Carbon coating of anatase-type TiO2 through their precipitation in PVA aqueous solution

Fine particles of photocatalytic anatase-type TiO₂ prepared through hydrolysis of titanium-tetraisopropoxide were coated by carbon through their precipitation in poly(vinyl alcohol) (PVA) aqueous solution, followed by heat treatment at high temperatures of 400-1000 °C in a flow of high purity Ar. Without carbon coating, the phase transformation from anatase to rutile started above 600 °C, but it was suppressed up to 800 °C with carbon coating. Suppression of the phase transformation depended on the amount of carbon coated, apparent suppression being observed with carbon content above 5 mass%. The amount of carbon coated on anatase was controlled by changing the concentration of PVA in the solution. In order to have a carbon content of about 5 mass%, a PVA solution with more than 2 mass% had to be used.     

Formation of nanosize ZnO particles by thermal decomposition of zinc acetylacetonate monohydrate

Formation of ZnO particles by thermal decomposition of zinc acetylacetonate monohydrate in air atmosphere has been investigated using XRD, DTA, FT-IR, and FE-SEM as experimental techniques. ZnO as a single phase was produced by direct heating at ≥200 °C. DTA in air showed an endothermic peak at 195 °C assigned to the ZnO formation and exothermic peaks at 260, 315 and 365 °C, with a shoulder at 395 °C. Exothermic peaks can be assigned to combustion of an acetylacetonate ligand released at 195 °C. ZnO particles prepared at 200 °C have shown no presence of organic species, as found by FT-IR spectroscopy. Particles prepared for 0.5 h at 200 °C were in the nanosize range from ∼20 to ∼40 nm with a maximum at 30 nm approximately. The crystallite size of 30 nm was estimated in the direction of the a₁ and a₂ crystal axes, and in one direction of the c-axis it was 38 nm, as found with XRD. With prolonged heating of ZnO particles at 200 °C the particle/crystallite size changed little. However, with heating temperature increased up to 500 or 600 °C the ZnO particle size increased, as shown by FE-SEM observation. Nanosize ZnO particles were also prepared in two steps: (a) by heating of zinc acetylacetonate monohydrate up to 150 °C and distillation of water and organic phase, and (b) with further heating of so obtained precursor at 300 °C.     

Preparation of carbon fiber web from electrostatic spinning of PMDA-ODA poly(amic acid) solution

Pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA) were copolymerized in a tetrahydrofuran (THF)/methanol (MeOH) mixed solvent to form a 12 wt.% poly(amic acid) (PAA) solution. It was electrostatically spun at 13-15 kV to form a PAA web of fine fibers with diameters less than 2-3 μm. The PAA web was heated to 150-250 °C to induce cyclization, transforming the PAA web into polyimide (PI) web. Then, the PI web was heat-treated at 700, 800, 900, 1000 and 2200 °C. The carbonization yield decreased monotonically from 64% at 700 °C to 53% at 1000 °C. The electrical conductivity of carbonized PI webs also increased with increasing heat treatment temperature, exhibiting 2.5 and 5.3 S/cm at 1000 and 2200 °C, respectively. The tensile strength and modulus of the carbonized web were 5.0 and 73.9 MPa, respectively.     

Exfoliation of nitric acid intercalated carbon fibers: effects of heat-treatment temperature of pristine carbon fibers and electrolyte concentration on the exfoliation behavior

Effect of heat treatment temperature of mesophase pitch-based carbon fibers on the exfoliation behavior of derived intercalation compounds with nitric acid was studied. Carbon fibers heat-treated above 2500 °C gave intercalation compounds with mass increase of more than 80 mass% and resulted in a marked exfoliation by a rapid heating to 1000 °C, where no memory of original single fiber was observed. On those below 2000 °C, on the other hand, their residue compounds showed mass increase less than 80 mass% and the appearance after exfoliation at 1000 °C was similar to the original single fiber. On 1150 °C-treated carbon fibers, mass increase was only 13 mass% and no evidence of intercalation was detected even after electrolysis and, as a consequence, the formation of only small fissures along their fiber axis was observed, with no apparent exfoliation. The dependence on electrolyte concentration was also examined on 3000 °C-treated carbon fibers.     

