Reduced grain boundary energies in rare-earth doped MgAl2O4 spinel and consequent grain growth inhibition

Grain growth inhibition in MgAl₂O₄ spinel nanostructure was achieved by grain boundary (GB) segregation of rare-earth dopants. Microcalorimetric measurements showed that dense spinel compacts doped with 3 mol% of R₂O₃ (R = Y, Gd, and La) had decreased GB energies as compared to the undoped spinel, representing reduction in the driving force for grain growth. Segregation energies of the three dopants to the Σ3 (111) GB were calculated by atomistic simulation. The dopants with higher ionic radius tend to segregate more strongly to GBs. The GB energies were calculated from atomistic simulation and, consistent with experiments, a systematic reduction in GB energy with dopant ionic size was found. High temperature grain growth experiments revealed a significant reduction of grain growth in the doped nanostructures as compared to the undoped one, which was attributed to increased metastability or possibly also a GB dragging originated from the dopant segregation.     

Unique mechanical properties of nanostructured transparent MgAl2O4 ceramics

Nanoindentation tests were performed on nanostructured transparent magnesium aluminate (MgAl₂O₄) ceramics to determine their mechanical properties. These tests were carried out on samples at different applied loads ranging from 300 to 9,000 μN. The elastic recovery for nanostructured transparent MgAl₂O₄ ceramics at different applied loads was derived from the force-depth data. The results reveal a remarkable enhancement in plastic deformation as the applied load increases from 300 to 9,000 μN. After the nanoindetation tests, scanning probe microscope images show no cracking in nanostructured transparent MgAl₂O₄ ceramics, which confirms the absence of any cracks and fractures around the indentation. Interestingly, the flow of the material along the edges of indent impressions is clearly presented, which is attributed to the dislocation introduced. High-resolution transmission electron microscopy observation indicates the presence of dislocations along the grain boundary, suggesting that the generation and interaction of dislocations play an important role in the plastic deformation of nanostructured transparent ceramics. Finally, the experimentally measured hardness and Young’s modulus, as derived from the load–displacement data, are as high as 31.7 and 314 GPa, respectively.     

Gel-casting of MgAl2O4 transparent ceramics using a common dispersant

The ethanolaminic salt of citric acid (commercial name Dolapix CE 64) has commonly been used as a dispersant for colloidal based ceramic forming process. In this paper, a surprise was presented that MgAl₂O₄ spinel slurries consisting of MgAl₂O₄ spinel nanoparticles and Dolapix CE 64 gelled in air at room temperature spontaneously. The MgAl₂O₄ spinel slurries with high solid loading (54 vol%) were prepared with Dolapix CE 64 and the green body with up to 57% relative density was obtained. MgAl₂O₄ transparent ceramics with small grain size (0.92 μm) and high transmittance (81.7% at 600 nm) were fabricated after pre-sintering at 1500°C and hot-isostatic sintering at 1550°C.     

Production and characterization of transparent MgAl2O4 prepared by hot pressing

Hot pressing has been investigated for the production of transparent MgAl₂O₄ aimed at the scaling up of the process. Other assessed techniques (hot isostatic pressing, spark plasma sintering) can hardly be used for the production of flat components with large dimensions and good planarity.Hot pressing of stoichiometric Al₂O₃–MgO powder mixtures has been preferred to the direct pressing of spinel powder for the readily availability of pure powders and to exploit the thermodynamic driving force of the spinel formation. LiF has been used as sintering additive.A thermodynamic investigation of the reactions involving LiF, MgO and Al₂O₃ has helped in the comprehension of the densification mechanisms affecting the transparency of spinel. Transparencies up to 70% in the visible range (highest value 78% at 1100 nm) have been obtained. Suitable soakings have been added for promoting the initial liquid phase sintering and the release of LiF through formation of vapour phases.     

