Modelling transparent ceramics to improve military armour

The dominant materials solution used for ballistic transparency protection of armoured tactical platforms in commercial and military applications is low cost glass backed by polycarbonate. Development of next generation ceramics is critical to offering enhanced protection capability and extended service performance for future armoured windows to the soldier. Due to the high cost of testing transparent ceramics, a modelling approach has been undertaken in parallel with ballistic testing to validate armour designs based on a transparent magnesium aluminate spinel, MgAl₂O₄, striking-ply backed by polycarbonate. A key purpose is to characterize the influence of defects on the failure of laminates, both statically and dynamically tested. Finite element modelling is used to predict unsuccessful designs and reduce number of laminate configurations in experimental testing. A notional ceramic armour system based on spinel/polycarbonate assemblies is used to report results on the effect of surface and interior, equal area defects on the ballistic behavior of a laminates.     

Preparation and properties of MgAl2O4 spinel ceramics by double-doped CeO2 and La2O3

Magnesium aluminate spinel (MgAl₂O₄) ceramics are high-performance and carbon-free materials widely used in both military and civilian fields. However, it is usually challenging to densify during the solid-state sintering process. The excellent properties of some rare earth oxides have been proved to promote the densification of MgAl₂O₄ spinel ceramics. But the mechanism of promoting sintering is not clear. In the present work, MgAl₂O₄ spinel ceramics have been successfully fabricated by co-doping CeO₂ and La₂O₃ via a single-stage solid-state reaction sintering. The effects of addition amounts of CeO₂ and La₂O₃ on phase compositions, microstructures, sintering characteristics, cold compressive strength, and thermal shock resistance of as-prepared MgAl₂O₄ spinel ceramics were systematically investigated. The results show that by co-doping CeO₂ and La₂O₃ can increase the defect concentration due to the lattice distortion. This could promote the movement of Al³⁺ and Mg²⁺ at high temperature, which is beneficial to the formation of more secondary MgAl₂O₄ spinel. t-ZrO₂ with more Ce⁴⁺ filling between spinel grains could prevent the growth of grains and promote the densification, besides the new-formed LaAlO₃ that was mainly distributed along the grain boundary of the MgAl₂O₄ phase, both of which were favorable for the formation of dense microstructure of MgAl₂O₄ spinel materials. At the same time, the formation of more secondary MgAl₂O₄ spinel and sintering densification also improve the mechanical properties of spinel ceramics. La³⁺ will segregate to the spinel grain boundary, preventing grain boundary movement and absorbing the main crack's fracture energy. With 3 wt% CeO₂ and 3 wt% La₂O₃ co-doping, the bulk density of the sample increased from 3.02 g∙cm⁻³ to 3.55 g∙cm⁻³; the apparent porosity decreased from 12.21% to 9.97%; the cold compressive strength increased from 172.88 MPa to 189.54 MPa; and the residual strength retention ratio after thermal shock increased from 84.92% to 89.15%.     

Fabrication and properties of Co:MgAl2O4 transparent ceramics for a saturable absorber from coprecipitated nanopowder

The 0.05 at.% Co:MgAl₂O₄ precursor was synthesized by the coprecipitation method from a mixed solution of magnesium, aluminum, and cobalt nitrates using ammonium carbonate as the precipitant. 0.05 at.% Co:MgAl₂O₄ transparent ceramics were successfully obtained via vacuum sintering and hot isostatic pressing (HIP) of 0.05 at.% Co:MgAl₂O₄ nanopowder calcined at 1100°C for 4 hours. The properties of powder and ceramics were comprehensively investigated. X-ray diffraction (XRD) results showed that Co:MgAl₂O₄ nanopowder had a pure spinel phase. Also, the in-line transmittances of the HIP posttreated Co:MgAl₂O₄ ceramics with the thickness of 1.2 mm were 82% at 400 nm and 84.7% at 900 nm. The average grain sizes of 0.05 at.% Co:MgAl₂O₄ ceramics before and after the HIP posttreatment were 11 and 28 μm, respectively. The calculated ground state absorption cross section of 0.05 at.% Co:MgAl₂O₄ ceramics was 2.9 × 10⁻¹⁹ cm², indicating that this ceramics is a promising material applied as a saturable absorber for passive laser Q-switches in the 1.3-1.7 μm domain.     

