Silica-coated nanocrystalline TiO2 with improved thermal stability

Deposition of a SiO₂ coating on anatase TiO₂ nanocrystals is shown to improve their thermal stability. As low as 0.5% Si was shown to preserve the small anatase crystallite size after calcination at 600?°C. Such treatment led to considerable sintering of TiO₂ nanocrystals without the silica with the average particle size growth from 9 to 50?nm, surface area decrease from 135 to 22?m²/g and partial anatase conversion to rutile. The phase composition, crystallite size, and surface area of 5%Si-TiO₂ samples were largely preserved till the temperatures as high as 800?°C whereas the anatase phase was mostly stably even after calcination at 1000?°C. The phase transformation from anatase to rutile in xerogel TiO₂ and TiO₂@SiO₂ samples apparently did not occur until the crystallites grew larger than the critical size about 50?nm. Electron-acceptor sites capable of ionizing perylene to its radical cations were observed on all samples with anatase crystalline structure. So, the silica shell deposition improves the TiO₂ thermal stability without limiting access to the surface active sites.     

Application of grits waste as a renewable carbonate material in manufacturing wall tiles

This work focuses on the reuse of grits waste, from cellulose industry, as a raw material to replace traditional carbonate material in ceramic wall tiles. Wall tile formulations bearing up to 15?wt% of the grits waste were prepared for replacement of calcareous. The tile manufacturing route consisted of dry powder granulation, uniaxial pressing, and firing at temperatures ranging from 1100?°C to 1180?°C by using a fast-firing cycle. The wall tile specimens were tested to determine their physical and mechanical properties (linear shrinkage, water absorption, apparent porosity, apparent density, breaking strength, and flexural strength). The firing behavior, phase transformations, and microstructure were evaluated by dilatometry, XRD, and SEM. The results showed that the fired wall tile specimens are composed of anorthite and quartz, as major mineral phases, and mullite as a minor phase. It was found that the grits waste had a positive influence on the properties and microstructure of the wall tile specimens. The results also revealed that the grits waste from cellulose industry could be used as a total replacement of traditional calcareous material in wall tile formulations.     

Effect of pressure on TiO2 crystallization kinetics using in‐situ high‐temperature synchrotron radiation diffraction

The phase transformation behavior of TiO₂ sol‐gel synthesized nanopowder heated in a sealed quartz capillary from room temperature to 800°C was studied using in‐situ synchrotron radiation diffraction (SRD). Sealing of the capillary resulted in an increase in capillary gas pressure with temperature. The pressures inside the sealed capillary were calculated using Gay‐Lussac's Law, and they reached 0.36 MPa at 800°C. The as‐synthesized material was entirely amorphous at room temperature, with crystalline anatase first appearing by 200°C (24 wt% absolute), then increasing rapidly in concentration to 89 wt% by 300°C and then increasing more slowly to 97 wt% by 800°C, with there being no indication of the anatase‐to‐rutile transformation up to 800°C. The best estimate of activation energy for the amorphous‐to‐anatase transformation from the SRD data was 10(2) kJ/mol, which is much lower than that observed when heating the material under atmospheric pressure in a laboratory XRD experiment, 38(5) kJ/mol. For the experiment under atmospheric pressure, the anatase crystallization temperature was delayed by ~200°C, first appearing after heating the sample to 400°C, after which crystalline rutile was first observed after heating to 600°C. The estimated activation energy for the anatase‐to‐rutile transformation was 120(18) kJ/mol, which agrees with estimates for titania nanofibers heated under atmospheric pressure. Thus, heating the nanopowders material under pressure promoted the amorphous‐to‐anatase transformation, but retarded the anatase‐to‐rutile transformation. This behavior is believed to occur in an oxygen‐rich environment and interstitial titanium is also expected to form when the material is heated under high gas pressure. This suggests that atmospheric oxygen appears to accelerate the amorphous‐to‐anatase transformation, whereas interstitial titanium inhibits TiO₂ structure relaxation, which is required for the anatase‐to‐rutile transformation.     

