Microstructure and mechanical properties of cold sintered porous alumina ceramics

New innovative approach to fabricate porous alumina ceramics by cold sintering process (CSP) is presented using NaCl as pore forming agent. The effects of CSP and post-annealing temperature on the microstructure and mechanical strength were investigated. Al₂O₃–NaCl composite with bulk density of 2.92 g/cm³ was compacted firstly using CSP and then a porous structure was formed using post-annealing at 1200°C–1500°C for 30 min. Brazilian test method and Vickers hardness test were used to determine the indirect tensile strength and hardness of the porous alumina, respectively. Meanwhile, the phases and the microstructure were respectively examined using X-ray diffractometer and scanning electron microscope (SEM) complemented by the 3D image analysis with X-ray tomography (XRT). SEM structural and XRT image analysis of cold sintered composite showed a dense structure with NaCl precipitated between Al₂O₃ particles. The NaCl volatization from the composite was observed during the annealing and then complete porous Al₂O₃ structure was formed. The porosity decreased from 48 vol% to 28 vol% with the annealing temperature increased from 1200 °C to 1500 °C, while hardness and mechanical strength increased from 14.3 to 115.4 HV and 18.29–132.82 MPa respectively. The BET analysis also showed a complex pore structure of micropores, mesopores and macropores with broad pore size distribution.     

Model for the cold sintering of lead zirconate titanate ceramic composites

A model was developed to describe the cold sintering process (CSP) of lead zirconate titanate (PZT) using moistened lead nitrate as a sintering aid. The densities of PZT powder with different volume fractions of lead nitrate were evaluated after cold sintering at 300°C and 500 MPa for 3 hours. The densities were categorized into three zones. In zone I, the relative density following cold sintering increases from 66% to 80%, as the lead nitrate contents rise from 0 to 14 vol%. In this case, the lead nitrate acts to fill some of the pore volume between PZT grains. Zone II serves as a transition region, where there is both pore filling and dilution of the PZT grains associated with lead nitrate contents from 14 to 34 vol%. In zone III, the relative density drops due to dilution at lead nitrate contents exceeding 34 vol%. To slow the process down so that the kinetics could be studied more readily, samples were cold sintered at room-temperature and 500 MPa. It was found that during the first few seconds of compaction, 85PZT/15Pb(NO₃)₂ rapidly densified from 51% to 61% relative density due to particle re-arrangement. For longer times at pressure, the CSP improved the packing relative to PZT compacted without the lead nitrate, yielding a higher relative density. The late stages of the PZT/Pb(NO₃)₂ CSP could be well described using a viscous sintering model for pressures from 50 MPa to 1000 MPa and temperatures from 25°C to 300°C.     

Light scattering by pores in YAG transparent ceramics simulated by DDA model

Discrete dipole approximation (DDA) simulation was applied to study the effect of pores on light scattering in ceramics. The results of the DDA method were compared with that of Mie theory. The DDA method was approved to be reliable for calculating the scattering coefficients of YAG ceramics. The dependences of scattering coefficients on pore size and porosity, and the equal K_sca (scattering coefficients) curves were all recalculated via DDA method. The results revealed that scattering coefficients increase with the increase of porosity and that small pores (diameters are about three-quarters of incident wavelength) produce much more light scattering than larger pores (diameters are several times larger than incident wavelength) at the same porosity. Furthermore, the equal K_sca (scattering coefficients) curves showed that relatively high porosity will not sacrifice the critical pore size any more when pore sizes are several times larger than incident wavelength. This discovery perfects the scattering critical curves and has guiding significance for experiment.     

