Applications of analytical electron microscopy to guide the design of boron carbide

Compositional analysis of boron carbide on nanometer length scales to examine or interpret atomic mechanisms, for example, solid-state amorphization or grain-boundary segregation, is challenging. This work reviews advancements in high-resolution microanalysis to characterize multiple generations of boron carbide. First, ζ-factor microanalysis will be introduced as a powerful (scanning) transmission electron microscopy ((S)TEM) analytical framework to accurately characterize boron carbide. Three case studies involving the application of ζ-factor microanalysis will then be presented: (1) accurate stoichiometry determination of B-doped boron carbide using ζ-factor microanalysis and electron energy loss spectroscopy, (2) normalized quantification of silicon grain-boundary segregation in Si-doped boron carbide, and (3) calibration of a scanning electron microscope X-ray energy-dispersive spectroscopy (XEDS) system to measure compositional homogeneity differences of B/Si-doped arc-melted boron carbides in the as-melted and annealed conditions. Overall, the improvement and application of advanced analytical tools have helped better understand processing–microstructure–property relationships and successfully manufacture high-performance ceramics.     

The effect of boron and aluminum additions on the microstructure of arc-melted boron carbide

In this work, B₄C, B₄C + 5 at.% Al, B₄C + B, and B₄C + B + 5 at.% Al were arc melted, and the resultant solid products were characterized. Results from x-ray diffraction and scanning electron microscopy showed that adding Al alone in B₄C did not result in Al doping; adding Al and B in B₄C led to Al doping. Al-doping also changed the surface energy of boron carbide in the liquid state, thus altered the wettability. Transmission electron microscopy revealed that stacking faults are more likely to form in the Al-doped sample, especially in the regions where the Al concentration is high.     

Amorphization‐induced volume change and residual stresses in boron carbide

The residual pressure surrounding quasistatic and dynamic Vickers indentations in boron carbide was quantitatively mapped in 3 dimensions using Raman spectroscopy. These maps were compared against similar maps of amorphization intensity and optical micrographs of deformed regions to determine the roles of amorphization and damage upon indentation‐induced residual stress. Stress relaxation was observed near radial cracks, spalled regions, and graphitic inclusions. A positive correlation was found between high levels of residual stress and the number of amorphized sites detected. Finite element simulations were conducted to model the indentation‐induced residual stress fields in the absence of amorphization and cracking. The simulations underpredicted the average residual pressure observed through Raman spectroscopy, implying that amorphization contributes to increased pressure in the material. This pressure is interpreted as potential evidence of volumetric expansion of the amorphized material which is less ordered and hence exerts compressive forces on the surrounding crystalline matrix.     

Rate‐Dependent Mechanical Behavior and Amorphization of Ultrafine‐Grained Boron Carbide

An investigation into mechanical properties and amorphization behavior of ultrafine‐grained (0.3 μm) boron carbide (B₄C) is conducted and compared to a baseline coarse‐grained (10 μm) boron carbide. Static and dynamic uniaxial compressive strength, and static and dynamic Vickers indentation hardness were determined, and Raman spectroscopy was then conducted on indented regions to quantify and compare the intensity of amorphization. In relation to coarse‐grained B₄C the ultrafine‐grained material exhibited, on average, a 33% higher static compressive strength, 20% higher dynamic compressive strength, 10% higher static Vickers hardness, and 23% higher dynamic Vickers hardness. In addition, there was an 18% reduction in indentation‐induced radial crack length in ultrafine‐grained B₄C, which corresponded to an increase in estimated fracture toughness. Although traditional coarse‐grained B₄C exhibits an 8.6% decrease in hardness from the static to dynamic regimes, ultrafine‐grained B₄C showed only negligible change under similar conditions, suggesting a reduced propensity for amorphization. Raman spectroscopic analysis confirmed this result by revealing significantly lower amorphization intensity in ultrafine‐B₄C compared to coarse‐grained B₄C. These results may have significant positive implications in the implementation of ultrafine‐grained boron carbide as a material for improved performance in impact and other high‐pressure applications.     

Optical characterization of boron carbide powders synthesized with varying B-to-C ratios

Boron carbide powders were synthesized from elemental powders and studied using X-ray diffraction (XRD) and UV–visible diffuse reflectance, Raman, and diffuse reflectance IR spectroscopies. Following reaction at 1400°C for 6 h, synthesized powders exhibited possible faulting as suggested by XRD patterns. B₃C, B_4.3C, and B₅C powders contained graphitic carbon whereas the boron carbides with higher B/C ratios contained no residual carbon, suggesting that the carbon rich phase boundary is likely temperature dependent. Analysis by Raman and IR spectroscopy suggested that Raman spectra are influenced by excitation frequency due to resonance. We suggest that measurement of boron carbides with resonant Raman lifts the selection rules to allow measurement of Raman silent modes that are present in the IR spectra. Optical reflectance of the boron carbide powders revealed that the B/C ratio governed the indirect and direct optical band gaps of the faulted powders. B₃C and B_4.3C powders were light gray in spite of the presence of the carbon, whereas B₅C, B_6.5C, B₁₀C, and B₁₂C were gray, green, brown, and dark brown, respectively. Increasing carbon content increased the optical indirect band gap from 1.3 eV for B₁₂C to 3.2 eV for B₃C, causing the observed color changes.     

