during continuous heating and subsequent isothermal holding at 850, 1000, and 1100℃ for 30 min. A grain growth model was proposed based on experimental results. It is indicated that the austenite grain size increases with austenitizing temperature and holding time. When the austenitizing temperature is above 1100℃, the austenite grains grow rapidly, and abnormal austenite grains occur. In addition, the effect of heating rate on austenite grain growth was investigated, and the relation between austenite grains and bainite morphology after bainitic transformations was also discussed.     

Isothermal oxidation behavior and mechanism of a nickel-based superalloy at 1000℃

The oxidation behavior of a nickel-based superalloy at 1000℃ in air was investigated through X-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy analysis. A series of oxides, including external oxide scales (Cr₂O₃, (TiO₂ + MnCr₂O₄)) and internal oxides (Al₂O₃,TiN), were formed on the surface or sub-surface of the substrate at 1000℃ in experimental still air. The oxidation resistance of the alloy was dependent on the stability of the surface oxide layer. The continuity and density of the protective Cr₂O₃ scale were affected by minor alloying elements such as Ti and Mn. The outermost oxide scale was composed of TiO₂ rutile and MnCr₂O₄ spinel, and the growth of TiO₂ particles was controlled by the outer diffusion of Ti ions through the pre-existing oxide layer. Severe internal oxidation occurred beneath the external oxide scale, consuming Al and Ti of the strength phase γ' (Ni₃(Al,Ti)) and thereby severely deteriorating the surface mechanical properties. The depth of the internal oxidation region was approximately 35 μm after exposure to experimental air at 1000℃ for 80 h.     

K2CO3 catalysis on the reactivity of top charged coke and stamp charged coke

The catalysis of K₂CO₃ on the reactivity of top charged coke and stamp charged coke from Pansteel in China was studied. The coke reaction index of the stamp charged coke was 1%–2% higher than that of the top charged coke. Under the catalysis of K₂CO₃, the coke reaction index of both cokes approximately increased by 4%, 6%, 10% and 6% at 900, 1000, 1100 and 1200°C, respectively. The reactivity of the K-enriched stamp charged coke was 1%–2% higher than that of the K-enriched top charged coke below 1100°C. However, only negligible differences were found in the temperature zone between 1100 and 1200°C. Scanning electron microscopy images illustrated that pores in the top charged coke were smaller and equally distributed, while relatively more big pores exist non-homogenously in stamp charged coke. Due to the different processes in production, the stamp charged coke was more porous and most of the pores tended to be applanate. Cracks were observed in the microstructure of the stamp charged coke during the carbon solution reaction, implying the inferior quality of the stamp charged coke to the top charged coke at high temperature. Diffusion of K during the carbon solution reaction was studied by the energy dispersive spectrometry. It is found that K gradually spreads into the center of lumpy coke with the rising of temperature and is equally distributed on the edges of pores at 1200°C. Besides, oxidation reactions of functional groups become faster with the catalysis of K.content     

Grain boundary characteristics and tensile properties of Ti14 alloy after semi-solid deformation

The microstructure and room-temperature tensile properties of Ti14, a new α+Ti₂Cu alloy, were investigated after conventional forging at 950℃ and semi-solid forging at 1000 and 1050℃, respectively. Results show that coarse grains and grain boundaries are obtained in the semi-solid alloys. The coarse grain boundaries are attributed to Ti₂Cu phase precipitations occurred on the grain boundaries during the solidification. It is found that more Ti₂Cu phase precipitates on the grain boundaries at a higher semi-solid forging temperature, which forms precipitated zones and coarsens the grain boundaries. Tensile tests exhibit high strength and low ductility for the semi-solid forged alloys, especially after forging at 1000℃. Fracture analysis reveals the evidence of ductile failure mechanisms for the conventional forged alloy and cleavage fracture mechanisms for the alloy after semi-solid forging at 1050℃.     

