Anatase–rutile transformation in doped titania under argon and hydrogen atmospheres

Abstract

Pure titania pulp containing amorphous titania was heated at different temperatures and times. Above 650°C anatase phase was evolved and between 900 and 1000°C, anatase–rutile transformation occurred. The anatase–rutile transformation in TiO₂ in the presence of different transition metal oxides, namely Fe₂O₃, Cr₂O₃, NiO, CuO and MnO₂ under argon and hydrogen atmospheres was investigated. The different phases of TiO₂ were determined using powder X-ray diffraction (XRD). The anatase–rutile transformation temperature was found to be lowered in the presence of transition metal oxides. The transformation temperature was found to vary much in argon and hydrogen atmospheres compared to air in the presence of the metal oxides. Also the method of preparation of metal oxide doped TiO₂ influences rutilation. Other methods such as chemical analysis, surface area measurements and crystallite size calculation were used for the characterisation of the samples. The surface area of heated samples was found to be decreased while crystallite size increased due to rutilation on heating. The samples were also observed under a scanning electron microscope to characterise the microstructural changes associated with each thermal treatment and atmosphere. The morphology of doped titania changes much on heating due to phase modification. The atmosphere of heating also has important effect on deciding the morphology of rutilated titania.     

High activation of apatite-coated titanium dioxide using heat treatment

The purpose of this study was to improve the photocatalytic activity of TiO₂. A composite material in which apatite crystals were precipitated on the surface of TiO₂ was synthesized by immersing TiO₂ powder in pseudo-body solution. The composite material was heated in an attempt to improve the crystallization without inducing the anatase to rutile phase transformation of TiO₂ or reducing the specific surface area. In contrast to using TiO₂ alone, apatite-coated TiO₂ had a higher anatase-to-rutile transition temperature and lower specific surface area. In the methylene blue decolorization test, the decolorization rate of apatite-coated TiO₂ gradually increased with an increase in the heating temperature from 100 °C to 500 °C, and rapidly increased from 700 °C to 900 °C. The apatite-coated TiO₂ heated at 800 °C had the highest decolorization speed, which was approximately three times faster than that of apatite-coated TiO₂ without heating. It is assumed that the crystallinity of the anatase part is enhanced by heating, and the photocatalytic activity is improved.     

HIPed TiO2 dense pellets with improved photocatalytic performance

The effects of heating method and temperature on physical, structural and photocatalytic behaviors of TiO₂ pellets prepared by conventional heating and hot isostatic pressing have been evaluated. The pellets of submicron TiO₂ powders were heated to 600, 650, 700, 750 and 1000 °C using both processing methods in order to compare anatase to rutile phase transformation and densification behaviors. Bulk densities and porosities were calculated using the Archimedes method. XRD analysis were performed to calculate anatase/rutile ratios. Microstructures were characterized using SEM. Photocatalytic experiments have been performed under full spectrum irradiation. Degraded methylene blue samples were periodically monitored through UV–vis spectrophotometer to determine degradation kinetics. Anatase to rutile transformation is slightly faster and densification is better for lower temperatures for conventional heating, however HIPing gives better densification above 750 °C as it also retards rutile transformation. Mixed phase structures and HIPed samples showed the best photocatalytic performance which makes this method advantageous.     

High‐Temperature Compression Deformation Behavior of Fine‐Grained Carbon‐Bonded Alumina

Carbon‐bonded alumina with 33 wt% residual carbon was tested in compression at room temperature and at temperatures between 700°C and 1500°C in quasi‐static tests, creep tests, and stress relaxation tests. Therefore, a new high‐temperature test set up with inert gas chamber and inductive heating was used. The tests were accomplished by investigations of microstructure and Young's modulus. At room temperature, the results exhibit a pronounced hysteresis for the first loading cycle, which almost completely disappeared in subsequent cycles. The creep tests showed characteristic curves for compression whereas primary and secondary (stationary) creep occurred. Above 1000°C, a strong increase in creep rate was detected, whereas almost no creep was observed below this temperature. All creep curves were approximated with the models of logarithmic and Andrade creep. The activation energy for creep was found to be 263 kJ/mol above 1150°C. The resistance against stress relaxation showed an anomaly with a minimum between 1000°C to 1200°C and a maximum between 1300°C and 1400°C.     