Fabrication and characterization of arc melted Si/B co-doped boron carbide

Boron carbide undergoes stress-induced amorphization when subjected to large non-hydrostatic stresses that exceed its elastic limit. This has been proposed as the source for the abrupt loss of shear strength in boron carbide which limits its engineering applications. Si/B co-doping was suggested as one of the means to suppress stress-induced amorphization but this has not been experimentally verified. Here, by utilizing arc melting, we prepared Si/B co-doped boron carbide with increased Si content as compared to conventional methods. Through Raman analysis in conjunction with indention and elemental analyses based on SEM and STEM (ζ-factor microanalysis), it is suggested that Si/B co-doping is a promising avenue for suppressing stress-induced amorphization. A comprehensive characterization of microstructure, chemistry, and structural change of boron carbide as a result of Si/B co-doping was elucidated.     

Models for the behavior of boron carbide in extreme dynamic environments

We describe models for the behavior of hot-pressed boron carbide that is subjected to extreme dynamic environments such as ballistic impact. We first identify the deformation and failure mechanisms that are observed in boron carbide under such conditions, and then review physics-based models for each of these mechanisms and the integration of these models into a single physics-based continuum model for the material. Atomistic modeling relates the composition and stoichiometry to the amorphization threshold, while mesoscale modeling relates the processing-induced defect distribution to the fracture threshold. The models demonstrate that the relative importance of amorphization and fracture are strongly dependent on the geometry and impact conditions, with the volume fraction of amorphized material being unlikely to be significant until very high velocities (~3 km/s) are reached for geometries such as ball impact on plates. These connections to the physics thus provide guidelines for the design of improved boron carbide materials for impact applications.     

Investigation of the effect of impurity of precursor materials on Si-doped boron carbide properties

Boron carbide is a notable ceramic, with its high hardness and low density. However, it suffers a sudden loss in strength under high shear stress. Doping boron carbide with Si/B is widely used to increase its resistance to amorphization. High purity boron and silicon hexaboride precursor powders are used for doping boron carbide, but these materials have high costs and supply chain constraints. This research investigated the effect of substituting lower purity B or using pure Si powder instead of SiB₆ on materials’ properties such as elastic and mechanical properties, microstructure, and amorphization resistances. It was observed that using lower-purity boron or pure Si powder instead of SiB₆ did not significantly affect critical properties, such as fracture toughness, hardness, or amorphization resistance. However, Young's modulus values decreased as B purity decreased and as Si was used instead of SiB₆. These findings demonstrate that substituting precursor materials in Si/B co-doped B₄C is possible with little change in the material's properties. This facilitates the use of easier-to-access, cheaper production routes to be used for silicon-doped boron carbide products.     

Addressing amorphization and transgranular fracture of B4C through Si doping and TiB2 microparticle reinforcing

Over the last two decades, many studies have contributed to improving our understanding of the brittle failure mechanisms of boron carbide and provided a road map for inhibiting the underlying mechanisms and improving the mechanical response of boron carbide. This paper provides a review of the design and processing approaches utilized to address the amorphization and transgranular fracture of boron carbide, which are mainly based on what we have found through 9 years of work in the field of boron carbides as armor ceramics.     

Microstructural Characterization of a Commercial Hot‐Pressed Boron Carbide Armor Plate

Detailed microstructural characterization was carried out on a commercial‐grade hot‐pressed boron carbide armor plate. The boron carbide grains have close to B₄C stoichiometry, and most of them have no planar defects. The most prominent second phase is intergranular graphite inclusions that are surrounded by multiple boron carbide grains. Submicrometer intragranular and intergranular BN and AlN precipitates were also observed. In addition, fine dispersions of AlN nanoprecipitates were observed in some but not all grains. No intergranular films were found. These microstructural characteristics are compared with the lab‐consolidated boron carbide and their effects on the mechanical properties of boron carbide are addressed.     