The effect of electric fields on grain growth in MgAl2O4 spinel

The application of electrostatic fields during processing of oxide ceramic microstructures was previously reported to enhance densification and grain growth. In this study effects of the externally applied electrostatic field strength on grain growth in MgAl₂O₄ were investigated. Free sintering of green bodies showed accelerated grain growth by about 20% in the presence of an applied nominal field strength of 0.95?kV/cm. In contrast to previous studies, annealing of dense microstructures in the presence of a nominal electric field strength as high as 2.22?kV/cm revealed no additional grain growth. A machine learning algorithm for grain size analysis enabled grain size distributions including up to 30,000 grains. Due to the resulting counting statistics for microstructure analysis, it was discovered that the applied electrostatic fields caused grain growth predominantly during the early stages of sintering, i.e., at lower green body densities, hence suggesting an enhancement of surface diffusion.     

TiO2含量对镁铝尖晶石烧结性能的影响

以分析纯氧化镁、氧化铝、氧化钛为原料,按氧化镁与氧化铝质量比28.33∶71.67配料,在合成体系中分别引入质量分数为0、0.5％、1％、2％、4％、6％、8％和10％的氧化钛,在钼丝炉中1600℃保温2h,烧结法合成镁铝尖晶石.用X射线衍射、扫描电子显微镜和能谱对烧后试样进行分析.结果表明:引入适量的TiO2可显著提高镁铝尖晶石的烧结性能;当TiO2含量低于4％时,随着TiO2的含量增加,试样的线变化率减小,显气孔率下降,体积密度增大,常温耐压强度增大.TiO2的引入提高了镁铝尖晶石晶体空位浓度,活化了晶格,促进镁铝尖晶石的烧结.当TiO2含量高于4％时,试样的线变化率、显气孔率和体积密度没有显著变化,常温耐压强度有所下降;尖晶石晶粒尺寸没有明显变化,且生成了一定量的Mg0.6Al0.8Ti1.6O5,阻碍了镁铝尖晶石之间的接触,影响镁铝尖晶石烧结性能的提高.     

Fabrication of transparent MgAl2O4 ceramics by gelcasting and cold isostatic pressing

Highly transparent MgAl₂O₄ ceramics have been fabricated by aqueous gelcasting combined with cold isostatic pressing (CIP), pressureless sintering and hot isostatic pressing (HIP) from high purity spinel nanopowders. The gelling system used AM and MABM as monomer and gelling agent. The influences of dispersant and PH on the rheological behavior of the MgAl₂O₄ slurries were investigated. The spinel slurry with low solids loading (25 vol%) and low viscosity (0.15 Pa s) was obtained by using 6 wt% Duramax-3005 (D-3005) as dispersant. After CIP, the green body had a relative density of 48% with a narrow pore size distribution. The influence of sintering temperature on densification and microstructure was studied, choosing 1500 °C as the sintering temperature. After HIP (1650 °C/177 MPa/5 h), transparent MgAl₂O₄ ceramic with the thickness of 3 mm was obtained, whose in-line transmittance was 86.4% at 1064 nm and 79.8% at 400 nm, respectively. The ceramic exhibited a dense microstructure with the average grain size of 23 μm. The Vickers hardness and flexure strength of the sample reached 13.6 GPa and 214 MPa, respectively.     

Influence of Gd2O3 on the microstructure and properties of transparent MgAl2O4: Cr3+ ceramic

In this work, MgAl₂O₄: Cr³⁺ transparent ceramics have been synthesized by the hot press sintering techniques, and the effect of the sintering aid Gd₂O₃ and its content on the densification, microstructure, and optical, photoluminescence was studied and discussed. The relative density reached 99.29% with 0.8 wt% Gd₂O₃ as a sintering aid, and the optical transmittance at 686 nm and 1446 nm were approximately 76%. As Gd₂O₃ content continued to increase, the grain size of the ceramics became smaller and uniform, accompanied by some pores with the size of ～1 μm. The ceramics with 4.0 wt% Gd₂O₃ showed a higher transmittance, of 82% at 1446 nm. Additionally, Gd₂O₃ was helpful for Cr³⁺ in the sites of octahedral symmetry, which increased the quantum yield. The quantum yield of MgAl₂O₄: Cr³⁺ with 0.8 wt% Gd₂O₃ was about 0.175, which was 36% higher than that of ceramic without Gd₂O₃. In short, the sintering aid Gd₂O₃ not only contributed to improving the densification, homogenizing the grain size, and heightening the optical transmittance but also enhanced the quantum yield of Cr³⁺.     