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.     

Preparation and optical properties of highly transparent MgAl1.9Ga0.1O4 ceramics via aqueous gel-casting method

The aqueous gel-casting technology has been widely used to prepare high-quality green body for various transparent ceramics with large dimension and complex shape. However, owing to the severe hydrolysis of MgAl₂O₄ powder, it is challenging to obtain thick aqueous slurry with high homogeneity and flowability. In this paper, the surface chemical state of MgAl₂O₄ powder was modified by introducing Ga³⁺, and stable MgAl_1.9Ga_0.1O₄ aqueous slurry with high solid-phase loading (52 vol. %) and low viscosity (136 mPa·s, at a shear rate of 50 s^-1) was successfully prepared. After pressureless presintering and hot isostatic pressing, the gel-cast sample exhibited much higher optical transmittance and more homogeneous microstructure than the dry-pressed sample, which is mainly derived from the improved homogeneity and densification of the green bodies and ceramics. The optical band gap, infrared cutoff wavelength, static refractive index and dispersion of both MgAl_1.9Ga_0.1O₄ and MgAl₂O₄ transparent ceramics were systematically compared. It is indicated that the transparent MgAl_1.9Ga_0.1O₄ ceramic has the increscent static refractive index of 1.695, the decrescent direct band gap energy of 6.15 eV and absorption coefficient of 0.49 cm^-1 at 5 µm, which could be ascribable to the fact that Ga³⁺ has different electronic structure, higher electronic polarizability and larger ionic radius in comparison with Al³⁺. This work provides a dependable solution for preparation of spinel oxide ceramics with superior optical properties and large dimension.     

Low cost foam-gelcasting preparation and characterization of porous magnesium aluminate spinel (MgAl2O4) ceramics

Porous MgAl₂O₄ ceramics were prepared via a low cost foam-gelcasting route using MgAl₂O₄ powders as the main raw material, ammonium polyacrylate as a dispersant, a small amount of modified carboxymethyl cellulose as a gelling agent, and TH-IV polymer as a foaming agent. The effects of additive's content, solid loading and gelling temperature on slurry's rheological behavior were investigated, and microstructures and properties of as-prepared porous MgAl₂O₄ ceramics examined. Based on the results, the roles played by the foaming agent in the cases of porosity, pore structure, pore size, mechanical properties and thermal conductivity were clarified. Porosity and pore sizes of as-prepared porous MgAl₂O₄ ceramics increased with increasing the foaming agent from 0.05 to 0.6 vol%. Porous MgAl₂O₄ ceramics with porosity of 75.1% and average pore size of 266 µm exhibited a compressive strength as high as 12.5±0.8 MPa and thermal conductivity as low as 0.24 W/(m K) (at 473 K).     

Effects of LiF on the microstructure and optical properties of hot-pressed MgAl2O4 ceramics

Transparent magnesium aluminate spinel (MgAl₂O₄) ceramics were fabricated by hot-pressing of the MgO and α-Al₂O₃ powder mixture using LiF as a sintering aid. Effects of the LiF additive on densification, microstructure and optical properties of MgAl₂O₄ ceramics were systematically investigated. It has been found that the addition of LiF can effectively remove the porosity and increase the optical transparency of MgAl₂O₄ ceramics. For the spinel ceramics HP-ed at 1550 °C for 3 h with 1 wt% LiF addition, the average grain size is about 36 µm and the in-line transmittance exceeds 60% at the wavelength of 800 nm.     