Effects of annealing temperature on the microstructure and hardness of TiAlSiN hard coatings

TiAlSiN hard coatings were synthesized on high-speed steel using an arc ion enhanced magnetic sputtering hybrid system.The microstructure and hardness of the coatings at different annealing temperatures were explored by means of XRD,TEM,EDAX and Vickers indentation.The as-deposited TiAlSiN coatings were confirmed to be amorphous due to high depositing rate and low deposition temperature during the film growth.The transformation from amorphous to nanocomposites of nano-crystallites and amorphousness were observed after the annealing treatment,the microstructure of TiAlSiN coatings annealed at 800°C and 1000°C were consisted of crystalline hcp-AlN,fcc-TiN and amorphous phase,however,the coatings were only consisted of fcc-TiN and amorphous phase when annealing at 1100°C and 1200°C.Meanwhile,the formation of Al2O3 was detected on the coating surface after annealing at 1200°C and it indicated the excellent oxidation resistance of the TiAlSiN coatings under the present experimental conditions.Furthermore,the average grain size of the TiAlSiN coatings after high temperature annealing even at 1200°C was less than 30 nm and the size increased with the increasing temperature.However,the hardness of the so-deposited coatings with HV0.2N=3300 dramatically decreased with the increase of temperature and reached nearly to the hardness of TiN coatings with HV0.2N=2300.     

Rapid reactive synthesis of TiAl3 intermetallics by thermal explosion and its oxidation resistance at high temperature

Porous TiAl₃ intermetallics were synthesized from Ti-75 at.% Al elemental powder mixtures using an energy-saving and rapid reactive method of thermal explosion (TE). The results demonstrated that the actual temperature of the compact climbed rapidly from 673 °C to 1036 °C within 24 s, indicating that an obvious TE reaction occurred during sintering process. The video graphs suggested that the TE in Ti–Al system behaved instant occurrence and overall heating whether from axial or radial direction. The silver wires and NaCl particles that pressed on the surface of the sample disappeared due to the heavy heat released during TE reaction. Only pure TiAl₃ phases were synthesized in TE products and the open porosity of 55.4% was easy to obtain. After high-temperature treatment at 1000 °C, large amounts of sintering-neck formed and then improved the compressive strength of porous TiAl₃ materials. Moreover, the mass gain curve of porous TiAl₃ intermetallics oxidized at 650 °C for 120 h exhibited the parabolic oxidation rate law. XPS analysis confirmed that the strong O 1s peak was 531.4 eV which was the typical binding energy of Al₂O₃. Therefore, the excellent oxidation resistance of porous TiAl₃ foams would be considered as good candidate materials for prolonging the service life at high temperatures.     

Abnormal thermal shock behavior in electrical conductivity of Ti2SnC

Some ternary carbide and nitride ceramics have been demonstrated to exhibit abnormal thermal shock behavior in mechanical properties. However, the influence of thermal shock on other properties is not clear. This work reports on the influence of thermal shock on electrical conductivity of Ti_2SnC as a representative member of ternary carbides. Abnormal change in electrical conductivity was first demonstrated during quenching Ti_2 SnC in water at 500-800 ℃. The residual electrical conductivity of the quenched Ti_2SnC gradually decreased with increasing temperature, but abnormally increased after quenching at 600 ℃. The microstructure of surface cracks was characterized. The main mechanism for the abnormal electrical conductivity recovery is that some narrow branching cracks are filled by metallic Sn precipitating from Ti_2SnC.     

Fabrication and Photocatalytic Characteristics of TiO2 Films on Silicon Substrates

Silicon ( 111 ) and Silicon (100) have been employed for fabrication of TiO2 films by metal organic chemical vapor deposition (MOCVD). Titanium (Ⅳ) isopropoxide (Ti[O (C3H7)4 ])was used as a precursor. The as-deposited TiO2 films have been characterized with Field emission scanning electron microscopy (FE-SEM), X ray diffraction (XRD) and atomic force microscopy (AFM). The photocatalytic properties were investigated by decomposition of aqueous orange Ⅱ. The crystalline and structural properties of TiO2 film had crucial influences on the photodegradation efficiency. For MOCVD in-situ deposited films on Si substrates, thephotoactivities varied following a shape of “M”: At lower (350 ℃ ) middle (500 ℃) and higher (800 ℃) temperature of deposition, relative lower photodegradation activities have been observed. At 400 ℃ and 700 ℃ of deposition, relative higher efficiencies of degradation have been obtained, because one predominant crystallite orientation could be obtained as deposition at those two temperatures, especially a single anatase crystalline TiO2 film could be obtained at 700 ℃ growth.     

Photoluminescence from Ge-SiO2 thin films and its mechanism

Ge-SiO₂ thin films were deposited on p-type Si substrates using the radio frequency (rf) magnetron sputtering technique with a Ge-SiO₂ composite target. Films were annealed in N₂ ambience for 30 min at 300℃—1000℃ with an interval of 100℃. Through the X-ray diffraction, the average size of Ge nanocrystals (nc-Ge) was determined. They increased from 3.9 to 6.1 nm with increasing annealing temperature in the range of 600℃—1000℃. Under ultraviolet excitation, all samples emit a strong violet band centered at 396 nm. With the formation of nc-Ge, the samples exhibit another emission of orange band with the peak at 580 nm and its intensity increases with the increasing size of nc-Ge. The peak positions of two bands do not shift obviously. Experimental data indicate that the violet band comes from GeO defect and the orange band originates mainly from the luminescence centers at the interface between the nc-Ge and SiO₂ matrix.     