Fabrication of carbon-coated boron carbide particle and its role in the reaction bonding of boron carbide by silicon infiltration

To tackle the dissolution problem of boron carbide particles in silicon infiltration process, carbon-coated boron carbide particles were fabricated for the preparation of the reaction-bonded boron carbide composites. The carbon coating can effectively protect the boron carbide from reacting with liquid Si and their dissolution, thus maintaining the irregular shape of boron carbide particles and preventing the growth of boron carbide particles and reaction formed SiC regions. Furthermore, the nano-SiC particles, originated from the reaction of the carbon coating and the infiltrated Si, uniformly coated on the surfaces of boron carbide particles, thus forming a ceramic skeleton of the nano-SiC particles-coated and -bonded boron carbide particles. The Vickers hardness, flexural strength and fracture toughness of the composites can be increased by 26 %, 45 %, and 37 % respectively, by using carbon-coated boron carbide particles as raw materials.     

Strengthening boron carbide by doping Si into grain boundaries

Grain boundaries, ubiquitous in real materials, play an important role in the mechanical properties of ceramics. Using boron carbide as a typical superhard but brittle material under hypervelocity impact, we report atomistic reactive molecular dynamics simulations using the ReaxFF reactive force field fitted to quantum mechanics to examine grain-boundary engineering strategies aimed at improving the mechanical properties. In particular, we examine the dynamical mechanical response of two grain-boundary models with or without doped Si as a function of finite shear deformation. Our simulations show that doping Si into the grain boundary significantly increases the shear strength and stress threshold for amorphization and failure for both grain-boundary structures. These results provide validation of our suggestions that Si doping provides a promising approach to mitigate amorphous band formation and failure in superhard boron carbide.     

Fabrication and characterization of hot-pressed B-rich boron carbide

Boron carbide has a wide solubility range owing to the substitution of B and C atoms in the crystal. In this study, boron carbides with different stoichiometric ratios were prepared using a hot-pressing sintering method, and the influences of the B/C atomic ratio on the microstructures and properties were explored in detail. X-ray diffraction analysis showed that excessive B atoms caused lattice expansion. Raman spectroscopy analysis showed disordered substitution of B atoms in the chains and icosahedra. Analysis of the densification process and microstructure evolution revealed that the addition of B promoted densification, and more stacking faults and twins occurred in B-rich boron carbide, and result in the densification mechanism gradually changes from atomic diffusion mechanism driven by thermal energy to plastic deformation mechanism dominated by the proliferation of dislocation and substructures. The introduction of chemical composition changes by dissolving excessive B into boron carbide further affected the microstructure and consequently the mechanical properties. The Vickers hardness, modulus, and sound velocity all decreased with the increase in B content. Moreover, the fracture toughness improved with increased B content. The flexural strength of the samples was optimised at the B/C stoichiometric ratio of 6.1.     

Raman spectroscopy mapping of amorphized zones beneath static and dynamic Vickers indentations on boron carbide

Three-dimensional models of amorphized zones beneath quasistatic and dynamic Vickers indentations on boron carbide were constructed using micro-Raman spectroscopy. The square of amorphized zone depth varied linearly with load and the maximum amorphized area occurred beneath the indentation imprint in accord with the maximum shear stress under Hertzian contact. Reduced measurements of amorphization intensity at loads above 10 N may be due to a loss of subsurface amorphized material through lateral cracks. Utilizing an expanding cavity model with power-law (n = 0.79–0.80) and linear (E_p = 0.39–0.45) strain hardening responses, finite element simulations were conducted to determine the critical values of stress and strain required to cause amorphization. These simulations suggest that amorphization may initiate at von Mises stresses and equivalent plastic strains above 6.6 GPa and 0.026, respectively. These results may be useful for validating computational models of boron carbide under complex loading scenarios (e.g., ballistic impact).     

Mechanical characterization of boron carbide single crystals

Out-of-plane anisotropy in the mechanical response of boron carbide was studied by performing nanoindentation experiments on four specific crystallographic orientations of single crystals, that is, , , , and . For each orientation of the single crystals, in-plane variations of indentation modulus and hardness were also studied by monitoring the relative rotation between the crystal surface and a Berkovich indenter tip. A significant out-of-plane anisotropy in indentation modulus was observed with ~80 GPa difference between the highest and lowest values. A smaller but measurable out-of-plane anisotropy in indentation hardness was also observed. In-plane anisotropy, on the other hand, was found to be significantly influenced by the scatter in the data and geometrical imperfections of the indenter tip. Investigations of indentation pop-in events suggested that deformation is entirely elastic prior to the first pop-in. Furthermore, quasi-plastic flow along the orientation of the single crystals was found to be more homogeneous than the other tested orientations. For select indents, cross-sectional transmission electron microscopy (TEM) of the indented regions showed formation of a quasi-plastic zone in the form of lattice rotation and various microstructural defects. The quasi-plastic zone grew in size with increasing the indentation depth. The TEM observations also suggested the crystal slip to be a potential mechanism of quasi-plasticity and a precursor for formation of amorphous bands that could eventually lead to cracking and fragmentation. The proposed failure mechanism provides valuable insights for calibrating constitutive computational models of failure in boron carbide.     