High dielectric permittivity and percolative behavior of polyvinyl alcohol/potassium dihydrogen phosphate composites

A new kind of anhydrous, transparent, and flexible potassium dihydrogen phosphate (KH₂PO₄ or KDP)/polyvinyl alcohol (PVA) composite in the form of film (0.10 mm) has been prepared by solution casting technique. KDP is well dispersed in the polymer matrix as observed from the microstructural studies. Frequency and temperature dependent dielectric properties of the composites have been studied with varying KDP concentrations. The PVA/KDP composite films exhibited extraordinarily high relative permittivity ε′ ∼ 430 (80 times higher compared with pure PVA and even higher than KDP) near the percolation threshold (ϕ_C = 2.5 wt % KDP) with low dielectric losses (∼ 0.15) at 1 kHz and room temperature. Such flexible, low loss and high dielectric permittivity material has enormous importance for application in devices. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Destruction of percolative network using green synthesized gold nanoparticles: Formation of high dielectric material

Gold nanoparticles (AuNPs) of about 5 nm in diameter were biosynthesized at room temperature (300 K). The PVA/2.5 wt% KH₂PO₄ or KDP composite film and PVA/2.5 wt% KDP/AuNPs nanocomposite films with different concentrations of AuNPs were prepared. Interestingly, addition of 0.05 wt% of AuNPs to the PVA/2.5 wt% KDP percolative composite film destroys percolative behavior of this composite film. Furthermore, the PVA/2.5 wt% KDP/0.05 wt% AuNPs nanocomposite film exhibited high room temperature dielectric permittivity (ε′ ∼ 590 at 1 kHz). The behavior of AC conductivity (σ_ac) of the nanocomposite films indicated correlated barrier hopping type of conduction mechanism. The Cole–Davidson dielectric response becomes evident as the interfacial polarization process acquires a more symmetric form, tending to Debye relaxation. High value of ε′ promises direct application in capacitors. Moreover, the novel feature of destroying the percolative behavior by AuNPs may be applied even in other systems.     

Mechanical and thermal properties of coconut shell powder filled polylactic acid biocomposites: effects of the filler content and silane coupling agent

The effects of the filler content and the coupling agent 3-aminopropyltriethoxysilane (3-APE) on the mechanical properties, thermal properties, and morphologies of polylactic acid (PLA)/coconut shell powder (CSP) biocomposites were investigated. It was found that increasing the CSP content decreased the tensile strengths and elongations at break of the PLA/CSP biocomposites. However, incorporating CSP increased their modulus of elasticity. The tensile strengths and modulus of elasticity of the PLA/CSP biocomposites were enhanced by the presence of 3-APE, which can be attributed to a stronger filler–matrix interaction. The thermal stabilities of the biocomposites increased with the filler content, and they were enhanced by 3-APE treatment. Meanwhile, the presence of CSP increased the glass transition temperatures (T _g) and crystallinities (X _c) of the PLA/CSP biocomposites at a filler content of 30 php. After 3-APE treatment, T _g and X _c of the PLA/CSP biocomposites increased due to enhanced interfacial bonding. The presence of a peak crystallization temperature (T _c) for the PLA/CSP biocomposites indicated that the CSP has a nucleating effect. The melting temperatures (T _m) and the T _c values of the biocomposites were not significantly affected by the filler content and 3-APE. PLA/CSP biocomposites that had been treated with 3-APE presented the strongest filler–matrix interaction, as confirmed by SEM.     

532 nm laser damage and nonlinear absorption of Cr2O72− doped KDP crystals

Potassium dihydrogen phosphate (KDP) single crystals doped with a series of trace dichromate (Cr₂O₇^2?) were prepared using “point seed” technique. The IR spectra suggest that the KDP crystal network becomes compact with trace of Cr₂O₇^2? while the lattice of crystal also can be destroyed by excessive doping. The UV–Vis spectra show that the transmittance percentage is descended of the doped KDP crystals. Z-scan analysis demonstrates that with increasing of Cr₂O₇^2? concentration, a gradual raise has been observed for the nonlinear absorption coefficient (β). The laser-induced damage threshold (LIDT) at 532 nm of the KDP crystal doped with 3000 ppm Cr₂O₇^2? is found to be 28.29 J/cm² which is higher than that of pure one under the R-on-1 model. However, as the doping concentration continues to increase, the LIDT decreases significantly. The variation of photoluminescence (PL) results is also consisted with the trend of LIDT for the doped samples. The LIDT of pyramidal sample is higher than that of prismatic one with the same doping concentration. The results suggest that the laser damage of doped crystal may be due to a synergistic effect of the concentration of micro defects and nonlinear absorption.     