Effect of heat treatment on the mechanical properties of PIP–SiC/SiC composites fabricated with a consolidation process

Continuous SiC fiber reinforced SiC matrix composites (SiC/SiC) have been considered as candidates for heat resistant and nuclear materials. Three-dimensional (3D) SiC/SiC composites were fabricated by the polymer impregnation and pyrolysis (PIP) method with a consolidation process, mechanical properties of the composites were found to be significantly improved by the consolidation process. The SiC/SiC composites were then heat treated at 1400 °C, 1600 °C and 1800 °C in an inert atmosphere for 1 h, respectively. The effect of heat treatment temperature on the mechanical properties of the composites was investigated, the mechanical properties of the SiC/SiC composites were improved after heat treatment at 1400 °C, and conversely decreased with increased heat treatment temperature. Furthermore, the effect of heat treatment duration on the properties of the SiC/SiC composites was studied, the composites exhibited excellent thermal stability after heat treatment at 1400 °C within 3 h.     

High-pressure sintered yttria stabilized zirconia ceramics

Fast densification of 8YSZ ceramics under a high pressure of 4.5 GPa was carried out at different temperatures (800, 1000, 1450 °C), by which a high relative density above 92% could be obtained. FT-Raman spectra indicate that the 8YSZ underwent a phase transition from partially tetragonal to partially cubic phase as temperatures increase from 1000 to 1450 °C when sintering under high pressure. The electrical properties of the samples under different high-pressure sintering conditions were measured by complex impedance method. The total conductivity of 0.92 × 10⁻² S cm⁻¹ at 800 °C has been obtained for 8YSZ under high pressure at 1450 °C, which is about 200 °C lower than that of the samples prepared by conventional pressureless sintering.     

Temperature-dependent morphology changes of noble metal tricalcium phosphate-nanocomposites

Calcium phosphates, functionalized with nano-sized metal particles, are a promising material class for the treatment of bone defects. However, a sintering process is required in principle to achieve sufficient strength of calcium phosphate scaffolds. In this work laser-generated nano-sized silver, gold and platinum particles were adsorbed on micro-sized β-tricalcium phosphate particles and further heat treated at temperatures between 600 and 1200 °C. Gold and platinum nanoparticles underwent exponential growth starting at about 600 °C, while sintering of β-tricalcium phosphate started at 800 °C. We hypothesise that this phenomenon is caused by a heat-induced evaporation and growth process where the decrease of the particle number is directly correlated with the size increase. The silver nanoparticles on the other hand formed a new phase with the calcium phosphate (AgCa₁₀(PO₄)₇) during the heat treatments and could not be observed within the ceramic scaffold anymore. Addressing the lack of information in nanoparticle-combined calcium phosphate scaffolds, this study contributes to the further modification of bone replacement materials with biologically relevant functions and molecules.     

Template assisted fabrication of TiO2 and WO3 nanotubes

Anodic aluminum oxide (AAO) templates with diameters of 200–500 nm were generated by anodizing a commercial aluminum (Al) substrate (99.7%) in 1 vol% phosphoric acid (H₃PO₄), with an applied voltage of 195 V. Titania and tungsten oxide nanotubes (NTs) were successfully grown on AAO template by the sol–gel process. Thermal gravimetric analyzer (TGA) curves showed that gel can be transfered to nanocrystalline particles after 19% weight loss of water molecule by evaporation. The results showed that the nanocrystalline TiO₂ NTs presented at 200 °C, and grains grew as temperature increased. At a temperature of 550 °C, the (101), (103), (004), (112), (200), (105), and (211) planes of anatase TiO₂ were detected clearly, whereas tungsten oxide NTs are amorphous after heat treatment at 200 °C or 300 °C. But the (110), (111), (002), (022), (222), and (004) planes of γ-WO₃ phase can be observed obviously after the heat treatment at 400 °C.     

