Effect of micro-sized alumina powder on the hydration products of calcium aluminate cement at 40 °C

In this work, the effect of different micro-sized alumina powders on the hydration products of calcium aluminate cement (CAC) during hydration at 40 °C is studied. The cement hydration at the designated times is terminated by the freeze-vacuum method. The phase development and microstructure evolution during the cement hydration are investigated by XRD and DSC, and SEM, respectively. It is found that 3CaO·Al₂O₃·6H₂O (C₃AH₆) is the dominant product of the pure CAC after hydration at 40 °C for 3.5 h. But 2CaO·Al₂O₃·8H₂O (C₂AH₈) is the dominant hydrate and C₃AH₆ is not found in the mixtures of CAC and micro-sized alumina powder under the same condition. The results indicate that the addition of alumina powders promotes the formation of C₂AH₈ and retards the conversion of C₂AH₈ to the C₃AH₆ phase. Moreover, such phase development with alumina addition is discussed.     

Multicomponent gas diffusion in hardened cement paste at temperatures up to 350 °C

Diffusional gas transport of a H₂/CO₂ mixture versus N₂ in the pore system of hardened cement pastes was studied at four temperatures up to 350 °C in a Wicke-Kallenbach cell. The pastes possessed separation factors α_H2,CO2 from 1.42 to 3.43, i.e. the diffusion of hydrogen took place considerably faster than the diffusion of carbon dioxide. The separation factors depended on the threshold radii of the pastes, smaller threshold radii leading to higher separation factors. The Knudsen numbers of the controlling constrictions of the pore system and the temperature dependence of the effective diffusion coefficients of the gases show that gas transport in these constrictions takes place in the transient regime between Knudsen diffusion and bulk diffusion, smaller constriction widths leading to predominating Knudsen diffusion. It is therefore possible to use cement paste membranes to separate gas components of low molecular weight from higher weight components.     

Influence of countersurface materials on dry sliding performance of CuO/Y-TZP composite at 600 °C

Dry sliding wear tests on 5 wt.% copper oxide doped yttria stabilized zirconia polycrystals (CuO–TZP) composite have been performed against alumina, zirconia and silicon nitride countersurfaces at 600 °C. The influences of load and countersurface materials on the tribological performance of this composite have been studied. The friction and wear test results indicate a low coefficient of friction and specific wear rate for alumina and zirconia countersurfaces at F = 1 N load (maximum Hertzian pressure ～0.5 GPa). Examination of the worn surfaces using scanning electron microscope/energy dispersive spectroscopy confirmed the presence of copper rich layer at the edge of wear scar on the alumina and zirconia countersurfaces. However, Si₃N₄ countersurface sliding against CuO–TZP shows a relatively higher coefficient of friction and higher wear at 1 N load condition. These results suggest that the countersurface material significantly affect the behavior of the third body and self-lubricating ability of the composite.     

Preparation of nanoporous alumina superinsulator with ultra-low thermal conductivity and improved heat resistance up to 1200 °C

Nanoporous alumina superinsulator (NanoASI) with ultra-low thermal conductivity and excellent thermal stability has been prepared by a low-cost and simple dry pressing method. The thermal conductivity of the NanoASI is as low as 0.11 W/m K at 1200 °C and the linear shrinkage is less than 2% after heating at 1200 °C for 1 h. These values are superior to that of previous reported nanoporous insulation materials. Thermal conductivities of this material in the temperature range of 25–1200 °C and pressure range of 10–10⁵ Pa were firstly measured by the transient hot-plane method. The mechanism that improves the heat resistance of the NanoASI is discussed and found that the stabilization of the alumina nanoparticles contributes significantly to the thermal stability of the NanoASI.     

Wear mechanisms of TiN–TiB2 ceramic in sliding against alumina from room temperature to 700 °C

TiN–TiB₂ ceramic was prepared by the reactive hot-pressing method using titanium and BN powders as raw materials. The friction and wear properties of TiN–TiB₂ ceramic were evaluated in sliding against alumina ball from room temperature to 700 °C in air. The TiN–TiB₂ ceramic has a relative density of 98.6%, a flexural strength of 731.9 MPa and a fracture toughness of 8.5 MPa m^1/2 at room temperature. The TiN–TiB₂ ceramic exhibits a distinct decrease in friction coefficient at 700 °C as contrasted with the friction data obtained at room temperature and 400 °C. Wear mechanisms of TiN–TiB₂ ceramic depend mainly upon testing temperature at identical applied loads. Lubricious oxidized products caused by thermal oxidation provide excellent lubrication effects and greatly reduce the friction coefficient of TiN–TiB₂ ceramic at 700 °C. However, abrasive wear and tribo-oxidation are the dominant wear mechanisms of TiN–TiB₂ ceramic at 400 °C. Mechanical polishing effect and removal of micro-fractured grains play important roles during room-temperature wear tests.     