Preparation and characterization of ceramic nanofiltration membrane prepared from hazardous industrial waste

Kiln rollers, which are widely used in ceramic tiles production, are usually subjected to surface grinding to remove the contaminations. The resulted fine powder is considered useless waste and a hazardous source of environmental pollution particularly as it contains health-threatening fine free silica. In the present paper, the grind waste from kiln rollers was reused as raw material in the fabrication of nanofiltration ceramic membrane. The samples of produced ceramic membranes were formed into disks by adding 15% (by weight) organic binder solution with 2% concentration, then pressed at 35 MPa, dried and fired at temperatures range from 1100°C to 1300°C for 1 hour soaking time. It was found that the best firing temperature to produce nanofiltration ceramic membrane is 1250°C, where the ceramic membrane provides high removal of turbidity and high monovalent, divalent, and trivalent salts separation percentage.     

Kinetics of structural transformations in silica gel and physicochemical processes involved in the firing of dinas refractories containing dry mineralizers

The laws of phase formation in silica gel products obtained using a limestone residue are established. Results of x-ray diffraction, petrographic, and other analyses show that the process of transformation of quartz into high-temperature modifications of silica gel proceeds at a markedly higher rate if the limestone residue is used in a mixture with pyrite cinder rather than with a conventional lime-iron additive. This is related to certain special features of the mineralizer composition and the physicochemical processes involved in the firing. The temperature dependence and kinetics of the conversion of silica gel into its high-temperature structural modifications during the firing of dinas with dry mineralizers were studied in the course of heating in the temperature range from 1200 to 1420°C and during a hold at the maximum heat-treatment temperature. Equations describing the structural transformation processes are derived. A relationship between the physico-chemical properties of the samples and the features of the phase formation processes is demonstrated. Translated from Ogneupory i Tekhnicheskaya Keramika, No. 2, pp. 17–21, February, 1997.     

Thermally stable and photocatalytically active titania for ceramic surfaces

The most photocatalytically active titania modification anatase must be stabilised to achieve high photocatalytic activity in ceramic processes at temperatures above 1000 °C. Thermally stable TiO₂ powders were prepared by the addition of silica and boehmite nanoparticles and deposited on corundum substrates and lead-free glazes. The powders and coatings were fired at increasing temperatures, and stabilisation of the anatase phase was achieved up to 1200 °C. In general, thermal stability was found to be lower when coated on substrates compared to the powder alone, and the extent of reduction depended on the chemical composition of the substrate. Only a slight modification of the titania electronic structure was found, indicating only weak interactions between silica and titania. Based on these results it is possible to assume an amorphous silica and alumina shell encases the titania particles which prevents grain growth and the anatase to rutile phase transformation.     

Complex mullite structures fabricated via digital light processing of a preceramic polysiloxane with active alumina fillers

By taking advantage of the multi-functional properties of preceramic polymers, their transformation into ceramic material at low sintering temperatures and the processing capabilities of polymer manufacturing processes, mullite components were fabricated by additive manufacturing. A photocurable silicone preceramic polymer resin containing alumina particles was shaped into complex structures via Digital Light Processing. Dense and crack-free, highly complex porous mullite ceramics were produced by firing a mixture of a commercially available photosensitive polysiloxane as the silica source, containing alumina powder as active filler, in air at a low sintering temperature (1300 °C). In particular, the developed formulations, coupled with the additive manufacturing approach, allow for precise control of the architecture of the porous ceramic components, providing better properties compared to parts with stochastic porosity.     

In situ synthesis of orange rutile ceramic pigments by non-conventional methods

Different precursor-mixtures of orange Cr,Sb-TiO₂ ceramic pigment have been obtained by non-conventional methods (heterogeneous ammonia coprecipitation, urea homogeneous coprecipitation, PECHINI polyester method and an original aqueous–organic coprecipitation method in water–diethylenglycol medium) in order to produce in situ the pigment through the ceramic body firing. The pigmenting performances of powders were appraised in two cases: (a) as ceramic pigment for glazed porcelain stoneware and (b) as ceramic inks for screen printing of porcelain stoneware. Samples were characterised by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), UV–vis-NIR spectroscopy by diffuse reflectance method, CIE-L*a*b* colour parameters, BET specific surface area and crystallite size measured by the Scherrer method. The colouring performance of raw powders obtained by non-conventional methods in glazed porcelain stoneware improves that of the ceramic samples fired at 1100 °C used as reference. TEM observations indicate nanostructured powders with pigmenting performance depending on factors such as their specific surface area (BET), the crystalline phases detected by XRD (e.g. anatase–rutile presence) and their crystallite size (Scherrer measurements). Ammonia coprecipitated samples, both in water and in water–diethylenglycol medium without surfactant addition, or modified by the addition of sodium dodecyl sulphate as surfactant, stand out by their colouring performance.     