Synthesis of ZnO nanoparticles by an aerosol process

Spherical nano-sized zinc oxide (ZnO) particles were produced by a spray pyrolysis method using the aerosol technique described in this study. The effects of reaction temperatures of 600, 800 and 1000 °C and collection locations of the particles, such as the flask collector and the tube exit, on the morphology and crystal structure of the ZnO particles were investigated. X-ray diffraction (XRD) studies showed that the crystallinity of the particles was increased by increasing the reaction temperature from 600 °C to 1000 °C. Fourier transform infrared spectroscopy (FTIR) measurements revealed that the particles were pure and similar to each other. Scanning electron microscopy (SEM) revealed that the synthesized nanoparticles had sizes between 200 nm and 400 nm, with uniform morphologies. A computational fluid dynamics (CFD) model of the horizontally positioned tube reactor was developed. Simulation results provided information about the residence time and the temperature distribution along the tube, which were found to be correlated to the particle morphology.     

Effects of oxidation and heat treatment of acetylene blacks on their electrochemical double layer capacitances

Correlations between the electrochemical double layer capacitances of various acetylene blacks modified by surface oxidation and heat treatment, and their morphologies are presented. The acetylene blacks were different from each other in primary structural unit size (equivalent to mean particle diameter). They were oxidized in air at 300 °C for 1 h to produce graphene sheets protruding from the surfaces of the spherical particles. In addition, the surfaces of the acetylene blacks were modified by heat treatments from 1000 °C to 2800 °C, which resulted in a morphological change from surfaces covered with protruding graphene sheets to ones wrapped with basal planes of graphite. Correlations between the capacitances of the acetylene blacks and the observed morphologies showed that the surface covered with protruding graphene sheets was roughly 10 times more effective in capacitive charging than the surface of graphite basal planes. Specifically, the surface specific capacitance of the edged-graphene-sheet-covering surface was 146 mF/m², while that of the basal-planes-wrapping surface was 16 mF/m². It was concluded that the capacitances of the acetylene blacks were mainly defined by surface morphology, which were in turn influenced by structural unit size and degree of oxidation.     

Synthesis and optimization of barium manganate nanofibers by electrospinning

Barium manganate nanofibers were successfully synthesized for the first time after heat treatment of composite nanofibers of polyvinyl pyrrolidone (PVP), barium acetate and manganese acetate using electrospinning technique. Different PVP concentrations were used and the results show that PVP concentration had played important role in the formation, uniformity, homogeneity and particularly in the reduction of nanofibers diameter. Crystal structure, microstructure, elemental analysis and surface morphology were studied using X-ray diffraction analysis, scanning electron microscopy, energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy. X-ray diffraction results show that at low temperature there is no crystallinity in the fibers sample and at ∼400 °C formations of barium manganate crystalline phase starts and finally at 700 °C all the nanofibers became single phase. The first two high intensity peaks (1 0 1) and (1 1 0) give an average crystallite size of about 20 nm. The scanning electron micrographs show that the morphology of the fibers is smooth and uniform at low temperature and become slightly porous at intermediate temperature and finally at high temperature of 700 °C the fibers become highly porous, shrank and their average diameter reduced from ∼400 nm to about 100 nm. These fibers are made of grains with sizes ranging from 15 to 30 nm. Energy dispersive X-ray spectroscopy and Fourier transform infra-red results are also in good agreement with XRD and SEM results.     

Structure changes of single-wall carbon nanotubes and single-wall carbon nanohorns caused by heat treatment

Raman spectra and transmission electron microscope images showed that diameter enlargement of HiPco, a kind of single-wall carbon nanotube, accompanied by tube-wall corrugation was caused by heat treatment (HT) at 1000 to 1700 °C. Further enlargement accompanied by straightening of the tube walls and incorporation of carbon fragments within the tubes became obvious after HT at 1800 to 1900 °C. The transformation of some single-wall carbon nanotubes into multi-wall nanotubes was observed after HT at 2000 °C, and most single-wall tubes were transformed into multi-wall ones by HT at 2400 °C. What influence the Fe contained in the HiPco tubes had on these structure changes was unclear; similar changes were observed in single-wall carbon nanohorns that did not contain any metal. This indicates that thermally induced changes in the structure of single-wall carbon nanotubes can occur without a metal catalyst. Heat treatment increased the integrity of the nanotube-papers, and this increase may have been due to tube-tube interconnections created by HT.     