Photoactivity of anatase–rutile TiO2 nanocrystalline mixtures obtained by heat treatment of homogeneously precipitated anatase

Nanosized titanium dioxide photocatalysts with varying amount of anatase and rutile phases have been synthesized. Homogeneous precipitation of aqueous solutions containing TiOSO₄ with urea was used to prepare porous spherical clusters of anatase TiO_2. Photoactive titania powders with variable amount of anatase and rutile phases were prepared by heating of pure anatase in the temperatutre range 800–1150 °C. The structure evolution during heating of the starting anatase powders was studied by XRD analysis in overall temperature range of phase transformation. The morphology and microstucture characteristics were also obtained by HRTEM, BET and BJH. The spherical particle morphology of TiO₂ mixtures determined by SEM was stable in air up to 900 °C. The photocatalytic activity of the sample titania TIT85/825 heated to 825 °C in air, contained 77.4% anatase and 22.6% rutile was higher than that nanocrystalline anatase powder. Titania sample TIT85/825 reveals the highest catalytic activity during the photocatalyzed degradation of 4-chlorophenol in aqueous suspension.     

Thermal decomposition kinetics of thermotropic copolyesters made from trans‐p‐hydroxycinnamic acid and p‐hydroxybenzoic acid

A series of thermotropic copolyesters were synthesized by direct thermal melt polycondensation of p‐acetoxybenzoic acid (PHB) with trans‐p‐acetoxycinnamic acid (PHC). The dynamic thermogravimetric kinetics of the copolyesters in nitrogen were analyzed by four single heating‐rate techniques and three multiple heating‐rate techniques. The effects of the heating rate, copolyester composition, degradation stage, and the calculating techniques on the thermostability and degradation kinetic parameters of the copolyesters are systematically discussed. The four single heating‐rate techniques used in this work include Friedman, Freeman–Carroll, Chang, and the second Kissinger techniques, whereas the three multiple heating‐rate techniques are the first Kissinger, Kim–Park, and Flynn–Wall techniques. The decomposition temperature of the copolyesters increases monotonically with increasing PHB content from 40 to 60 mol %, whereas their activation energy exhibits a maximal value at the PHB content of 50 mol %. The decomposition temperature, activation energy, the order, and the frequency factor of the degradation reaction for the thermotropic copolyester with PHB/PHC feed ratio of 50/50 mol % were determined to be 374°C, 408 kJ/mol, 7.2, and 1.25 × 10²⁹ min^?1, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 445–454, 2004     

Processing–Nanostructure–Property Relationships of All‐Polyethylene Composites Reinforced by Flow‐Induced Oriented Crystallization of UHMWPE

All‐polyethylene composites exhibiting substantially improved toughness/stiffness balance are readily produced during conventional injection molding of high density polyethylene (HDPE) in the presence of bimodal polyethylene reactor blends (RB40) containing 40 wt% ultrahigh molar mass polyethylene (UHMWPE) dispersed in HDPE wax. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) analyses shows that flow‐induced crystallization affords extended‐chain UHMWPE nanofibers forming shish which nucleates HDPE crystallization producing shish‐kebab structures as reinforcing phases. This is unparalleled by melt compounding micron‐sized UHMWPE. Injection molding of HDPE with 30 wt% RB40 at 165 °C affords thermoplastic all‐PE composites (12 wt% UHMWPE), improved Young's modulus of 3400 MPa, tensile strength of 140 MPa, and impact resistance of 22.0 kJ/m². According to fracture surface analysis, the formation of skin‐intermediate‐core structures accounts for significantly improved impact resistance. At constant RB40 content both morphology and mechanical properties strongly depend upon processing temperature. Upon increasing processing temperature from 165 °C to 250 °C the average shish‐kebab diameter increases from the nanometer to micron range, paralleled by massive loss of self‐reinforcement above 200 °C. The absence of shish‐kebab structure at 250 °C is attributed to relaxation of polymer chains and stretch‐coil transition impairing shish formation.     

Phase change and crystal growth of TiO2 in metatitanic acid

The transformation of anatase titanium dioxide (TiO₂) to its rutile form generally occurs above 600 °C. The anatase to rutile transformation is influenced by the factors such as heating temperature, heating time and the states of particles of anatase TiO₂. In the calcination of metatitanic acid, the phase transformation of anatase is a key step to form rutile TiO₂ particles with desirable morphological and pigmentary characteristics. However, the precise roles of temperature and time are not clear in the construction of so called calcination intensity for promoting the anatase-rutile transformation to form pigmentary TiO₂ from metatitanic acid. Here we show how the temperature and time have affected the anatase to rutile transformation and the crystal growth of metatitanic acid during the calcination. Through thermal analysis, XRD and SEM measurements, we found that the rutilization in metatitanic acid shows a similar growing trend in the most of phase transformation process. However, the trend of the transformation undergoes an abrupt change when rutilization is approaching to its completion. The changes of the morphology of metatitanic acid are related to the coarsening of the particles in the metatitanic acid during the calcination. Our results demonstrate that anatase to rutile transformation and coarsening of particles are affected by the heating temperature and heating time and the growth of TiO₂ particles can be controlled through calcination intensity.     