Joining transparent spinel ceramics using refractive index–matched glass

Ceramic joining by glass is a promising method of the preparation of large transparent ceramics from small blocks. The chemical composition of glass was optimised to match the coefficient of thermal expansion and refractive index of transparent magnesium aluminate (MgAl₂O₄) ceramics. A two-step joining method was developed to join MgAl₂O₄ ceramics with a reduced number of bubbles in the joint, and the thermal properties of the optimised glass were evaluated to determine the joining temperature. Two transparent MgAl₂O₄ blocks were joined by a glass layer that was approximately 20 µm thick. The joint area could not be distinguished with a naked eye. The transmittance of the joined body vertical to or parallel through the glass layer was approximately the same as that of the ceramics. The average three-point bending strength of the joint reached 202 ± 33 MPa, which was 64% that of the ceramic body.     

Single and Polycrystalline Transparent Ceramic Armor with Different Crystal Structure

Contrary to the moderate ballistic advantage of Al₂O₃ ceramics over MgAl₂O₄ polycrystals, the present study shows a reverse ratio of the ballistic strength of alumina and spinel single crystals: Spinel single crystals outperform sapphire and exhibit a similarly high stability as submicrometer Al₂O₃ ceramics. The results correlate with different cleavage of single crystalline spinel and sapphire, changing the fragmentation on ballistic impact.     

Highly transparent Mg0.27Al2.58O3.73N0.27 ceramic fabricated by aqueous gelcasting,pressureless sintering,and post-HIP

Magnesium aluminum oxynitride (Mg_0.27Al_2.58O_3.73N_0.27, termed as MgAlON) ceramics with high transparency and complicated shape was prepared by aqueous gelcasting, pressureless sintering, and followed by hot isostatic pressing. No obvious hydration was found by the characterizations of X-ray diffraction, pH value, Fourier transform infrared and thermal analysis for the interaction between MgAlON spinel powders and water, leading to the stable MgAlON slurry with high solid loading (52 vol%) and low viscosity. This result may be due to different composition of MgAlON from that of MgAl₂O₄ and AlON. Besides, transparent MgAlON ceramic (1.95 mm in thickness) with a high in-line transmittance ~86.3% at 3.7 μm was fabricated. The refractive index ~1.7499 at 589.3 nm and absorption coefficient ~1.2 cm⁻¹ at 5 μm of MgAlON are between those of AlON and MgAl₂O₄ transparent ceramics, and Abbé number ~73.66 of MgAlON is the highest.     

Sintering,hardness and cation inversion of nanocrystalline Beryllium – Magnesium aluminate ceramics

Beryllium-magnesium aluminate (Be_0.1Mg_0.9Al₂O₄ and Be_0.2Mg_0.8Al₂O₄) nanoparticles are synthesized by a coprecipitation method and sintered using Spark Plasma Sintering (SPS) to achieve near full density ceramics with grain sizes at the nanoscale. The sintered nanoceramics display grain sizes ranging from 14 to 33 nm, which are analyzed for optical transmission, Vickers hardness, and cation site inversion. When compared to Be-free MgAl₂O₄ nanoceramics, both Be_0.1Mg_0.9Al₂O₄ and Be_0.2Mg_0.8Al₂O₄ show transmissions ～30% lower at wavelength in the infrared range. The samples show a Vickers hardness of ～19.2 GPa with no apparent dependence on grain size. These values are consistently lower to those reported for beryllium-free MgAl₂O₄ spinel with similar grain size. ²⁷Al and ⁹Be Nuclear Magnetic Resonance (NMR) spectroscopy reveals that beryllium does not have a significant effect on cationic site inversion in the spinel and, similar to beryllium-free MgAl₂O₄, inversion remains solely a function of grain size. The results indicate beryllium ions form solid-solutions with MgAl₂O₄ spinel structure and do not alter the grain boundaries significantly enough to influence the mechanical properties of nanocrystalline ceramics.     