Synthesis of nanocrystalline Mn-Zn ferrite powders through thermolysis of mixed oxalates

Nanocrystalline Mn-Zn ferrite powders were synthesized by thermal decomposition of an oxalate precursor. Two polymorphs of a mixed Mn-Zn-Fe oxalate dihydrate were obtained by precipitation of metal ions with oxalic acid: monoclinic α-(Mn, Zn, Fe)₃(C₂O₄)₃·6H₂O is obtained after precipitation and ageing at 90 °C, whereas the orthorhombic β-type is formed after precipitation at room temperature. The morphology of the oxalate crystals can be controlled by the precipitation conditions. The α-polymorph of the mixed oxalate consists of prismatic and agglomerated particles. The β-oxalate forms non-agglomerated crystallites of submicron size. Thermal decomposition of the oxalate at 350 °C in air results in an amorphous product. Nanosize Mn-Zn ferrite powders are formed at 500 °C and a mixture of haematite and spinel is observed at 750 °C. The thermal decomposition of the mixed oxalate is monitored by thermal analysis, XRD and IR-spectroscopy. The morphology of the oxalate particles is preserved during thermal decomposition; the oxide particle aggregates display similar size and shape as the oxalates. The primary particles are much smaller; their size increases from 3 nm to 50 nm after decomposition of the oxalates at 350 and 500 °C, respectively. The powder synthesized by decomposition at 500 °C was sintered at 1150 °C to dense and fine-grained Mn-Zn ferrites.     

Synthesis of TiO2 scaffold by a 2 step bi-layer process using a molten salt synthesis technique

TiO₂ scaffolds of anisotropic rutile particles were grown from rutile seeds by using molten salt synthesis techniques. The rutile seeds were either in the form of a separate layer applied on a substrate or a sintered bulk pellet. Mixtures of amorphous titanium hydroxide and salt applied as coatings on the rutile seeds were heat treated. Depending on the morphology of the seed layer, heat treatment temperature, time and salt medium, rutile was grown with different morphologies and microstructures. For NaCl-KCl eutectic salt mixture and heat treatment at 700 °C for 5 h, nano-whiskers of 20-50 nm diameter and 0.5-1 μm length were obtained. For the NaCl salt sample treated at 850 ºC for 20 h, rutile platelets of 2-5 μm thick, 2-10 μm wide and 5-25 μm in length were produced. X-ray diffraction and Raman scattering were used to identify and characterize the rutile phase of the nanowhiskers.     

Influence of heat treatment on the activity and structure of CoTETA/C catalysts for oxygen reduction reaction

The influence of heat treatment on the improvement of the catalytic activity of CoTETA/C catalysts is investigated. These non-precious metal oxygen reduction catalysts are prepared from carbon-supported cobalt triethylenetetramine (CoTETA/C) and heat treated in the temperature interval from 500 to 1000 °C in Ar atmosphere. Electrochemical characteristics are demonstrated in oxygen-saturated acid electrolyte by rotating disk electrode, cyclic voltammetry, as well as single fuel cell tests. The results show that the effect of heat treatment is important on the catalytic activity of CoTETA/C catalysts for the ORR and a maximum catalytic activity is obtained after heat treatment at 800 °C. The ORR reaction mechanism on the catalysts heat treated at 700, 800 and 900 °C is mainly through a 4e reaction path, while a 2e reaction is dominant on the catalysts heat treated at 500, 600 and 1000 °C. Tafel slopes of the CoTETA/C catalysts are all around −200 mV/dec. X-ray absorption measurements reveal that the CoN₄ centers are no longer detected after heat treatment. XRD results clearly confirm the formation of nanometallic α-Co with different sizes aggregated. A possible interpretation of the catalytic active sites is also discussed.     

Microstructural changes induced in “stacked cup” carbon nanofibers by heat treatment

Systematic studies of structural changes in stacked cup carbon nanofibers by heat treatment from 1800 to 3000 °C are carried out. The most prominent feature upon heat treatment of these nanofibers is the formation of energetically stable loops between adjacent active end planes both on the inner and outer surfaces. The appearance of the jagged outer and inner surfaces at 3000 °C is due to a combinational effect, perhaps caused by improved stacking within domains connected by loops having limited crystallite size, accompanied by structural reorganization between domains. Consequently, a low degree of graphitizability is ascribed to this unusual stacked cup morphology of pristine carbon nanofibers.     