Thermal behavior and morphological properties of novel magnesium salt–polyacrylamide composite polymers

Magnesium salt–polyacrylamide composite polymers have been prepared by blending magnesium chloride and magnesium hydroxide, respectively, with polyacrylamide aqueous solution. The thermal behavior of the dried magnesium salt–polyacrylamide composite polymers has been studied. Differential scanning calorimetric (DSC) analysis and thermal gravimetric analysis (TGA) were carried out to investigate the changes of the composite polymers' behavior with temperature. The kinetics of the thermal decomposition of magnesium salt–polyacrylamide composite polymers was investigated over temperature range of 35–800°C with three heating rates of 10, 20, and 40°C/min under nitrogen atmosphere. Flynn and Wall's model was usedto determine the activation energies of thermal decomposition for magnesium salt–polyacrylamide composite polymers. The activation energies needed to decompose 50 wt% of magnesium hydroxide‐polyacrylamide (MHPAM) composite polymer ranged from of 28.993–174.307 kJ/mol which are higher than the values for magnesium chloride–polyacrylamide (MCPAM) composite polymer (21.069–39.412 kJ/mol). Therefore, MHPAM composite polymer has a better thermal stability compared with MCPAM composite polymer. The morphological properties of magnesium salt–polyacrylamide composite polymers were studied using scanning electron microscopy (SEM). Energy‐dispersive X‐ray (EDX) spectroscopy was used to determine the composition of the chemical elements. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Thermal degradation of Kevlar fiber by high‐resolution thermogravimetry

A novel high‐resolution thermogravimetry (TG) technique in a variable heating rate mode that maximizes resolution and minimizes the time required for TG experiments has been performed for evaluating the thermal degradation and its kinetics of Kevlar fiber in the temperature range ∼ 25–900°C. The degradation of Kevlar in nitrogen or air occurs in one step. The decomposition rate and char yield at 900°C are higher in air than in nitrogen, but the degradation temperature is higher in nitrogen than in air. The initial degradation temperature and maximal degradation rate for Kevlar are 520°C and 8.2%/min in air and 530°C and 3.5%/min in nitrogen. The different techniques for calculating the kinetic parameters are compared. The respective activation energy, order, and natural logarithm of preexponential factor of the degradation of Kevlar are achieved at average values of 133 kJ/mol (or 154 kJ/mol), 0.7 (or 1.1), and 16 min⁻¹ (or 20 min⁻¹) in air (or nitrogen). The technique based on the principle that the maximum weight loss rate is observed at the minimum heating rate gives thermal degradation results that were in excellent agreement with values determined by traditional TG experiments. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 565–571, 1999     

Fast scanning calorimetry clarifies the understanding of the complex melting and crystallization behavior of polyesteramide multi‐block copolymers

Fast scanning calorimetry has been applied in order to understand the phase transitions in thermoplastic elastomers (TPEs) based on well‐defined multi‐block copolymers made of ‘soft’ polytetrahydrofuran and ‘hard’ terephthalate ester diamides. The intrinsically complex chemical structure of TPEs leads to complex phase transitions. By changing their thermal history over a wide range of temperature (from ?100 °C to 200 °C) and cooling rates (from 10 to 4000 °C s^?1), we clarify the origins of the various phases present in these materials. In particular, we study the different possibilities for the hard segments to associate depending on their mobility during the quenching phase, forming either strong and stable structures or weaker and metastable ones. Besides, we demonstrate that a minimal cooling rate of 800 °C s^?1 is necessary to keep these TPEs (made of short and monodisperse hard segments) amorphous leading to a subsequent cold crystallization when heating back, at around 30 °C. Finally, we validate our interpretations by varying the copolymer composition (from 10 wt% to 20 wt% hard segments), revealing the thermal invariance of poorly organized domains. Based on these data, we also discuss the importance of chain diffusion in the crystallization process. Applying fast scanning calorimetry allows us to link fundamental understanding to industrial application. © 2018 Society of Chemical Industry     

Blends of bacterial poly[(R)‐3‐hydroxybutyrate] with oligo[(R,S)‐3‐hydroxybutyrate]‐diol