Nonlinear Absorption of Submicrometer Grain‐Size Cobalt‐Doped Magnesium Aluminate Transparent Ceramics

Transparent cobalt‐doped magnesium aluminate spinel (Co:MgAl₂O₄) ceramics with a submicrometer grain size were prepared by spark plasma sintering. For the first time, the nonlinear absorption of Co:MgAl₂O₄ transparent ceramics was experimentally demonstrated. Both ground state absorption (σ_GSA) and excited state absorption (σ_ESA) were estimated using the solid‐state slow saturable absorber model based on absorption saturation measurements performed at 1.535 μm. σ_GSA and σ_ESA for 0.03 at.% Co:MgAl₂O₄ were found to be 4.1 × 10^?19 cm² and 4.0 × 10^?20 cm², respectively. In the case of 0.06 at.% Co:MgAl₂O₄ ceramics, σ_GSA = 2.6 × 10^?19 cm² and σ_ESA= 5.3 × 10^?20 cm² were determined.     

Influence of post-HIP temperature on microstructural and optical properties of pure MgAl2O4 spinel: From opaque to transparent ceramics

Transparent MgAl₂O₄ spinel ceramics were processed from sub-micrometric commercial powder by applying a two-step procedure: pressureless sintering under vacuum followed by hot isostatic pressing. To limit grain growth and to avoid secondary reactions or impurities, no additives or sintering aids were added to the powder. First, pressureless sintering at 1500 °C during 2 h under vacuum led to opaque samples due to a high level of porosity. To improve the optical quality of the MgAl₂O₄ ceramics and the in-line transmission in the visible range, a post-treatment by hot isostatic pressing was applied. Highly transparent ceramics were obtained after a post-treatment at 1800 °C for 10 h with an in-line transmission of 81% at 400 nm and 86% from 950 to 3000 nm for a thickness of 2 mm (98.8% of the theoretical transmission).     

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.     

Gelling behavior of MgAl2O4 slurries with a common dispersant

MgAl₂O₄ transparent ceramics were shaped by a commonly used polyacrylic acid (PAA), which acted as both dispersant and gelling agent. The spinel slurries were prepared by ball-milling MgAl₂O₄ powder, PAA, and water in an attrition mill. The gelling of slurries happened at room temperature in air atmosphere without any other organic additive. The gelling mechanism was the formation of chelates between Mg²⁺ and carboxyl groups (-COO⁻) of PAA. The frequency-based testing method was applied to investigate the gelling process of the as-prepared slurry. In addition, a novel in situ characterization method based on a modified indentation testing was invented to better understand the strengthening of the wet green body with time and to guide when demolding could be carried out. After sintering, transparent MgAl₂O₄ ceramics with high in-line transmittance were resulted.     

Radiation heating test and development of porous MgAl2O4 ceramics with high thermal shielding effect based on Mie theory

Porous MgAl₂O₄ ceramics designated as THERMOSCATT^TM have diffuse reflectance based on the Mie theory. The reflectance greatly suppresses radiation heat transfer and has low emissivity at 1–5 μm wavelengths. Their thermal conductivity has been measured as less than 0.3 W/(m K) at 1500°C. Furthermore, porous MgAl₂O₄ ceramics have near-zero hemispherical spectral emissivity values at 0.35–5 μm wavelengths. High heat resistance and low emissivity materials in the atmosphere are useful for the innermost layer of industrial furnaces to confine energy efficiently. Additionally, this material is useful as a radiation reflectors, such as in stand-off thermal protection systems. This study elucidated the suppression of radiation transfer in porous MgAl₂O₄ ceramics attributable to low thermal emissivity. Therefore, the thermal insulation performance under radiation heating in vacuum, the emissivity validity evaluation of low-emissivity porous materials using finite element analysis, and microstructure effects on radiation heating performance and mechanical properties were investigated.     