Kinetics and mechanism of titanium hydride powder and aluminum melt reaction

Based on the measurement of the released hydrogen gas pressure (P_H2), the reaction kinetics between TiH₂ powder and pure aluminum melt was studied at various temperatures. After cooling the samples, the interface of TiH₂ powder and aluminum melt was studied. The results show that the 2 H P_H2-time curves have three regions; in the first and second regions, the rate of reaction conforms zero and one order, respectively; in the third region, the hydrogen gas pressure remains constant and the rate of reaction reaches zero. The main factors that control the rate of reaction in the first and second regions are the penetration of hydrogen atoms in the titanium lattice and the chemical reaction between molten aluminum and titanium, respectively. According to the main factors that control the rate of reaction, three temperature ranges are considered for the reaction mechanism:(a) 700-750℃, (b) 750-800℃, and (c) 800-1000℃. In the first temperature range, the reaction is mostly under the control of chemical reaction; at the temperature range of 750 to 800℃, the reaction is controlled by the diffusion and chemical reaction; at the third temperature range (800-1000℃), the dominant controlling mechanism is diffusion.     

Evolution of carbides and carbon content in matrix of an ultra-high carbon sintered steel during heat treatment process

DTA, thermal expansion, XRD, and SEM were used to evaluate the effect of quenching temperature on the mechanical properties and microstructure of a novel sintered steel Fe-6Co-1Ni-5Cr-5Mo-1C. Lattice parameters and the mass fraction of carbon dissolved in the matrix of the steel quenched were investigated. It is discovered that the hardness of the steel increases with quenching temperature in the range of 840-900℃ and remains constant in the range of 900 to 1100℃. It decreases rapidly when the temperature is higher than 1100℃. The mass fraction of carbon dissolved in the matrix of the steel quenched at 840℃ is 0.38, but when the quenching temperature is increased to 1150℃, it increases to 0.98. The carbides formed during sintering are still present at grain boundaries and in the matrix of the steel quenched at low quenching temperatures, such as 840℃. When the quenching temperature is increased to 1150℃, most of the carbides at grain boundaries are dissolved with just a small amount of spherical M₂₃C₆ existing in the matrix of the quenched steel.     

Austenite grain growth behavior of Q1030 high strength welded steel

The austenite grain growth behavior of Q1030 steel was studied under different heating conditions. The austenite grain size increases with the heating temperature and holding time increasing. Austenite grains grow in an exponential manner with rising heating temperature and in a parabolic manner with prolonging holding time. A mathematical model for describing the austenite grain growth behavior of Q1030 steel was obtained on the basis of experimental results using regression analysis. When the heating temperatures lie between 1000 and 1100℃ at a certain holding time, abnormal grain growth appears, which causes mixed grains in Q1030 steel.     

Thermal treatment and utilization of Al-rich waste in high calcium fly ash geopolymeric materials

The Al-rich waste with aluminium and hydrocarbon as the major contaminant is generated at the wastewater treatment unit of a polymer processing plant. In this research, the heat treatment of this Al-rich waste and its use to adjust the silica/alumina ratio of the high calcium fly ash geopolymer were studied. To recycle the raw Al-rich waste, the waste was dried at 110℃ and calcined at 400 to 1000℃. Mineralogical analyses were conducted using X-ray diffraction (XRD) to study the phase change. The increase in calcination temperature to 600, 800, and 1000℃ resulted in the phase transformation. The more active alumina phase of active θ-Al₂O₃ was obtained with the increase in calcination temperature. The calcined Al-rich waste was then used as an additive to the fly ash geopolymer by mixing with high calcium fly ash, water glass, 10 M sodium hydroxide (NaOH), and sand. Test results indicated that the calcined Al-rich waste could be used as an aluminium source to adjust the silica/alumina ratio and the strength of geopolymeric materials. The fly ash geopolymer mortar with 2.5wt% of the Al-rich waste calcined at 1000℃ possessed the 7-d compressive strength of 34.2 MPa.     

