Reactive Hydrothermal Liquid‐Phase Densification (rHLPD) of Ceramics – A Study of the BaTiO3[TiO2] Composite System

A densification process called reactive hydrothermal liquid‐phase densification (rHLPD), based on principles of hydrothermal reaction, infiltration, reactive crystallization, and liquid‐phase sintering, is presented. rHLPD can be used to form monolithic ceramic components at low temperatures. The densification of barium titanate–titania composite monoliths was studied to demonstrate proof of concept for this densification model. Permeable, green titania (anatase) compacts were infiltrated with aqueous barium hydroxide solutions and reacted under hydrothermal conditions in the temperature range 90°C–240°C. The effects of reaction time and temperature on the conversion of titania (anatase) into barium titanate were studied. Utilizing a 72 h reaction at 240°C between l.0 M Ba(OH)₂, an anatase (TiO₂) powder compact, and a corresponding Ba/Ti ratio of 1.5, it was possible to crystallize a composite 95 wt% (88 mol%) BaTiO₃ and 5 wt% (12 mol%) TiO₂. The composite had a relative density of ~90% with a compressive strength of 172 ± 21 MPa and a flexural strength of 49 ± 4 MPa.     

Effect of graphite content on properties of B4C‐W2B5 ceramic composites by in situ reaction of B‐Gr‐WC

Strip‐shaped W₂B₅ reinforced B₄C ceramic composites were prepared via in situ reaction of boron(B)‐graphite(Gr)‐WC system by powder metallurgy (P/M). In order to study the effect of the graphite content on the properties of the as‐fabricated ceramic composites, the powder mixture of B‐Gr‐WC with various amounts of Gr powder were blended and consolidated by spark plasma sintering (SPS). The sintering parameters were shown as following: sintering pressure was set as 30 MPa; The three‐step sintering temperature was 1100‐1550‐1700°C and the duration time was set as 5‐5‐6 minutes, respectively. In situ formed strip‐shaped W₂B₅ particles were dispersed homogeneously in B₄C matrix, which resulted in a remarkable improvement on the fracture toughness and mechanical properties. Appropriate 5vol% residual Gr in the composite shows positive effect on the mechanical properties which achieved an optimal counter‐balance of fracture toughness and hardness, the relative density was 99.8%, the Vickers hardness can reach 30.2 GPa, and the fracture toughness was 11.9 MPa·m^1/2 when the sintering temperature was set at 1700°C.     

Translucent Yttria‐ and Silica‐Doped Mullite Ceramics with Anisotropic Grains Produced by Spark Plasma Sintering

Translucent, high‐performance, mullite ceramics with anisotropic grains were prepared by the spark plasma sintering (SPS) of a powder mixture consisting of commercial mullite powder, which already contained small amounts of alumina (θ and α) and silica (cristobalite) (≤3 wt% in total), to which 2 and 1 wt% of yttria and amorphous silica was admixed, respectively. The combination of low‐viscosity Y₂O₃–Al₂O₃–SiO₂ transient liquid formation and SPS sintering provided enhanced densification, also provoking anisotropic grain growth (which became exaggerated after 20 min of SPS dwell time), at a relatively low sintering temperature of 1370°C. In this way, it was possible to meet the conflicting demands for obtaining a dense mullite ceramic with anisotropic grains, ensuring good mechanical properties, while preserving a noticeable light transmittance. In terms of mechanical and optical properties, the best results were obtained when SPS dwell times of 5 and 10 min were employed. The as‐sintered samples possessed densities in the range 3.16–3.18 g/cm³, anisotropic grains with an aspect ratio (AR) of 7 and a grain thickness of approximately 0.45 μm, a flexural strength between 350 and 420 MPa, a Vickers indentation toughness and a hardness of approximately 2.45 MPa·m^1/2 and 15 GPa, respectively, and an optical transmittance of between 30% and almost 50% in the IR range.     