Microstructure of carbon/carbon composites reinforced with pitch-based ribbon-shape carbon fibers

Carbon/carbon composites were prepared with ribbon-shape pitch-based carbon fibers serving as reinforcement and thermosetting PFA resin and thermoplastic pitch as matrix precursors. The composites were heat treated to 1000, 1600 and 2700 °C. Microstructural transformations taking place in the reinforcement, carbon matrix, and the interface were studied using polarized optical and scanning electron microscopy. The fiber/matrix bond and ordering of the carbon matrix in heat-treated composites was found to vary depending on the heat treatment temperature of the fibers. Stabilized fiber cleaved during carbonization of resin-derived composites. In contrast, fibers retain their shape during carbonization of pitch matrix composites. Optical activity was observed in composites made with carbonized fibers; the extent decreases with increased heat treatment of the fibers. Studies at various heat treatment temperatures indicate that ribbon-shape fibers developed ordered structure at 1600 °C when co-carbonized with thermosetting resin or thermoplastic pitches.     

Crack-healing behavior of hot-pressed TZ3Y20A-SiC ceramics

Crack healing behavior of hot-pressed TZ3Y20A-SiC ceramics has been investigated by high-temperature oxidation. Semi-elliptical surface cracks with a length of 100 μm have been set on the tensile side of each specimen using a Vickers hardness indenter. Based on flexural strength and observations of crack appearance, the effect of crack healing is finally judged. Cracks on ZrO₂(Y₂O₃)–Al₂O₃ (TZ3Y20A) ceramics cannot be healed by heat treatment. However, for TZ3Y20A-SiC ceramics, complete crack-healing has been realized by heat treatment at 800 °C, 1000 °C and 1100 °C for 30 h, 10 h and 5 h, respectively. The crack-healing mechanism is attributed to the formation of SiO₂ caused by high temperature oxidation during heat treatment.     

Organically modified layered-silicates facilitate the formation of interconnected structure in the reaction-induced phase separation of epoxy/thermoplastic hybrid nanocomposite

We incorporated organic modified layered silicates (OLS) into the mixture of epoxy and poly(ether imide) (PEI) to obtain a ternary hybrid nanocomposite and investigated its reaction-induced phase separation behavior. We found that OLS had dramatic impact to the phase separation process and the final phase morphology. The onset of phase separation and the gelation or vitrification time were greatly brought forward and the periodic distance of phase-separated structure was reduced when OLS was incorporated. Phase separation of the unfilled specimens was greatly suppressed at temperatures higher than 190 °C, and no etch hole of PEI-rich phase could be observed in the SEM images. An interconnected, or bicontinuous morphology could only be observed at cure temperatures lower than 140 °C. On the contrary, the OLS-filled hybrid nanocomposites carried out obvious phase separation at cure temperatures ranging from 120 to 220 °C. Even at cure temperatures higher than 190 °C, the hybrid nanocomposites had an interconnected phase-separated microstructure. These phenomena were related to the preferential wettability, chemical reaction of OLS with epoxy oligomer and the enhanced viscosity of the mixture.     

Effect of ethylene glycol on the mullite crystallization

Mullite is one of the most important aluminosilicate due to its unique thermal properties. In this work, mullite was obtained by sol-gel process at low temperature using sodium metasilicate, water, aluminum nitrate and ethylene glycol. The samples were prepared with a volume ratio of ethylene glycol/water equal to 0/1, 1/1, 2/1 and 3/1. The ethylene glycol effect on mullite crystallization was studied by X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR), Scanning Electron Microscopy (SEM) and Differential Thermal Analysis (DTA). The sample prepared without ethylene glycol, the less homogeneous one, formed amorphous silica, spinel-phase and α-alumina at 1000 °C, and then crystallized mullite at 1200 °C, with an alumina molar fraction of 0.58. The other samples formed amorphous silica at 900 °C and crystallized mullite as the only crystalline phase at 1000 °C. However, the alumina content in mullite formula depends on the thermal treatment, reaching 0.58 at 1250 °C.