TiO2加入量对富铝尖晶石烧结性能的影响

以α-Al2O3、分析纯的MgO及分析纯的TiO2为原料,研究了在1400℃、1500℃、1600℃保温3 h下,TiO2加入量(分别为0、1%、2%、4%)对Al2O3与MgO物质的量比为21的富铝尖晶石烧结性能的影响,并利用XRD进行物相组成分析,利用SEM和EDAX进行显微结构分析.结果表明由于TiO2与MgAl2O4的固溶作用,加入TiO2可显著改善富铝尖晶石的烧结性能;随着TiO2加入量的增加,试样的体积密度增加,显气孔率降低,特别是在1600℃烧结后的试样尤为显著.     

Fabrication of transparent MgAl2O4 spinel via spray freeze drying of microfluidized slurry

Spherical granules were prepared from a monodispersed slurry by combining the microfluidization (MF) method and the spray freeze-drying (SFD) process. Starting with the prepared granules, transparent MgAl₂O₄ ceramics were fabricated through pressureless sintering followed by hot isostatic pressing. A comparison with a polydispersed slurry prepared by the ball-milling method showed successful fabrication of a mono-dispersed state by microfluidization method, and 80% visible in-line transmittance was obtained at a 600-nm wavelength from a process starting with a monodispersed slurry of low solid content. Microstructural analysis of the green bodies, the pre-sintered bodies, and the hot isostatic pressed bodies of the prepared MgAl₂O₄ ceramics revealed that the slurry dispersion should be controlled to a high level in order to suppress scattering sources such as pores and microcracks, which affect the in-line transmittance of visible light.     

Effect of grain size on the static and dynamic mechanical properties of magnesium aluminate spinel (MgAl2O4)

Samples of transparent polycrystalline spinel with average grain size varying from 0.14 to 170 μm were prepared by different sintering approaches. The effect of grain size on the flexural strength, hardness and Hugoniot elastic limit (impact loading) was investigated. It was found that values of hardness divided by three for samples with grain size in the 0.14–15 μm range were almost equal to the dynamic yield strength values, estimated based on the Hugoniot elastic limit. This led to the assumption that the onset of inelastic deformation at the Hugoniot elastic limit was brittle rather than ductile. The observed departure of the dynamic yield strength from the hardness divided by three value for ceramics with grain size >15 μm was associated with either impact-induced shear banding or twinning. The feasibility of such banding/twinning intervention in initiating inelastic deformation in the spinel is supported by the values of apparent Hall-Petch coefficients in the corresponding grain size domains.     

Interfacial evolution mechanism of MgAl2O4/MgAl2O4 joints bonded with lanthanum glass

The La₂O₃-SiO₂-B₂O₃ (LSB) glass filler with high softening temperature was first used to join MgAl₂O₄ ceramic. An interfacial layer composed of Al₂O₃ was formed due to the solubility difference of MgO and Al₂O₃ in the LSB glass filler. As a result, the addition of Al₂O₃ into the LSB glass filler caused the increase of interfacial layer thickness. On the contrary, the addition of MgO into the LSB glass filler led to the decrease of interfacial layer thickness. When the adding content of MgO was 6 wt%, the interfacial layer disappeared and completely amorphous brazing seam was obtained. The in-line transmittance of joints decreased with the increase of the thickness of interfacial layer. The optimal in-line transmittance of joint bonded with La₂O₃-SiO₂-B₂O₃-MgO (LSB6M) glass filler reached 82.9% at 1000 nm. Meanwhile, the average flexural strength of joints was about 196.2 MPa, which was equal to the strength of MgAl₂O₄ substrate.     