Preparation of poly(methyl methacrylate‐co‐maleic anhydride)/SiO2?TiO2 hybrid materials and their thermo‐ and photodegradation behaviors

The optically transparent poly(methyl methacrylate‐co‐maleic anhydride) P(MMA‐co‐MA)/SiO₂? TiO₂ hybrid materials were prepared using 3‐aminopropyl triethoxysilane as a coupling agent for organic and inorganic components. Real‐time FTIR was used to monitor the curing process of hybrid sol, indicating that imide group formation decreased with increasing titania content. scanning electron microscopy, atomic force microscopy, and differential scanning calorimetry results confirmed their homogeneous inorganic/organic network structures. TGA analysis showed that incorporated titania greatly prohibits the thermodegradation of hybrid films, especially at the content of 5.3 wt %, showing an increase of about 32.6°C at 5% loss temperature in air. The UV degradation behavior of P(MMA‐co‐MA) studied by quasi‐real‐time FTIR showed that TiO₂ incorporated in the hybrid network provides a photocatalytic effect rather than a UV‐shielding effect. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1714–1724, 2005     

Effects of ZnO and B2O3 on the Microstructure and Microwave Dielectric Properties of 5Li2O‐1Nb2O5‐5TiO2 Ceramics

The effects of ZnO and B₂O₃ addition on the sintering behavior, microstructure, and the microwave dielectric properties of 5Li₂O‐1Nb₂O₅‐5TiO₂ (LNT) ceramics have been investigated. With addition of low‐level doping of ZnO and B₂O₃, the sintering temperature of the LNT ceramics can be lowered down to near 920°C due to the liquid phase effect. The Li₂TiO₃ss and the “M‐phase” are the two main phases, whereas other phase could be observed when co‐doping with ZnO and B₂O₃ in the ceramics. And the amount of the other phase increases with the ZnO content increasing. The addition of ZnO does not induce much degradation in the microwave dielectric properties but lowers the τ_f value to near zero. Typically, the good microwave dielectric properties of ε_r = 36.4, Q × f = 8835 GHz, τ_f = 4.4 ppm/°C could be obtained for the 1 wt% B₂O₃ and 4 wt% ZnO co‐doped sample sintered at 920°C, which is promising for application of the multilayer microwave devices using Ag as internal electrode.     

Optimizing the mechanical properties of TiO2/PA12 nano-composites fabricated by SLS 3D printing

In this paper, the selective laser sintering process was used to fabricate the TiO₂/PA12 nano-composite parts by considering the parameters of laser power, scanning speed, and TiO₂ content. The response surface methodology was used to improve the mechanical properties of TiO₂/PA12 nano-composite parts. The fracture surface characteristics of the specimens were examined using the scanning and transmission electron microscopy. The results indicated that the increase in laser power from 10 to 15 W improved the tensile strength, modulus, and impact strength of the nano-composite parts because of the fine dispersion of TiO₂ nano-particles. An increase in the scanning speed from 2000 to 3000 mm/s resulted in the reduction of tensile strength and modulus due to lower heat input and consequently incomplete densification of polyamide-12. In addition, the increase of TiO₂ content up to 5 wt% can improve the tensile strength, modulus, and impact strength, but requires increasing the laser power. However, the mechanical properties of the nano-composite parts were enhanced simultaneously at laser power of 12.4 W, scanning speed of 2000 mm/s and TiO₂ content of 1.9 wt%. Moreover, the addition of TiO₂ up to 5 wt% showed a slight influence on thermal stability and crystallinity of the sintered specimens.     

Nano- and micrometre additions of SiO2, ZrO2 and TiO2 in fine grained alumina refractory ceramics for improved thermal shock performance

The present contribution investigates the influence of micro-metre- as well as nano-metre-additions of zirconia (ZrO₂), titania (TiO₂), silica (SiO₂) and magnesia (MgO) into alumina-rich fine grained ceramic materials for refractory applications. Slip casted samples in the system alumina–zirconia–titania (AZT), alumina–zirconia–titania–silica (AZTS) and alumina–zirconia–titania–magnesia (AZTM) were sintered and the physical as well as mechanical properties were investigated as fired and after thermal shock treatments. The generation of a micro-crack network after sintering due to the formation of phases with different thermal expansion coefficients and the formation and decomposition of aluminium titanate (Al₂TiO₅) before and after thermal shock exposure leads to higher strengths after thermal shock attack.     