Pore development during gasification of South African inertinite-rich chars evaluated using small angle X-ray scattering

Pore development arising from steam and CO₂ gasification of a char, prepared from an inertinite-rich Witbank Seam 4 coal, was investigated using small angle X-ray scattering. The char, ∼75 μm, was gasified to specific conversions (10, 25, 35 and 50%) using two gasification reagents, CO₂ and steam. A novel ratio analysis technique was developed to study the pore development from experimental data. Differently sized pores grow at different rates with the difference not being simply due to gas accessibility. In particular, the pores between 1 and 40 nm in size showed more pore growth than larger or smaller sizes. Steam gasification created a more porous char with increased pore growth of pore sizes between 1 and 40 nm than CO₂ gasification. The pore growth rate of steam was up to a factor 7 times faster than CO₂, compared at the highest gasification temperatures. For the smaller pores, <1 nm, it was found that the rate of pore generation was slower compared to larger pores, though pore growth was still evident with the critical cross over pore size for CO₂ to be 1 nm compared to 0.6 nm for steam. This may be a direct consequence of CO₂'s greater kinetic diameter.     

Small-angle neutron scattering characterization of the structure of nanoporous carbons for energy-related applications

We used small-angle neutron scattering (SANS) and neutron contrast variation to study the structure of four nanoporous carbons prepared by thermo-chemical etching of titanium carbide TiC in chlorine at 300, 400, 600, and 800 °C with pore diameters ranging between ∼4 and ∼11 Å. SANS patterns were obtained from dry samples and samples saturated with deuterium oxide (D₂O) in order to delineate origin of the power law scattering in the low Q domain as well as to evaluate pore accessibility for D₂O molecules. SANS cross section of all samples was fitted to Debye-Anderson-Brumberger (DAB), DAB-Kirste-Porod models as well as to the Guinier and modified Guinier formulae for cylindrical objects, which allowed for evaluating the radii of gyration as well as the radii and lengths of the pores under cylindrical shape approximation. SANS data from D₂O-saturated samples indicate that strong upturn in the low Q limit usually observed in the scattering patterns from microporous carbon powders is due to the scattering from outer surface of the powder particles. Micropores are only partially filled with D₂O molecules due to geometrical constraints and or partial hydrophobicity of the carbon matrix. Structural parameters of the dry carbons obtained using SANS are compared with the results of the gas sorption measurements and the values agree for carbide-derived carbons (CDCs) obtained at high chlorination temperatures (>600 °C). For lower chlorination temperatures, pore radii obtained from gas sorption overestimate the actual pore size as calculated from SANS for two reasons: inaccessible small pores are present and the model-dependent fitting based on density functional theory models assumes non-spherical pores, whereas SANS clearly indicates that the pore shape in microporous CDC obtained at low chlorination temperatures is nearly spherical.     

Reassessing cold sintering in the framework of pressure solution theory

Cold sintering densification and coarsening mechanisms are considered from the perspective of the non-equilibrium chemo-mechanical process known in Earth Sciences as pressure solution creep (or dissolution-precipitation creep). This is an important mechanism of densification and deformation in many geological rock formations in the Earth’s upper crust, and although very slow in nature, it is of direct relevance to the cold sintering process. In cold sintering, we select particulate materials and identify experimental processing parameters to significantly accelerate the kinetics of dissolution-precipitation phenomena, with appropriate consideration of chemistry, applied stress, particle size and temperatures. In the theory of pressure solution, pressure-driven densification is considered to involve the consecutive stages of dissolution at grain contact points, then diffusive transport along the grain boundaries towards open pore surfaces, and then precipitation, all driven by chemical potential gradients. In this study, it is shown that cold sintering of BaTiO₃, ZnO and KH₂PO₄ (KDP) ceramic materials proceeds by the same type of serial process, with the pressure solution creep rate being controlled by the slowest kinetic step. This is demonstrated by the values of activation energy (E_a) for densification, which are in good agreement with the existing literature on dissolution, precipitation, or coarsening. The influence of pressure on the morphology of ZnO grains also supports the pressure solution mechanism. Other characteristics that can be understood qualitatively in terms of pressure solution are observed in the in systems such as BaTiO₃ and KDP. We further consider activation energies for grain growth with respect to the precipitation process, as well as evidence for coalescence and Ostwald ripening during cold sintering. For completeness we also consider materials that show significant plastic deformation under compression. Our findings point the way for new advances in densification, microstructural control, and reductions in cold sintering pressure, via the use of appropriate transient solvents in metals and hybrid organic-inorganic systems, such as the Methylammonium lead bromide (MAPBr) perovskite.     