Luminescence of MgAl2O4 and ZnAl2O4 spinel ceramics containing some 3d ions

The luminescence properties of ceramic phosphors based on two spinel hosts MgAl₂O₄ and ZnAl₂O₄ doped with manganese ions have been studied. It has been found that the spectral properties of these phosphors can be strongly varied by changing synthesis conditions. Both types of doped ceramic spinel can serve as efficient Mn²⁺ green-emitting phosphors having peak emissions at 525 and 510 nm, respectively. Mn-doped MgAl₂O₄ spinel can also be prepared as an efficient Mn⁴⁺ red-emitting phosphor having peak emission at ~651 nm by using specific temperatures of heat treatment in air. It has also been shown that the conversion of Mn²⁺ to Mn⁴⁺ and viсe versa, as well as the coexistence of Mn²⁺ green and Mn⁴⁺ red emissions, can be accomplished by properly chosen annealing conditions of the same initially synthesized MgAl₂O₄:Mn sample. Manganese doped MgAl₂O₄ spinel with an optimal intensity ratio of green and red emissions can be a promising single-phase bicolor phosphor suitable for the development of warm white phosphor-converted LED lamps. On the other hand, it has been determined that perfectly normal ZnAl₂O₄ spinel cannot be doped with Mn⁴⁺ ions in contrast to partially inverse MgAl₂O₄ spinel. However, ZnAl₂O₄ samples unintentionally doped with impurity Cr³⁺ ions show emission spectra in the far-red region with well pronounced R, N and vibronic lines of Cr³⁺ luminescence due to the perfect normal spinel structure of synthesized ZnAl₂O₄ ceramics. Also, by partially substituting Al³⁺ cations for Mg²⁺ in ZnAl₂O₄ there is an opportunity to obtain Mn⁴⁺ doped or Mn⁴⁺/Cr³⁺ codoped far-red emitting phosphors which can be suitable for indoor plant growth lighting sources.     

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.     

Fabrication and optical properties of transparent fine-grained Zn1.1Ga1.8Ge0.1O4 and Ni2+ (or Cr3+)-doped Zn1.1Ga1.8Ge0.1O4 spinel ceramics

For the first time, a Zn_1.1Ga_1.8Ge_0.1O₄ transparent spinel ceramic has been fully densified by spark plasma sintering. XRD measurements show that this ceramic is composed of a pure cubic spinel phase. SEM analysis revealed a homogeneous and dense microstructure with the average grain size being 200 ± 100 nm. The transmittance of these fine-grained ceramics reached 70 % in the visible range and is very close to 80 % at 2 µm, thus close to the T_max value deduced from the measurement of the refractive index. The ceramics exhibit excellent mechanical properties with a Young modulus of 222 GPa, a Vickers hardness of 14.25 GPa and a thermal conductivity of 7.3 W.m⁻¹. K⁻¹. By doping with Cr³⁺ ions, transparent Zn_1.1Ga_1.8Ge_0.1O₄ ceramics present both a red luminescence and a long-lasting afterglow during several minutes. Moreover, a near infrared broadband emission at 1.3 µm is also achieved with Ni²⁺ ions.     

Synthesis,Microstructure, and Microwave Dielectric Properties of Spinel ZnGa2O4 Ceramics

Spinel ZnGa₂O₄ ceramics were synthesized by conventional solid‐state method and their microwave dielectric properties were investigated. The phase evolution and microstructures of specimens were studied by XRD and SEM. The textured surface microstructures of ZnGa₂O₄ ceramics formed at high sintering temperatures. The spinel‐structured ZnGa₂O₄ ceramics sintered at 1385°C exhibited excellent microwave dielectric properties: a dielectric constant (ε_r) of 10.4, a quality factor (Q × f) of 94.600 GHz, and a temperature coefficient of resonant frequency (τ_f) of ?27 ppm/°C. ZnGa₂O₄ ceramics have a low sintering temperature, a wide temperature region, and a small negative τ_f value. They are promising candidate materials for millimeter‐wave devices.