Preparation,characterization, and properties of TiO2/PLA nanocomposites by in situ polymerization

In situ polymerization method was used to prepare TiO₂/polylactide (PLA) nanocomposites with different contents of TiO₂ in this work. The size of the organically modified TiO₂ particles was investigated by X‐ray diffraction (XRD) analysis. Scanning electron microscope (SEM) shows that nano‐TiO₂ particles disperse in the PLA evenly when the content of TiO₂ is low (less than 3 wt%). The differential scanning calorimeter (DSC), thermogravimetry analysis (TGA), and tensile test were used to study the thermal and mechanical properties of the composites. Results show that both the thermal and mechanical properties are markedly improved when the content of TiO₂ is 3 wt%. UV light irradiation and solution degradation experiment show that degradation of the composites is higher when the content of TiO₂ increases and due to the introduction of TiO₂ particles in the nanocomposites, the TiO₂/PLA nanocomposites exhibit remarkable bacteriostasic activity. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Effect of TiO2 addition on microstructure and mechanical properties of alumina-based cores prepared by sol-gel method

Alumina-based ceramic cores have widespread applications especially in the investment casting of turbine blades due to chemical inertness with most of the superalloys, capability of machining in the green state, and their mechanical stability at high temperatures. The present work studied the effects of TiO₂ addition to the alumina-based cores. These cores were prepared via the sol-gel method process by mixing alumina powders with NH₄Cl and silica sol. The effects of adding different amounts of titania from 5 to 30 wt% and different sintering procedures on mechanical, physical, thermal, chemical, and microstructural features of the bodies were investigated. According to the results of rheology measurements of the slurries and flexural strength of the green bodies, the suitable amount of solid loading was 45 vol. %. The results showed that there is an optimum content for TiO₂ addition. The specimen contained 15 wt. % titania and sintered at 1400°C for 2 hours had the thermal expansion coefficient as low as 4.8 × 10⁻⁶/°C (25-900°C), suitable mechanical properties as a result of tialite formation, and apparent porosity of 28 vol. %, respectively. The result of creep deformation test showed that this specimen had near zero deformation at 1650°C.     

Aluminum‐borate‐whiskers‐reinforced bismaleimide composites. 1: preparation and properties

Aluminum‐borate‐whiskers‐reinforced bismaleimide (BMI/Al₁₈B₄O₃₃) composites were prepared, and the mechanical and thermal properties were investigated. Results show that the coupling agent used for surface treatment of whiskers has a great effect on the properties of these materials. Composites containing surface‐untreated whiskers, or silane‐compound‐KH 921‐treated whiskers, exhibited initially only a slight increase in the flexural strength when the whiskers weight content increased up to 5 wt%; thereafter, they showed a sharp decrease when the whiskers content was higher than 5 wt%. On the other hand, impact strength tests showed that the addition of the two kinds of whiskers decreased the impact strength of the composites. However, studies of the composite containing borate (BE4)‐treated whiskers showed that its flexural strength greatly increased with increasing whisker content. Moreover, the composite showed initially an increase in impact strength with a whisker content up to 10 wt%, then showing a slight decrease when the whisker content reached 15 wt%. Scanning electron microscopy observations revealed that the two coupling agents (KH 921 and BE4) employed in this work tend to change the fracture features of the composites from brittleness to that of ductile behaviour. Copyright © 2004 Society of Chemical Industry     

Effect of TiO2 Doping on the Sintering Process,Mechanical and Magnetic Properties of NiFe2O4 Ferrite Ceramics