The miscibility, melting and crystallization behaviour of poly[(R)‐3‐hydroxybutyrate], PHB, and oligo[(R,S)‐3‐hydroxybutyrate]‐diol, oligo‐HB, blends have been investigated by differential scanning calorimetry: thermograms of blends containing up to 60 wt% oligo‐HB showed behaviour characteristic of single‐phase amorphous glasses with a composition dependent glass transition, T_g, and a depression in the equilibrium melting temperature of PHB. The negative value of the interaction parameter, determined from the equilibrium melting depression, confirms miscibility between blend components. In parallel studies, glass transition relaxations of different melt‐crystallized polymer blends containing 0–20 wt% oligo‐HB were dielectrically investigated between ?70 °C and 120 °C in the 100 Hz to 50 kHz range. The results revealed the existence of a single α‐relaxation process for blends, indicating the miscibility between amorphous fractions of PHB and oligo‐HB. © 2002 Society of Chemical Industry     

Design guidelines for titania-silica-alumina ceramics with tuned anatase to rutile transformation

Titania-based ceramics with adjustable anatase-rutile fractions were obtained by milling of anatase, quartz and corundum precursors, uniaxial pressing and firing at 1100?°C. The influence of silica and alumina, combined with milling time and compaction pressure, was studied by design of experiments. The L9 orthogonal array with a three-level noise factor was employed. Firing of pure titania at 1100?°C yielded complete anatase to rutile transformation (ART), whereas stabilized samples show that an optimum amount of 9% silica and 33% alumina reduces phase transformation to only about 5?wt% rutile. An extended correlation matrix combined with analysis of variance (ANOVA) was applied to assess the combined effects of quartz, alumina, milling time and uniaxial compressing pressure on relative density, and anatase to rutile transformation. Results show absence of ART after milling, and controlled partial conversion of anatase to rutile after firing. Very good fitting was obtained by multivariate analysis on considering first and second order terms for dependence on silica contents and interactions between silica and each of the remaining factors, including milling time. This empirical dependence could be interpreted on a sound physicochemical basis, allowing the prediction of suitable compositions and processing conditions to obtain rutile-free samples by conventional ceramic processing, and to design ceramic samples with controlled fractions of anatase and rutile.     

Drop‐and‐catch (DnC) calorimetry using aerodynamic levitation and laser heating

Design, calibration, and operation of a system for drop‐and‐catch (DnC) calorimetry on oxides from temperature above 1500°C are described. This system allows the measurement of heat contents and heats of fusion by drop calorimetry of small (100 mg or less) samples held by containerless levitation at high temperature and dropped in a calorimeter at room temperature. The spheroids, 2‐3 mm in diameter, prepared by laser melting of powders, are aerodynamically levitated in a splittable nozzle levitator and laser heated to the desired temperature monitored by radiation thermometry. The sample is dropped by splitting the nozzle and caught by splittable water‐cooled calorimetric plates at 25°C, which provide complete enclosure of the sample to avoid heat loss by radiation. The drop time is ~0.1 seconds, calorimeter equilibration time after the drop is ~15 minute. DnC experiments are automated with software‐controlled laser power and programmable delay between splitting the nozzle and catching the sample. The fusion enthalpy of Al₂O₃ measured by DnC calorimeter, 120 ± 10 kJ/mol, agrees well with previously reported values. The system can be used for measurements of fusion enthalpies of refractory oxides amenable to laser heating as well as for splat quenching of oxide melts.     

Low‐Cost Silicon Nitride from β‐Silicon Nitride Powder and by Low‐Temperature Sintering

Aiming to manufacture low‐cost silicon nitride components, a low‐cost β powder was chosen as a raw powder and low‐temperature sintering at 1550–1600°C under atmospheric pressure nitrogen was carried out. The silicon nitride from β powder with 5 wt% Y₂O₃ and 5 wt% MgAl₂O₄ additives and sintered at 1600°C for 8 h was successfully densified, and it exhibited moderate strength and toughness of 553 MPa ± 22 and 3.5 MPa m^1/2, respectively. The results indicate that the low‐temperature sintering of the low‐cost β powder has a potential to reduce cost of components.     