Optimization of spray freeze drying parameters for spark plasma sintering of transparent MgAl2O4 spinel

Magnesium aluminate spinel (MgAl₂O₄) is considered as one of the most important spinels possessing desirable mechanical properties, with a wide range of applications at high temperatures. Powder granulation by spray freeze drying can lead to better powder flow and distribution in the mold, resulting in a specimen with high green density and strength. Accordingly, this study aimed at investigating the influential parameters on the granulation process of spinel powders via the spray freezing drying method. At first, spinel powders with various weight percents of 20, 25, 30, 35 and 50, and PVA binders with 0, 1, 2 and 8 wt% were investigated to prepare the optimal solution. Finally, the granules were sintered using the SPS method. The obtained bodies were tested by X-ray diffraction, SEM, FE-SEM, Viscosity and UV–Vis. The results showed that the optimal amount of the binder to obtain uniform granules in this process was 3%. Also, 35 wt% of solid loads represented the optimum amount for slurries, forming granules with the size range of 10–50 μm. By powder granulation, density experienced an increase of about 20%, leading to the growth of more than 15% in the in-line transmission for the IR range.     

Co2+:MgAl2O4 saturable absorber transparent ceramics fabricated by high-pressure spark plasma sintering

Single-stage processing of high-quality transparent functional polycrystalline ceramics is desirable but challenging. In the present work, spark plasma sintering (SPS) was employed for fabrication of Co²⁺:MgAl₂O₄ saturable absorbers for laser passive Q-switching. Densification of commercial MgAl₂O₄ powders, doped via co-precipitation, was carried out by conventional SPS and high-pressure SPS (HPSPS) under pressures of 60 and 400 MPa, respectively. The presence of LiF, a common sintering additive, was detrimental to optical properties as it promoted reaction of cobalt with sulfur impurities and the formation of Co₉S₈ inclusions. Densification by HPSPS without LiF allowed to obtain highly transparent Co²⁺:MgAl₂O₄. The optical properties of samples, with doping concentrations varying between 0.01 and 0.1 at.% Co²⁺, were assessed and saturable absorption was demonstrated at ~1.5 µm wavelength, exhibiting ground-state (σ_gs) and excited (σ_es) cross-sections of 3.5×10^-19 and 0.8×10^-19 cm², respectively. Thus, it was established that HPSPS is an effective method to fabricate transparent Co²⁺:MgAl₂O₄ ceramics.     

Effect of preparation method on sinterability and properties of nanocrystalline MgAl2O4 and ZrO2-MgAl2O4 materials

Abstract

Nanocrystalline MgAl₂O₄ and ZrO₂-MgAl₂O₄ powders were synthesised by combustion and conventional solid state reaction routes. The synthesised powders were processed, dry pressed, and sintered for 3 h at temperatures ranging from 1550 to 1625°C. The sintered pellets were then characterised in terms of phase (XRD), microstructure (SEM), relative density, apparent porosity, water absorption, hardness, three point bend strength, and fracture toughness. The XRD studies revealed that ZrO₂ was present in tetragonal form in the case of combustion synthesised powders (CSP), whereas in powders obtained by solid state reaction (SSP) it was present in the monoclinic form. This study also revealed that the addition of ZrO₂ improved the mechanical properties of sintered MgAl₂O₄ samples: 20 wt-%ZrO₂-MgAl₂O₄ composites prepared from CSPs and conventional SSPs and sintered at 1625°C for 3 h had fracture toughness of 5·96 and 4·33 MPa m^1/2 and three point bend strength of 269 and 98 MPa respectively. Higher sintered density, the presence of tetragonal zirconia as a major phase, and the finer microstructure are probably responsible for the superior mechanical properties exhibited by sintered CSP materials as compared with the sintered SSPs.     

The influence of microstructure on the static and dynamic strength of transparent Magnesium Aluminate Spinel (MgAl2O4)

The dynamic flexural strength of transparent ceramics is an important property for demanding applications. Therefore, this work reports a systematic study of the grain size influence on the dynamic and static flexural strength of Magnesium Aluminate Spinel (MgAl₂O₄), utilizing a modified split Hopkinson (Kolsky) apparatus. An ultra-high-speed camera (8?×?10⁶ frames/sec), was extensively used and provided precious insight of the dynamic crack initiation and propagation. It was found that fine microstructure Spinel exhibits slightly higher static flexural strength than coarser microstructure. However, in the dynamic regime, no significant difference was found. Moreover, the fracture timing method, i.e. fracture gauge or high-speed camera, influences significantly the dynamic strength results. While the fracture gauges indicate complete fracture, the high-speed camera captures the onset of the fracture as a true material property. Consequently, Spinel’s dynamic flexural strength is not rate sensitive, based on high-speed imaging.     