Synthesis of nano onion-like fullerenes by using Fe/Al2O3 as catalyst by chemical vapor deposition

Nano-carbon materials were synthesized by the catalytic decomposition of acetylene at 400℃ by using Fe/Al₂O₃ as catalyst. The product was refluxed in 36% concentrated HCl at 60℃ for 48 h in order to remove the catalyst support. The samples were examined by scanning and high resolution transmission electron microscopy, energy dispersive spectroscopy and X-ray diffraction. The results show that nano onion-like fullerenes encapsulating a Fe₃C core were obtained. These had a structure of stacked graphitic fragments, with diameters ranging from 15―50 nm. When the product was further heat- treated at 1100℃ for 2 h, nano onion-like fullerenes with a clear concentric graphitic layer structure were obtained. The growth mechanism of nano onion-like fullerenes encapsulating metal cores is suggested to follow a vapor-solid growth model.     

Ultrahigh-pressure (4.5–5.5 GPa) experimental research on pyroxene-garnet transition and its significance

Conclusions The transition from natural Al-enstatite to garnet and Al-poor pyroxene has taken place under the condition of about 1000°C and 4.5–5.5 GPa, and new phases of garnet and corundum have formed when 15% Al₂O₃ was added to the initial natural Al-enstatite. This experimental result has explained the ultrahigh pressure (3.5–5.0 GPa) and relatively low temperature (< 1000°C) genesis of the ultramafic rock of high-pressure metamorphic zone in Dabieshan-northern Jiangsu-Jiaodong and of red corundum garnetite coexisting with garnet peridotite. From the genetic mineralogy, petrology andP-T equilibrium conditions of garnet peridotite of the high-pressure metamorphic zone, kimberlite and Cenozoic basalt and the ultrahigh pressure experimental result, it is inferred that the upper mantle garnet peridotite is transformed with the increase of depth from Al-rich pyroxene garnet peridotite (80–120 km) to Al-poor pyroxene garnet peridotite (greater than 120–150 km).     

Photocatalytic degradation of microcystin-LR using TiO2 nanotubes under irradiation with UV and natural sunlight

In order to investigate the catalytic performance of anodic TiO2 nanotubes and their practical application in the treatment of refractory microcystins(MCs) in natural-water samples,TiO2 nanotubes of diameter of 50-80 nm were fabricated by anodization in C2H2O4·2H2O containing NH4F.Under irradiation with natural sunlight,MC-LR was totally degraded after 1 d using the anodic TiO2 nanotubes.In contrast,the removal efficiency without TiO2 nanotubes was as low as 47.7% within 20 d.In addition,a mixture of anatase and rutile TiO2 gave higher photocatalytic activity than the single phase did.The pH also influenced the adsorption capacity of the TiO2 nanotubes.The order of MC-LR degradation efficiencies at different pH values was 3.5 > 8.0 > 10.0.After five repeated experiments on the degradation of MC-LR for 7 h,the degradation efficiency was still stable.     

Rutile U-Pb age for the ultrahigh pressure eclogite from the Dabie Mountains,central China: Evidence for rapid cooling

The U-Pb isotope compositions of rutile, omphacite and garnet in the eclogite from the Jinheqiao area in the Southern Dabie ultrahigh-pressure metamorphic zone were analyzed. The consistent high precision U-Pb age (218 ± 1.2) Ma of rutile in eclogite from the Dabie Mountains was obtained by two ways of isochron and common Pb correction based on the composition of omphacite. This proves that the omphacite in eclogite has a U/Pb ratio (m = 2.8) low enough to be used for common Pb correction in the analyses of rutile. Under the rapid cooling condition (40℃/Ma) the closure temperature for U-Pb diffusion in rutile is about 470℃. Thus, this U-Pb age of rutile proves that 218 Ma should be the cooling age of eclogite at 470℃ instead of the peak metamorphic age.     

Photocatalytic property of TiO2 sensitized by different crystal phase CdS

TiO2 samples sensitized by different crystal phase CdS(CT) are synthesized by hydrothermal process at different reaction temperature. The samples are characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM), and UV-Vis diffuse reflectance(UV-Vis). The XRD result reveals that the crystal phase of CdS is transformed from cubic phase to hexagonal phase with the increase of hydrothermal reaction temperature(120-160 ℃). The absorption edge of CT is extended from 498 nm to 546 nm. The photocatalytic degradation of rhodamin B(RhB) in aqueous solution is used to evaluate the photocatalytic activity of CT. With the increase of the preparation temperature, the photocatalytic activity of CT becomes stronger. The degradation rate of RhB by CdS/TiO2 at 160 ℃(CT-160 ℃)reaches 78%.