Impact of a 70 °C temperature on an ordinary Portland cement paste/claystone interface: An in situ experiment

Radioactive wastes in future underground disposal sites will induce a temperature increase at the interface between the cementitious materials and the host rock. To understand the evolution of Portland cement in this environment, an in situ specific device was developed in the Underground Research Laboratory in Tournemire (France). OPC cement paste was put into contact with clayey rock under water-saturated conditions at 70 °C. The initial temperature increase led to ettringite dissolution and siliceous katoite precipitation, without monosulfoaluminate formation. After 1 year of interaction, partial decalcification and diffuse carbonation (calcite precipitation) was observed over 800 μm in the cement paste. At the interface, a layer constituted of phillipsite (zeolite), tobermorite (well-crystallised C-S-H) and C-(A)-S-H had formed. Globally, porosity decreased at both sides of the interface. Geochemical modelling supports the experimental results, especially the coexistence of tobermorite and phillipsite at 70 °C, minerals never observed before in concrete/clay interface experiments.     

Influence of slag chemistry on the hydration of alkali-activated blast-furnace slag — Part II: Effect of Al2O3

The hydration and microstructural evolution of three alkali activated slags (AAS) with Al₂O₃ contents between 7 and 17% wt.% have been investigated. The slags were hydrated in the presence of two different alkaline activators, NaOH and Na₂SiO₃·5H₂O. The formation of C(A)–S–H and hydrotalcite was observed in all samples by X-ray diffraction, thermal analysis and scanning electron microscopy. Higher Al₂O₃ content of the slag decreased the Mg/Al ratio of hydrotalcite, increased the Al incorporation in the C(A)-S-H and led to the formation of strätlingite. Increasing Al₂O₃ content of the slag slowed down the early hydration and a lower compressive strength during the first days was observed. At 28 days and longer, no significant effects of slag Al₂O₃ content on the degree of hydration, the volume of the hydrates, the coarse porosity or on the compressive strengths were observed.     

Thermal corrosion behavior of Yb4Hf3O12 ceramics exposed to calcium-ferrum-alumina-silicate (CFAS) at 1400 °C

In current work, the interaction between representative CFAS deposit (33CaO-10FeO_1.5-13AlO_1.5-44SiO₂) and Yb₄Hf₃O₁₂ ceramics at 1400 °C was investigated. Results indicated that the Yb₄Hf₃O₁₂ ceramics are of high resistance to infiltration of CFAS melt. Microstructure characterization revealed that Yb₄Hf₃O₁₂ reacted with CFAS to form a continuous reaction layer mainly composed of Yb-Ca-Si apatite, which inhibits CFAS further infiltration. Before the formation of the reaction layer, CFAS melts underwent a crystallization process at high temperatures, precipitating CaYbFeAlSi-garnet, which raised the viscosity of CFAS and thus inhibited the fluidity of CFAS.     

The effect of a graphite addition on oxidation of ZrB2–SiC in air at 1500 °C

Dense ZrB₂ containing 15 vol.% SiC and 15 vol.% graphite was exposed to flowing air at 1500 °C. A layered scale structure developed that consisted of (1) a uniform SiO₂-rich layer on the surface, (2) a layer of ZrO₂ and SiO₂, (3) a layer of ZrO₂ (4) a partially oxidized layer composed of porous ZrB₂, ZrO₂, and graphite, and (5) unaffected ZrB₂–SiC–C. A thermodynamic model based on volatility diagrams and consistent with the experimental observations was constructed to explain the development of the layered structure. Oxidation behavior was consistent with passive oxidation and formation of a protective surface layer. Analysis indicated that it may not be possible to form a protective surface layer without actively oxidizing SiC and producing a porous partially oxidized layer between the outer protective layer and the underlying unoxidized material.     