TiO₂‐doped NiFe₂O₄ samples were prepared via ball‐milling and two‐step sintering processes. Besides NiFe₂O₄ phase, two new phases, NiTiO₃ and Fe₂TiO₅, formed in TiO₂‐doped samples. The temperature of sintering onset for 1.0 wt% TiO₂‐doped samples is 230°C lower than that of undoped samples. Early‐stage synthesis process of TiO₂‐doped NiFe₂O₄ ceramics is controlled by grain boundary diffusion mechanism. Increasing TiO₂ content from 0 to 1.0 wt%, the apparent activation energy decreased from 813.919 KJ/mol to 639.361 KJ/mol. The values of relative density and bending strength reached their maximum value with 1.0 wt% TiO₂. Saturation magnetization, residual magnetization ratio and coercivity decrease with increasing TiO₂ content.     

Reliability studies of gelcast fused silica between organic and inorganic binder systems

Fused silica ceramics was prepared by using conventional organic binder, mathacrylamide‐N,N′‐methylenebisacrylamide (MAM‐MBAM) system by gelcasting process. Mechanical properties of green bodies were studied as a function of solid loading varying from 60 to 72 vol%. After evaluating the green body mechanical properties, the samples were densified at different sintering temperature from 1200 to 1450°C with definite intervals of 50°C and subjected to flexural strength analysis. Variation in flexural strength with sintering temperature was observed and correlated with the quantity of devitrification of fused silica during sintering. Quantification of devitrified cristobalite was carried out by using 20 wt% rutile (TiO₂) as an internal standard by X‐ray diffraction. It was found that, as the cristobalite content increased, flexural strength decreased. Reliability studies were carried out for the samples having maximum flexural strength with and without crystalline content. Reliability studies have shown that for this organic binder system the sample sintered at 1300°C is crystalline free and most reliable product. The mechanical properties and reliability of this product processed with organic binder are compared with inorganic binder system. Results indicate that the sample fabricated using inorganic binder system is exhibiting high Weibull modulus and thus better reliability.     

Role of Nano‐ and Micron‐Sized Particles of TiO2 Additive on Microwave Dielectric Properties of Li2ZnTi3O8 – 4 wt% TiO2 Ceramics

Microwave dielectric ceramics with the composition of Li₂ZnTi₃O₈ – 4 wt% TiO₂ were synthesized by the conventional solid‐state reaction. 4 wt% TiO₂ powders with different particles size were added to the Li₂ZnTi₃O₈ ceramic. Then the ceramic samples were sintered at temperatures 1075°C, 1050°C, 1000°C, and 950°C for 4 h. The effect of the particles size of TiO₂ additive on the microwave dielectric properties of the ceramics has been investigated. In the study two categories of particles size of TiO₂ additive have been used; (i) Nanoparticle (50 nm), (ii) Micron sized (40, 5, 1 μm) powder. X‐ray showed that the TiO₂ additive has not solved in the LZT structure and has not almost undergone chemical reaction with the LZT ceramic. The results showed that the addition of TiO₂ nanoparticles to the LZT ceramics significantly improved the density and a dense and uniform microstructure and also abnormal grain growth were observed by SEM. The use of TiO₂ nanoparticle reduces porosity and leads to an increase in green density. The maximum density was found to be 98.5% of the theoretical density and the best relative permittivity of 28, quality factor of 68000 GHz and τ_f value of ?2 ppm/°C were obtained for the samples added with 4 wt% of the TiO₂ nanoparticles, sintered at 1050°C for 4 h.     

Atomic oxygen erosion resistance of titania–polyimide hybrid films derived from titanium tetrabutoxide and polyamic acid