Effects of preform pore structure on infiltration kinetics and microstructure evolution of RMI-derived Cf/ZrC-ZrB2-SiC composite

Reactive melt infiltration (RMI) is often used to fabricate highly dense ceramic matrix composite by infiltration of alloy melt into porous preform. Here, C_f/B₄C-C preforms with various pore structures were prepared, and the effects of pore structure on the ZrSi₂ melt infiltration and the as-received C_f/ZrC-ZrB₂-SiC composites were investigated. Compared with the preform prepared by slurry impregnation (SI), the preform prepared by sol impregnation shows more uniform pore size distribution, which leads to more homogeneous melt infiltration, as well as more uniform formation of ZrC-ZrB₂-SiC and better mechanical properties in the composites. The calculation results of infiltration kinetics indicate that the pore radius decreases quickly during the melt infiltration. As the time needed for pore closure in sol-preform is longer than that in SI-preform, it makes the infiltration kinetics more favorable in the former preform. This study can provide guidance for the pore structure regulation in the fabrication of RMI-composites.     

Nano-to-macroporous TiO2 (anatase) by cold sintering process

Cold Sintering Process (CSP) was applied on commercial nanopowders to produce nanostructured TiO₂ anatase with nano-to-macro porosity. Nanoporous TiO₂ based materials were obtained by applying CSP at 150 °C and pressures up to 500 MPa on three TiO₂ nanopowders with different specific surface area (s.s.a. = 50, 90 and 370 m²/g), using water as transient aqueous environment. Although TiO₂ is insoluble in water, a density of 68% and s.s.a. = 117 m²/g were achieved from the powder with the highest specific surface area. A post annealing process at 500 °C increased the density up to 73% with a s.s.a. = 59 m²/g, and the crystallites dimensions passed from 110 Å in the powder to 130 Å in CSP material and 172 Å after post annealing. Finally, macroporosity was produced by using thermoplastic polymer beads as sacrificial templates within TiO₂ nanopowder during CSP, followed by a debonding at 500 °C.     

Evaluation of pore scattering in transparent ceramics: A simplified model for nanometric spherical pores

It is well known that light scattering by nanometric pores is adverse to realize a high transparency in ceramics; however, a suitable model that gives this phenomenon a quantitative evaluation is still lacking. In this work, a simplified model based on Rayleigh's theory was developed in order to unravel the light scattering by nanometric pores, taking polycrystalline KNNB-xSm ceramics with high transparency (>67% at 780 nm) as example. The validity of this model was further verified by its good agreement with experimental results. Based on detailed simulations, we came to the conclusion that the pore volume fraction p is a more important parameter on the transparency of KNNB-xSm ceramics than pore size d_pore. Our findings in this work might provide inspiring insight to obtain highly transparent KNN-based ceramics and more.     