Hot corrosion behavior of YSZ/ZrW2O8 composites exposed to V2O5 at 700 °C and 850 °C in air

The hot corrosion behavior of YSZ/ZrW₂O₈ composites as a promising thermal barrier coating system exposed to V₂O₅ at 700 °C and 850 °C was investigated in order to better understand the influence of the incorporated ZrW₂O₈ with isotropic negative thermal expansion performance on the corrosion resistance. Results indicate that the ZrW₂O₈ incorporation could retard the degradation of YSZ from V₂O₅ attack and the corrosion process is significantly related to the inclusion content and the temperature. The corrosion resistance could be determined by the incorporation content, while the reaction products are only temperature dependent. At 700 °C, ZrV₂O₇, YVO₄ and m-ZrO₂ were the main corrosion products, while ZrW₂O₈ recrystallized under the acidic environment provided by V₂O₅. At 850 °C, ZrW₂O₈ decomposed and only WO₃, YVO₄ and m-ZrO₂ could be detected as final corrosion products. The corrosion mechanisms of YSZ/ZrW₂O₈ composites at 700 °C and 850 °C were discussed based on the phase diagrams and Lewis acid-base rule as well as the volume compensation of the positive and negative expansion ceramics.     

High temperature oxidation behavior of porous MoAlB ceramic from 800 °C to 1100 °C in air

MoAlB possesses the characteristics of both metals and ceramic materials, which has attracted extensive attention due to its excellent high-temperature oxidation resistance. For this reason, porous MoAlB is considered applicable to the practice of filtration under harsh environment. In this study, the high-temperature oxidation behavior of porous MoAlB ceramics is systematically studied at the temperatures ranging from 800 to 1100 °C. According to the results, the porous MoAlB exhibits good oxidation resistance at a maximum temperature of 1000 °C. The oxidation kinetics of porous MoAlB can be divided into three stages, and the estimated activation energies of the three stages are 253.83 kJ·mol⁻¹, 367.48 kJ·mol⁻¹ and 317.84 kJ·mol⁻¹, respectively. In the stable stage at 1000 °C, the quadratic mass gain per unit area shows linearity over time, and the oxidation rate of porous MoAlB reaches 37.31 mg²·cm⁻⁴·h⁻¹. As revealed by the analysis of the composition and microstructure of oxide layers, the main components of the oxide layer include MoO₃, MoO₂, Al₂O₃, B₂O₃. With the extension of oxidation time, the content of Al₂O₃ in the oxide films increases. The average pore size, permeability and open pore porosity of porous MoAlB show a trend of first decreasing and then tending to be stable. In addition, a discussion is conducted on the high-temperature oxidation mechanism of porous MoAlB.     

The role of activating solution concentration on alkali–silica reaction in alkali-activated fly ash concrete

To enable commercial use of alkali-activated fly ash concrete, its durability must be better understood. Alkali–silica reaction is a primary concern since highly alkaline solutions are generally used for activation. This study investigated the effect of NaOH activating solution concentration on pore solution alkalinity and subsequent alkali–silica reaction in alkali-activated fly ash concrete. It was found that pore solution alkalinity increased with increasing activating solution NaOH concentration, and this effect was amplified at concentrations above an optimum, defined as the concentration that resulted in the highest mortar compressive strength. Expansion of concrete prisms containing highly reactive fine aggregate and activating solution concentrations above the optimum concentration was approximately three times that of concrete with optimum activating solution concentrations, but only about 5% of the expansion observed in the ordinary portland cement control. The low expansion may be attributed to the low calcium levels in the alkali-activated fly ash concrete.     

Hot corrosion behavior of CoWSi/WSi2 coating exposed to Na2SO4+NaCl salt at 900 °C

In this study, the high temperature hot corrosion behavior of a CoWSi/WSi₂ composite coating was investigated. Hot corrosion studies were performed on CoWSi/WSi₂ coated nickel specimens after exposure to a molten Na₂SO₄+NaCl salt environment at 900 °C under cyclic conditions. Thermogravimetric technique was used to establish the kinetics of corrosion. XRD and SEM/EDS techniques were used to analyze the corrosion products. The oxide scale formed on the coating surface was complex and the hot corrosion resistance of coating may be attributed to the formation of oxides and spinels of silicon, cobalt and tungsten. Also, NaCl accelerated the degeneration of the coating because of producing the volatile CoCl₂ and thereby oxygen and sulfur could easily penetrate into the coatings and caused the formation of internal oxide and sulfide.     