A series of polyimide/titania (PI/TiO₂) hybrid films have been successfully synthesized based on titanium tetrabutoxide (Ti(OEt)₄), 3,3′,4,4′‐bezonphenone tetracarboxylic dianhydride (BTDA), 4,4′‐oxydianiline (ODA), and 1,3‐bis(aminopropyl) tetramethyldisiloxane (APrTMOS) by a sol–gel process. The atomic oxygen (AO) exposure tests were carried out using a ground‐based AO effects simulation facility. The chemical structure of PI/TiO₂ films was characterized by Fourier transform‐infrared (FT‐IR) spectroscope before and after AO exposure. The glass transition temperature (T_g) and mechanical properties were examined by dynamic mechanical analysis (DMA) and universal mechanical testing machine, respectively. The tensile strength and elongation of the hybrid film decreased with the increase of TiO₂ content, whereas the T_g increased with the increase of TiO₂ content. The effects of TiO₂ content on the morphology and structure evolvement of PI/TiO₂ hybrid films were also investigated using field emission scanning electron microscopy (FE‐SEM) and X‐ray photoelectron spectroscope (XPS), respectively. The results indicated that a TiO₂‐rich layer resulting from the Ti(OEt)₄ formed on the PI film after AO exposure, which decreased the mass loss rate and obviously improved the AO resistance of PI films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fabrication of functionally graded nano‐TiO2‐reinforced epoxy matrix composites

Functionally graded nano‐TiO₂ epoxy matrix composites were successfully fabricated using a centrifugal method. In the preparation of the composite, the aggregation of nano‐TiO₂ occurred during curing, which had a negative effect on the composite performance. To solve this problem, we introduced a silane coupling agent to modify the surface of the nano‐TiO₂, thereby improving the performance and mechanical properties simultaneously. The modified nano‐TiO₂ (s‐TiO₂) had better dispersion in the epoxy resin, making it possible to produce depth gradients of the mechanical properties of functionally graded materials (FGMs). The s‐TiO₂ was characterized with respect to functional groups, morphology, and chemical elements using transmission electron microscopy, X‐ray photoelectron spectroscopy, and Fourier‐transform infrared spectroscopy. The results show that a silane layer was successfully coated on the surface. Also, the gradients of the mechanical and permittivity properties of the FGM indicated that by modifying the surface of the nano‐filler, it is possible to fabricate nano‐filler‐reinforced epoxy matrix FGMs using a centrifugal method. POLYM. COMPOS., 35:557–563, 2014. © 2013 Society of Plastics Engineers     

ZSM-5/TiO<Subscript>2</Subscript> Hybrid Photocatalysts: Influence of the Preparation Method and Synergistic Effect

In this work, the influence of the preparation method of ZSM-5/TiO₂ hybrids on the photocatalytic performance for removal of formaldehyde (HCHO) or trichloroethylene (C₂HCl₃) in gas phase was analyzed. For this purpose, two methods for the synthesis of the hybrids, the incipient wetness impregnation (I) and the mechanical mixing method (M), were selected. The photocatalysts were characterized by N₂ adsorption–desorption, TEM, UV–Vis spectroscopy, XRD and electrophoretic migration. Also, the adsorption ability of the individual materials and hybrids was analyzed. ZSM-5/TiO₂ hybrids showed higher photocatalytic activity than bare TiO₂, independently of the preparation method selected. Mechanical mixing is a simple and easily scalable method to prepare highly active photocatalyst with high amounts of titania. The internal diffusion processes of the reactants to the active sites could be improved due to the micro–mesoporous structure developed on these hybrids. Incipient wetness impregnation method leads to photocatalysts with higher photodegradation rates per active site. The hybrids synthetized by this method show TiO₂ nanoparticles homogeneously dispersed on the ZSM-5 phase. The fraction of TiO₂ exposed on the surface ca. 75 mol% was similar for materials prepared by both methods, explaining the similar adsorption and photocatalytic properties, independently of the TiO₂ content. The nature of the pollutant has an important role in the adsorption and photocatalytic properties of the composites. Finally, the effect of the incorporation of the zeolite in the photocatalytic system was analyzed. For this purpose, the influence of the zeolite and titania arrangement in the sample holder on the photodegradation rate was analyzed. Although the incorporation of the zeolite induces a positive effect on the photocatalytic performance, independently of the position on the sample holder, a clear synergistic effect when both phases were in intimate contact such as in the ZSM-5/TiO₂ hybrid was observed.     