碳化硼微粉的低温合成

以聚乙烯醇和硼酸为原料,首先合成聚乙烯醇硼酸酯前驱物凝胶,然后将前驱物热解及碳热还原制备碳化硼粉末。考察了聚乙烯醇与硼酸的物质的量比,前驱物热解温度,碳热还原温度以及还原时间等因素对碳化硼合成的影响。采用IR、化学分析、XRD、离心粒度分析、SEM等方法对中间物及产物进行了表征,确定了中间物及产物的组成、物相、粒度分布及形貌。研究结果表明：前驱物合成的适宜原料配比是n(聚乙烯醇)∶n(硼酸)=4∶1;前驱物在600 ℃下热解2 h,在1 300 ℃下碳热还原2 h,得到粒径为10 μm左右的碳化硼微粉。     

The effect of the third invariant on the strength and failure of boron carbide and silicon carbide

This article presents new test data to assess the effect the third invariant has on the strength and failure of two ceramic materials: boron carbide and silicon carbide. Two experimental techniques are used: the Brazilian test that produces a biaxial state of stress, and a new technique that uses a high-pressure confinement vessel to load a specially designed dumbbell specimen in triaxial extension. The dumbbell geometry provides two important advantages over the typically used cylindrical specimen: no adhesive is required to bond the specimen to the load cell because the dumbbell geometry naturally takes the specimen into tension, and any loading asymmetries are essentially eliminated due to the axisymmetric geometry. The results show that when the stress state is on the tensile meridian the equivalent stress at failure is constant, independent of the hydrostatic pressure. The average equivalent stress at failure is for boron carbide and for silicon carbide. The Brazilian test was only performed on boron carbide and failed at , much higher than when on the tensile meridian () indicating that the effect of the third invariant is significant (because of the difference in the failure strength) and must be accounted for to accurately predict when failure will occur.     

Formation of metastable wurtzite phase boron nitride by emulsion detonation synthesis

Emulsion detonation synthesis (EDS) is a newly developed process to synthesize nano‐sized ceramic powders based on the detonation of 2 water‐in‐oil emulsions. The process provides high pressure and temperature along with rapid quenching. In this work, we report the formation of wurtzite phase BN (w‐BN) for the first time by EDS process, using hexagonal BN (h‐BN) as the precursor. Characterization studies demonstrated the formation of w‐BN with sizes varying from nanometer to micrometer scale either embedded in or grown from h‐BN matrix. These findings provide a new avenue to synthesize metastable and superhard BN phases.     

Coarsening of boron carbide grains during the infiltration of porous boron carbide preforms by molten silicon

This work investigates the coarsening of boron carbide grains during the infiltration of porous boron carbide preforms by molten silicon with respect to fabrication of reaction-bonded boron carbide ceramics. Experimental results reveal that the shape of boron carbide grains evolve from the irregular shape to faceted shape due to dissolution-precipitation during infiltration. For infiltration temperatures below 1750 °C, the boron carbide grains are irregular and exhibit an unimodal size distribution, which can be ascribed to the normal grain growth. The growth of the irregular grains follow a cubic law of diffusion control. In contrast, for infiltration temperatures above 1750 °C, the boron carbide grains become faceted and exhibit a bimodal size distribution, indicative of the typical abnormal grain growth. The abnormal growth of faceted grains is proposed to be controlled by coalescence-enhanced two-dimensional nucleation.     

Intrinsic hardness of boron carbide: Influence of polymorphism and stoichiometry

Boron carbide comprises of polymorphs that differ in crystallographic arrangement and stoichiometry. Consequently, specimens extracted from the same batch can exhibit variability in mechanical properties depending on the constituent mixture of polymorphs. In this work, density functional theory simulations and estimates from three models (bond resistance model, bond strength model, and electronegativity model) are utilized to (i) investigate the influence of polymorphism and stoichiometry on the intrinsic hardness of boron carbide, (ii) reveal the sensitivity of the estimates to the model used, and (iii) test their conformance to experimental data. The study finds intrinsic hardness of boron carbide to be primarily a function of stoichiometry, with polymorphism having a lower influence. Furthermore, hardness estimates are shown to exhibit substantial sensitivity to the model used, differing by as much as 9 GPa for the same polymorph. Thus, the search for new superhard materials should be guided by more than just one model. Our analysis finds bond resistance model to offer the best conformance to experimental data, indicating that bond length is a much stronger influencer of intrinsic hardness in covalent crystals than coordination numbers and electronegativities of bonding atoms.