Enhanced piezoelectric property in Mn-doped K0.5Na0.5NbO3 ceramics via cold sintering process and KMnO4 solution

Through mixing the KMnO₄ solution with K_0.5Na_0.5NbO₃ (KNN) powders, cold sintering process (CSP) was employed to fabricate high-density Mn-doped KNN green pellets and ceramics. The microstructure, doping effect of Mn and electrical properties of these ceramics were studied in detail. Compared with conventional sintering (CS), the CSP supports the homogeneity of dopants and then promotes grain growth and ceramic densification; thus the Mn-doped KNN ceramics prepared by CSP show the obviously higher density and larger grain size. Besides, the less alkalis volatilization and oxygen vacancies result in more Mn³⁺ but less Mn⁴⁺ in CSP ceramics compared to CS ones, which endows the pinning effect and good poling characteristics in CSP ceramics. All the previous results contribute to the high dielectric constant and remnant polarization in CSP ceramics, which support the enhanced piezoelectric coefficient and are much superior than Mn-doped KNN ceramics prepared by CS. This work reveals that CSP can be a new doping strategy to perform chemical modification of electrical properties in KNN ceramics.     

Polyhedral carbon nanofoams with minimum surface area partitions produced using silica nanofoams as templates

Polyhedral silica nanofoam (PNF-SiO₂) analogues of dry soap froths with minimal surface area were used as templates for making polyhedral carbon nanofoams (PNF-C). Furfuryl alcohol or triblock copolymers were used as carbon sources. The volume of carbon precursor relative to the internal pore volume of PNF-SiO₂’s was systematically varied between 50% and 100% in order to investigate the effect of filling fraction on internal structure of the corresponding PNF-C’s. Transmission electron microscopy, small-angle X-ray scattering and nitrogen physisorption were used to characterize the samples. To aid the interpretation of the experimental data, a model for X-ray scattering from spherical shells was used to approximate scattering from the polyhedral foam cells. PNF-C’s cast from the PNF-SiO₂’s, displayed the characteristic Plateau borders of minimal surface area foams defining interconnected, slit-like pore systems at all filling fractions. At relatively high filling fractions, inverse foam structures were obtained with the slit-like pores systems interpenetrating aggregated, close-packed, relatively low density polyhedral carbon nanoparticles co-joined by carbon struts. At relatively low filling fractions, polyhedral carbon nanofoams with relatively thin, fused double-wall structures and interconnected polyhedral pore systems were obtained.     

Increment of specific heat capacity of solar salt with SiO2 nanoparticles

Thermal energy storage (TES) is extremely important in concentrated solar power (CSP) plants since it represents the main difference and advantage of CSP plants with respect to other renewable energy sources such as wind, photovoltaic, etc. CSP represents a low-carbon emission renewable source of energy, and TES allows CSP plants to have energy availability and dispatchability using available industrial technologies. Molten salts are used in CSP plants as a TES material because of their high operational temperature and stability of up to 500°C. Their main drawbacks are their relative poor thermal properties and energy storage density. A simple cost-effective way to improve thermal properties of fluids is to dope them with nanoparticles, thus obtaining the so-called salt-based nanofluids. In this work, solar salt used in CSP plants (60% NaNO₃ + 40% KNO₃) was doped with silica nanoparticles at different solid mass concentrations (from 0.5% to 2%). Specific heat was measured by means of differential scanning calorimetry (DSC). A maximum increase of 25.03% was found at an optimal concentration of 1 wt.% of nanoparticles. The size distribution of nanoparticle clusters present in the salt at each concentration was evaluated by means of scanning electron microscopy (SEM) and image processing, as well as by means of dynamic light scattering (DLS). The cluster size and the specific surface available depended on the solid content, and a relationship between the specific heat increment and the available particle surface area was obtained. It was proved that the mechanism involved in the specific heat increment is based on a surface phenomenon. Stability of samples was tested for several thermal cycles and thermogravimetric analysis at high temperature was carried out, the samples being stable.