Development of TiO2 white glazes for ceramic tiles

The objective of this work was the use of titania polymorphs (rutile and anatase) in substitution of zirconia as the main component for producing white opacity in ceramic glazes for tile coatings. Initially, total zirconia (12% mass fraction) was replaced in the standard frit by rutile and by anatase in mass fractions of 5%, 10% and 15%, forming two frit groups processed as ceramic glazes. The glaze color was determined by spectrophotometry and the glaze microstructure by XRD and SEM. The results showed the frit containing 10% anatase formed a totally white glaze presenting excellent coating capacity. The frits containing rutile produced yellow opacity. The results of microscopy and X-rays diffraction revealed that opacity was caused by tiny rutile crystals in the anatase frits and by titanite crystals in the rutile frits.     

Effect of alkali roasting and sulfatization on the extraction of different metal oxides from waste alum sludge

Water treatment plants (WTP) generate a significant amount of sludge as byproducts with environmentally harmful elements. Thus, this work focused on the recycling of alum sludge through the extraction of different metal oxides, i.e., Al₂O₃, Fe₂O₃ and SiO₂, for use in different applications, such as ceramics, cement, and agriculture. The extraction of Al₂O₃, Fe₂O₃, and SiO₂ from alum sludge was performed using sulfatization and roasting to compare which of the two processes could produce the metal oxides of the highest purity. Precipitated powders were calcined at 700°, 900° and 1100 °C. Moreover, the obtained prepared and calcined powders were characterized by studying their phase compositions, microstructure, particle size, and surface area. Results indicated that roasting achieved the highest yield of alumina. Iron oxide was extracted mostly in maghemite form through roasting after calcination at 1100 °C. Further, silica was obtained in cristobalite and quartz phases after calcination at 1100 °C for the samples prepared through sulfatization. However, these phases of silica were combined with albite and obtained after calcination at 1100 °C for the samples prepared through roasting method.     

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.     

EFFECT OF SIZE AND SHAPE OF TITANIUM OXIDE CRYSTALS ON SPECTROPHOTOMETRIC PROPERTIES OF TITANIUM-BEARING PORCELAIN ENAMELS*

Color changes of three titanium enamels given varied firing treatment were investigated. The size and shape of titanium oxide particles were studied with the electron microscope, the relative amounts of anatase and rutile were determined from X-ray analyses, and spectrophotometric curves of the fired panels were made. Electron micrographs showed that rutile particles recrystallized as needles or “sticks,” whereas anatase appeared as ill-defined, irregularly shaped, rounded particles. With increasing firing temperature or firing time (1) rutile particles showed a greater increase in size than anatase particles, (2) the amount (by weight or volume) of anatase crystals decreased and the amount of rutile crystals increased, and (3) a color change from blue-white to cream-white was observed. The change in color seemed to be related to the scattering of blue light by small particles at lower temperatures or shorter periods of firing. As the size of opacifying particles increased, the scattering of blue light decreased, and the characteristic absorption of visible light in the shorter wave lengths was more apparent. In enamels containing both anatase and rutile, the smaller anatase crystals were predominant at lower and the larger rutile crystals at higher temperatures, so that sharp changes of color were observed as the firing temperature was increased.     

Phase Transformation of Nanocrystalline Anatase Powders Induced by Mechanical Activation

The microstructural evolution of nanocrystalline anatase TiO₂ during high-energy planetary ball milling was studied. The results show that mechanical activation induces the transformations of nanocrystalline TiO₂ from anatase to srilankite and rutile at room temperature and under ambient pressure. As the milling time increases, more anatase powder transforms to the srilankite and rutile phase, and the particle size of the powder decreases. There is no indication of the formation of amorphous phase during ball milling.     