Sintering and microstructural study of mullite prepared from kaolinite and reactive alumina: Effect of MgO and TiO2

Mullite ceramic was prepared using kaolinite and synthesized alumina (combustion route) by solid-state interaction process. The influence of TiO₂ and MgO additives in phase formation, microstructural evolution, densification, and mechanical strengthening was evaluated in this work. TiO₂ and MgO were used as sintering additives. According to the stoichiometric composition of mullite (3Al₂O₃·2SiO₂), the raw materials, ie kaolinite, synthesized alumina, and different wt% of additives were wet mixed, dried, and uniaxially pressed followed by sintering at different temperature. 1600°C sintered samples from each batch exhibit enhanced properties. The 1 wt% TiO₂ addition shows bulk density up to 2.96 g/cm³ with a maximum strength of 156.3 MPa. The addition of MgO up to 1 wt% favored the growth of mullite by obtaining a density and strength matching with the batch containing 1 wt% TiO₂. These additives have shown a positive effect on mullite phase formation by reducing the temperature for complete mullitization by 100°C. Both additives promote sintering by liquid phase formation. However, the grain growth, compact microstructure, and larger elongated mullite crystals in MgO containing batch enhance its hardness properties.     

Effect of talc and titania on the microstructure and mechanical properties of alumina ceramics

Alumina (Al₂O₃) ceramics were prepared with nucleating agent of titania (TiO₂) and fluxing agent of talc by the normal pressure sintering method. The effects of TiO₂ and talc on phase composition, microstructure, and mechanical properties of Al₂O₃ ceramics, as well the strengthening and toughening mechanism were investigated. It was found that the introduction of TiO₂ could be favorable for mullite formation and the improved densification of ceramics, resulting in improved mechanical properties of ceramics as well. Ceramics possess the best comprehensive mechanical performance with fracture toughness of 3.69 MPa·m^1/2 and flexural strength of 255.9 MPa when 4 wt.% TiO₂ and 15 wt.% talc were added. Mineral bridges and nanocrystallites were found in the glass‐ceramics, which caused the deflection of cracks so that it strengthened the grain boundary and improved the mechanical properties of ceramics.     

Sintering and mechanical properties of titanium diboride with aluminum nitride as a sintering aid

Titanium diboride (TiB₂) was hot-pressed at 1800 °C with aluminum nitride (AlN) as a sintering aid. The presence AlN had a strong influence on the sinterability and mechanical properties of the TiB₂. When a small amount (⩽5 wt.%) of AlN was added to the TiB₂ the titania (TiO₂) present on the surface of the TiB₂ powder was eliminated by a reaction with AlN to form TiN and Al₂O₃. The elimination of TiO₂ markedly improved the sinterability and consequently the mechanical properties of TiB₂. However, when too much AlN was added (⩾10 wt.%), the sinterability and the mechanical properties decreased, apparently due to the remaining unreacted AlN.     

Polycarbonate composites: Effect of filler type and melt‐blending process on the light diffusion properties

Transmittance and haze are key properties of light diffusion materials. Hybrid light diffusion agents (LDAs) and melt‐blending process are introduced to study optical performance and mechanical properties of polycarbonate (PC) light diffusion materials. Optical properties of PC composites prepared by two‐step melt‐blending process has better repeatability compared to one‐step method due to the better dispersion state of hybrid fillers in PC matrix. The hybrid fillers silicate microspheres (SMS)/nano titania particles (nTiO₂) are more suitable for PC matrix compared to cross‐linked poly(methyl methacrylate) microspheres (PMMA)/nTiO₂, for the reason that the PC/SMS/nTiO₂ composites exhibit favorable optical performance and almost no deterioration of mechanical properties. The good balance between high transmittance and substantial haze can be achieved when the SMS/nTiO₂ content is 1.2 wt% (the transmittance and haze are 60.97% and 88.73%, respectively). POLYM. ENG. SCI., 57:374–380, 2017. © 2016 Society of Plastics Engineers