Effect of sintering conditions on optical and mechanical properties of MgAl2O4/Al2O3 laminated transparent composite fabricated by spark-plasma-sintering (SPS) processing

To realize a high hardness in transparent MgAl₂O₄, the MgAl₂O₄/Al₂O₃ laminated composite was fabricated by a one-step spark-plasma-sintering (SPS) method. By sintering at a temperature of 1225 °C for 10 min and at a heating rate of ≤ 10 °C/min under a pressure of 300 MPa, the MgAl₂O₄/Al₂O₃ laminated composites can attain a high hardness with maintaining the wide band transparency. The in-line and IR transmission were ～50 % at the visible wavelength of 500 nm and >77 % at the wavelength of 4 μm, respectively. The Vickers hardness measured on the surface of the Al₂O₃ layer perpendicular to the MgAl₂O₄/Al₂O₃ stacking exhibited 29 GPa, which is higher than those of the monolithic Al₂O₃ (26.6 GPa) and MgAl₂O₄ (17.2 GPa). The wide band transparency and mechanical properties can be realized by simultaneously attaining smaller grain sizes and higher densities of both the MgAl₂O₄ and Al₂O₃ phases in the laminated composite by optimizing the SPS conditions.     

尖晶石对Al2O3-SiC-C质铁沟浇注料性能的影响

以新型亚白刚玉(8~5 mm、5~3 mm、3~1 mm、≤1 mm、≤0.044 mm)、SiC(≤1 mm、≤0.088 mm)、尖晶石粉(≤0.044 mm)、SiO2微粉、α-Al2O3微粉、铝酸钙水泥、Si粉和球状沥青等为主要原料,在Al2O3-SiC-C质铁沟浇注料的配料组成中分别加入质量分数为0、4%、7%、10%、13%的镁铝尖晶石粉,混练均匀后振动成型为40 mm×40 mm×160 mm的条状试样和50/20 mm×50/20mm的坩埚试样,经110℃24 h和1 450℃3 h热处理后测定试样的体积密度、显气孔率、常温抗折强度、常温耐压强度、烧后线变化率和抗渣性能,并且进行了XRD、SEM和EDS分析。结果表明:加入适量镁铝尖晶石粉后,由于改善了试样的成型密度,促进了试样的烧结,因而提高了试样的密度、强度、体积稳定性和抗渣性;但是,由于尖晶石和刚玉的热膨胀系数不同,加入过多的镁铝尖晶石粉会导致试样中产生过多的微裂纹,从而对试样的密度、强度、体积稳定性和抗渣性不利;本试验中,尖晶石粉的最佳加入量(质量分数)为10%;尖晶石加入量为10%的试样中有长度为30~80μm的SiC晶须生成,并且其颗粒与基质之间结合紧密。     

Effect of MgAl2O4 nanoparticles addition on the densification and properties of MgO-CaO refractories

MgAl₂O₄nanoparticles were added to MgO–CaO refractory ceramic composites in the range of 0–8 wt%. Refractory specimens were obtained by sintering at 1650 °C for 3 h in an electric furnace. Refractory specimens were characterized by measurements of bulk density, apparent porosity, hydration resistance, cold crushing strength, crystalline phase formation, and microstructural analysis. Results show that with additions of MgAl₂O₄ nanoparticles the bulk density of the samples increased. But the apparent porosity and cold crushing strength decreased and increased, respectively with addition MgAl₂O₄ nanoparticles up to 6 wt% and for further MgAl₂O₄ nanoparticles, due to the thermal expansion mismatch, the results is reversed. Also, the hydration resistance of the samples was appreciably improved by the addition of MgAl₂O₄ nanoparticles due to its effect on decreasing the amount of free CaO in the refractory composite and promotion of densification by creating a dense microstructure.