Crystallization and Phase Transformation in TiO2-Opacified Porcelain Enamels: I, Theory

The theory of nucleation and growth was used to develop equations describing the crystallization and phase transformation processes occurring during the firing of a TiO₂-opacified porcelain enamel. The concentrations of ana-tase and of rutile depend on four parameters: the rate of inversion of anatase to rutile, the percentage of crystallization which is to anatase, the solubility, and a crystallization rate constant.     

Preparation and characterization of photocatalytic titania–alumina composite membranes by sol–gel methods

Titania–alumina composite membranes containing 10 and 20 mol% alumina were prepared by two different sol–gel methods; co-hydrolysis and separately peptized. The samples were characterized by different techniques. XRD results showed that for the composite membranes the anatase to rutile transformation temperature was increased by 200 and 300 °C. According to specific surface area results, alumina effectively increased the specific surface area of composite membranes compared to pure titania membranes. Microstructure of composite supported membranes was considered by scanning electron microscopy and showed a crack-free layer with 1 μm thickness. The photocatalytic activity of composite samples showed that alumina addition up to an optimum amount can slightly affect the photocatalytic activity of titania.     

Recycling detoxified cement asbestos slates in the production of ceramic sanitary wares

The recycling of cement asbestos slates (CASs) thermally treated in air at 1100 °C as secondary raw material in the production of Vitreous China (VC) sanitary wares has been investigated. Deactivated cement asbestos powder (DCAP) has been used in individual substitutions (5 wt%) of quartz and feldspar. The single raw materials, the ceramic technological properties before and after firing, and the phases and microstructure evolution during firing have been investigated with a variety of techniques, including those commonly used for production quality checks and instrumental methods for mineralogical analyses. DCAP acts as flux rather than as inert in the firing process, promoting greification. Although the substituted samples have some critical aspects that need to be addressed before processing, such as the presence of sulphate salts that increase the dispersant demand and the colour of the fired ceramic body, the overall technological properties are comparable to those of normal production, suggesting the possible reuse of DCAP powder in the production of sanitary wares.     

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.     

Kinetics of Opacification of a TiO2-Opacified Cover Coat Enamel

Quantitative X-ray diffraction measurements were used to study the firing behavior of a typical TiO₂-opacified cover coat enamel. A model was developed for predicting the anatase and rutile concentrations as a function of time and temperature of firing. The model consists of three first order reactions: crystallization of anatase, crystallization of rutile, and inversion of anatase to rutile. It predicts successfully over a wide range of time-temperature conditions. Discrepancies are found, however, for short-time, low-temperature firings. The reflectance data do not correlate well with the crystalline concentration data. The correlation with color data is better, but is not perfect.     

The effects of mechanical activation on the sintering of mullite produced from kaolin and aluminum powder

In this work, the effects of mechanical activation on the sintering of mullite produced from kaolin and aluminum metal powder was investigated. Because of the higher content of silica in kaolin it is necessary to add alumina or aluminum oxide in order to obtain the stoichiometric mullite composition. After mechanical treatment for different milling time, the reactions and phase transformations between kaolin and aluminum metal powder were studied using thermal techniques (DTA/TG), X-ray diffraction (XRD) and infrared spectroscopy (FT-IR). The heated samples at different temperatures were studied by XRD, apparent density, open porosity measurements and SEM analysis. The results showed the formation of silicon, quartz and small amount of nacrite after 40 h of milling at room temperature. All mixture powders milled for different time showed the formation of several alumina transitions during heat treatment. The formation of alumina transitions, α-alumina, cristobalite crystallization of and mullite (primary and secondary) formation was affected by ball milling time. The mixture of kaolin and aluminum milled for 40 h show the formation of kyanite (Al₂SiO₅) at 1300 °C. The mechanical treatment enhances the formation and sintering of mullite.     

Crystallization and Phase Transformation in TiO2-Opacified Porcelain Enamels: 11, Cornparison of Theory with Experiment

Equations were developed to predict the concentrations of anatase and rutile in a TiO₂opacified porcelain enamel as a function of the time and temperature of firing. These equations were applicable over the entire useful firing range: from 660° to 940°C and from 1 to 64 min. The constants in these equations yield solubility data as well as the appropriate rates. The solubility versus temperature curve is bimodal. The activation energies are 87.4 kcal/mol for inversion of anatase to rutile, 32.0 kcal/mol for crystallization of anatase, and 28.3 kcal/mol for crystallization of rutile.