PACS

65.: Thermal properties of condensed matter; 65.20.-w: Thermal properties of liquids; 65.20.Jk: Studies of thermodynamic properties of specific liquids     

Studies on phase separation rate in porous polyimide membrane formation by immersion precipitation

Phase separation rate during porous membrane formation by immersion precipitation was investigated by light scattering in a polyimide/N‐Methylpyrrolidone (NMP)/water system. In the light scattering measurement, plots of scattered intensity against scattered angle showed maxima in all cases, which indicated that phase separation occurred by a spinodal decomposition (SD). Characteristic properties of the early stage of SD, such as an apparent diffusion coefficient D_app and an interphase periodic distance Λ, were obtained. The growth process of Λ was also followed by light scattering. The growth rate had the same tendency as D_app when water content in the nonsolvent bath and the polymer concentration in the cast solution were changed. The pore size of the final membrane increased with decreasing water content, which was opposite to the tendency of Λ growth rate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 292–296, 2003     

Dielectric and structural characterization and effective piezoelectric coefficient of KDP/p-Benzoquinone ceramic composites

A study of the interaction between an inorganic phase, KH₂PO₄ (KDP) and an organic phase C₆H₄O₂ (BZQ) in composites KDP/BZQ is presented here. Studies by X-ray powder diffraction and Raman spectroscopy confirm the interaction by a variation in the volume of the unit cell and new bands identified corresponding to the formation of new hydrogen bonds between KDP and BZQ in the Raman spectra. Relaxation process and conductivity were studied using an impedance analyzer in a wide frequency range (10²–10⁶?Hz) between room temperature and 90?°C allowing seeing the dielectric character of the composites and the proton conductivity behavior. Also the effective piezoelectric coefficient was determined by piezo response microscopy; it was observed a decrement of the KDP coefficient on increasing the concentration of BZQ, probably due to the interaction between them.     

Wavelength dependence of Kubelka–Munk scattering spectra for studies of TiO2 microstructure and aggregation in paints

The wavelength exponent β is easily determined from diffuse reflectance spectra as the gradient of a log–log plot of the Kubelka–Munk scattering coefficient (S) against wavelength. Previous work suggests that β provides a useful relative measure of the size of scattering units applicable to many particulate systems. This article examines the applicability of β to paints, specifically studies of TiO₂ aggregation, and comments on its wider use for pigmented coatings. Modelling using multisphere T-matrix Mie methods shows that β varies nearly linearly with the mean aggregate size. Experimental data shows good correlation between the state of aggregation and β. However, β depends strongly on the volume fraction of TiO₂ owing to the effects of dependent scattering arising from crowding, therefore comparisons between paints can only be made at constant effective TiO₂ volume fraction. A simple effective medium refractive index model in conjunction with Mie scattering appears to give a good account of the behavior of both S and β with increasing TiO₂ volume concentration. When air is incorporated into the coatings at high pigment volume fractions, scattering is much more complicated. In this case it appears very difficult to relate β directly to coating microstructure properties such as pore diameter.     

Decarbonising ceramic manufacturing: A techno-economic analysis of energy efficient sintering technologies in the functional materials sector

The rising cost of energy and concerns about the environmental impact of manufacturing processes have necessitated the need for more efficient and sustainable manufacturing. The ceramic industry is an energy intensive industrial sector and consequently the potential to improve energy efficiency is huge, particularly through the introduction of modern sintering technologies. Although several energy efficient sintering processes have been developed, there is no comprehensive techno-economic analysis which compares and contrasts these techniques. This paper presents a critical review and analysis of a number of sintering techniques and compares them with the recently developed cold sintering process (CSP), including mode of operation, sintering mechanism, typical heating rates, duration of sintering, energy consumption profile and energy saving potential, limitations, key challenges for further development and current research efforts. By using a figure of merit, pounds per tonne of CO₂ saved (£/tCO₂-eq), which links initial capital investment with energy savings, within a framework derived from ranking principles such as marginal abatement cost curves and Pareto optimisation, we have demonstrated that under the scenarios considered for 3 separate functional oxides ZnO, PZT and BaTiO₃, CSP is the most economically attractive sintering option, indicating lower capital costs and best return on investment as well as considerable energy and emission savings. Although the current work establishes the viability of CSP as a competitive and sustainable alternative to other sintering techniques, the transition from laboratory to industry of CSP will require hugely different facilities and instrumentation as well as relevant property/performance validation to realise its full potential.