Microstructure and mechanical performance evolution of C/C–ZrC composites exposed to oxyacetylene flame

C/C–ZrC composites were prepared by isothermal chemical vapor infiltration (ICVI) combined with reactive melt infiltration (RMI). The ablation behavior of the C/C–ZrC was investigated using an oxyacetylene flame. The effect of ablation time on the microstructure and mechanical property evolution of the composite was studied. The results showed that as the ablation time prolonged, the linear and mass ablation rates of the composite increased firstly and then stabilized. After 15 s ablation, the flexural strength and modulus of the C/C–ZrC were interestingly increased by 141.8% and 40.9%, which reached 138.42 MPa and 6.45 GPa, respectively. During ablation, the preferential oxidation effect of ZrC could mitigate the oxidation of pyrolytic carbon (PyC) and carbon fibers, and the volume change induced by the ZrC →ZrO₂ phase transformation could weaken its bonding with PyC, which was beneficial for releasing the internal residual stresses of the C/C–ZrC and then contributed to the mechanical performance improvement.     

Elastic properties of high alumina cement castables from room temperature to 1600°C

High-alumina refractory castables with compositions in the systems CaO–Al₂O₃ and CaO–Al₂O₃–SiO₂ were studied using an ultrasonic technique. The technique allows in-situ, non-destructive measurement of Young's modulus from room temperature to 1600°C. Elastic and dilatometric properties were investigated in relation to phase changes (followed by XRD) and sintering phenomena. The conversion of CAH₁₀, the hydration of still-anhydrous cement phases, and the dehydration of C₃AH₆ and AH₃ are related with events in Young's modulus evolution. Addition of 1 wt% of silica fume strongly decreases the high-temperature mechanical properties.     

The effect of annealing at 1400 °C on the structural evolution of porous C-rich silicon (boron)oxycarbide glass

A precursor SiBOC glass was annealed at 1400 °C for 1, 3, 5 and 10 h and then it was HF etched in order to dissolve the SiO₂/B₂O₃ phase and to obtain a porous C-rich oxycarbide glass. The porous material was studied by N₂ absorption. The pore diameter of the porous C-rich SiBOC glass ranges between 2 and 5 nm and continuously increases with increasing annealing time. The pore volume also increases with the annealing time up to ≈1.0 cm³/g which is close to the pore volume estimated from the chemical composition (1.04 cm³/g) assuming complete dissolution of the silica-based phase.     

Solid-state pressureless sintering of silicon carbide below 2000 °C

To date, solid-state pressureless sintering of silicon carbide powder requires sintering aids and high sintering temperature (>2100 °C) in order to achieve high sintered density (>95% T.D.). Two-step sintering (TSS) method can allow to set sintering temperature lower than that conventionally required. So, pressureless two-step sintering process was successfully applied for solid-state sintering (boron carbide and carbon as sintering additives) of commercial SiC powder at 1980 °C. Microstructure and mechanical properties of TSS-SiC were evaluated and compared to those obtained with the conventional sintering (SSiC) process performed at 2130 °C. TSS-SiC showed finer microstructure and higher flexural strength than SSiC with very similar density (98.4% T.D. for TSS-SiC and 98.6% T.D. for SSiC).     

Oxidation behavior of ZrB2-SiC-ZrC at 1700 °C

The oxidation behaviors of four compositions of ZrB₂-SiC-ZrC and one composition of ZrB₂-SiC were studied at 1700 °C in air and under low oxygen partial pressure. Volatility diagrams for ZrB₂-SiC-ZrC and ZrB₂-SiC were used to thermodynamically elucidate the oxidation mechanisms. SiO₂ and ZrO₂ layers formed on the surfaces of ZrB₂-SiC-ZrC and ZrB₂-SiC oxidized at 1700 °C. A SiC-depleted layer only formed on the surface of the ZrB₂-SiC oxidized under low oxygen partial pressure. The oxide layer thickened with increasing ZrC volume content during oxidation in air and under low oxygen partial pressure. The ZrB₂-SiC-ZrC oxide surface exploded in air when the ZrC volume content was more than 50%. Under low oxygen partial pressure, the oxide surfaces of all the ZrB₂-SiC-ZrC specimens bubbled.