Preparation and thermal properties of bio‐based gallic acid epoxy/carbon nanotubes composites by cationic ring‐opening reaction

In order to prepare the bio‐based polymeric materials, a gallic acid epoxy resin (GA‐ER) is synthesized by using biodegradable gallic acid, and the nanocomposites of GA‐ER/glycidyl methacrylate (GMA)/multiwalled carbon nanotubes (MWCNTs) were prepared by dual hybrid cationic ring‐opening reaction. Differential scanning calorimetry (DSC) results show that the curing reaction temperature of the nanocomposites is between 150 and 225°C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results suggest that MWCNTs are homodispersing in the GA‐ER/GMA matrix when the MWCNTs content is not more than 1.0 wt%. The glass transition temperature of the nanocomposite with 0.5 wt% MWCNTs is 9.3°C higher than that of pure resin system. The initial thermal degradation temperature and degradation activation energies E_a of the nanocomposite with 1.0 wt% MWCNTs is 10°C and 68.6 kJ/mol higher than that the pure resin system, respectively. POLYM. COMPOS., 37:3093–3102, 2016. © 2015 Society of Plastics Engineers     

Catalytic para‐xylene maximization: III. Hydroisomerization of meta‐xylene on H‐ZSM‐5 catalysts containing different platinum contents

Hydroisomerization of meta‐xylene was carried out using catalysts containing 0.15–0.60 wt% Pt on H‐ZSM‐5 zeolite, in a pulsed microreactor system connected to a gas chromatograph at a flow of hydrogen of 20 cm³ min⁻¹ and temperatures of 275–500 °C. Increasing temperature, increased isomerization with low rates. Increasing Pt content of the catalyst, decreased hydrodealkylation considerably via masking strong acid sites as revealed by temperature programmed desorption of ammonia measurements. Formation of trimethylbenzenes was inhibited by Pt incorporation in the H‐ZSM‐5 zeolite. The activation energies obtained for meta‐xylene hydroisomerization were relatively low (24.4–61.6 kJ mol⁻¹) on all catalysts under study. Para‐xylene yields in the xylenes mixture of product relative to the corresponding thermodynamic equilibrium values amount to about 0.8–0.9 at temperatures of 400–500 °C but were lower at lower temperatures. © 1999 Society of Chemical Industry     

High‐resolution thermogravimetry of poly(2,6‐dimethyl‐1,4‐phenylene oxide)

The thermal degradation and kinetics of poly(2,6‐dimethylphenylene oxide) (PPO) were studied by high‐resolution thermogravimetry. The thermogravimetry measurements were conducted at an initial heating rate of 50°C min⁻¹, resolution 4.0, and sensitivity 1.0 in both nitrogen and air from room temperature to 900°C. A two‐step degradation process was clearly revealed in air at the temperatures of 430°C and 521°C. The thermal degradation temperatures and kinetic parameters of the PPO appear to be higher in air than in nitrogen, indicative of a higher thermostability in air. The temperature, activation energy, order, and frequency factor of the thermal degradation of the PPO in nitrogen are 419°C, 100–120 kJ mol⁻¹, 0.5, and 13–17 min⁻¹, respectively. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1887–1892, 1999     

Thermal characteristics and pyrolysis of methyl‐di(phenylethynyl)silane resin

Thermal stability of a recently synthesized polymeric methyl‐di(phenylethynyl)silane (MDPES) resin was studied using a number of thermal and spectrometric analytical techniques. The polymer exhibits extremely high thermal stability. Thermogravimetric analysis (TGA) shows that the temperature of 5% weight loss (T_d5) was 615°C and total weight loss at 800°C was 8.9%, in nitrogen atmosphere, while in air, T_d5 was found to be 562°C, and total weight loss at 800°C was found to be 55.8% of the initial weight. Differential thermal degradation (DTG) studies show that the thermal degradation of MDPES resin was single‐stage in air and two‐stage in nitrogen. The thermal degradation kinetics was studied using dynamic TGA, and the apparent activation energies were estimated to be 120.5 and 114.8 kJ/mol in air, respectively, by Kissinger and Coats–Redfern method. The white flaky pyrolysis residue was identified to be silicon dioxide by FTIR and EDS, indicating that the thermal stability of polymer may be enhanced by the formation of a thin silicon dioxide film on the material surface. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 103: 605–610, 2007     

High‐resolution thermogravimetry of cellulose esters

Cellulose dinitrate (CDN), cellulose diacetate (CDA), and cellulose triacetate (CTA) were subjected to high‐resolution thermogravimetry (TG) at a variable heating rate in air. The TG curves, the derivative TG curves, the second derivative TG curves, and heating rate curves are discussed. The thermal degradation temperature and kinetic parameters are presented and compared to those obtained with traditional TG at a constant heating rate. The degradation process of the cellulose esters is speculated. Among the three cellulose esters, CDN exhibits the lowest degradation temperature of (213°C) but the largest degradation activation energy of (237–269 kJ/mol). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 573–578, 1999