Pressureless Sintering of Zirconium Diboride with Carbon and Boron Carbide Nanopowder

Zirconium diboride ceramics with and without carbon and boron carbide nano powder additives were prepared by ball milling with ZrB2 grinding media and pressureless sintering. Additions of up to 1 wt% nano-B4C and 0.5 wt% C were made to the ZrB2 powder. The materials were then sintered between 1800 and 2300 °C for between 90 and 360 min in an Ar/10H2 atmosphere. After sintering at 2200 °C for 90 min, densities ranged from 88.3 to 90.7% for the ZrB2 with 0–1.0% nano-B4C addition. Carbon additions of 0.5 wt% and nano-B4C additions from 0 to 1.0 wt% resulted in densities ranging from 90.9 to 91.9% after sintering at 2100 °C for 90 min. Grain size ranged from 16.6 to 21.7 μm for ZrB2 with nano-B4C content increasing from 0 to 1.0 wt%, sintered at 2200 °C. For the ZrB2 with 0.5 wt% C, increasing the nano-B4C content from 0 to 1.0 wt% resulted in a decrease in grain size from 25.4 to 18.5 μm. The densities achieved in this study were lower than previous pressureless sintering studies of ZrB2 that used WC-6Co grinding media, presumably due to the absence of WC and Co that can also act as sintering aids

Processing and Mechanical Properties of Hot-Pressed Zirconium Diboride – Zirconium Carbide Ceramics

ZrB2 was mixed with 0.5 wt% carbon and up to 10 vol% ZrC and densified by hot-pressing at 2000 °C. All compositions were \u3e 99.8% dense following hot-pressing. The dense ceramics contained 1–1.5 vol% less ZrC than the nominal ZrC addition and had between 0.5 and 1 vol% residual carbon. Grain sizes for the ZrB2 phase decreased from 10.1 µm for 2.5 vol% ZrC to 4.2 µm for 10 vol% ZrC, while the ZrC cluster size increased from 1.3 µm to 2.2 µm over the same composition range. Elastic modulus was ~505 GPa and toughness was ~2.6 MPa·m½ for all compositions. Vickers hardness increased from 14.1 to 15.3 GPa as ZrC increased from 2.5 to 10 vol%. Flexure strength increased from 395 MPa for 2.5 vol% ZrC to 615 MPa for 10 vol% ZrC. Griffith-type analysis suggests ZrB2 grain pullout from machining as the strength limiting flaw for all compositions

Robots Working with Hazardous Materials

While many research and development activities take place at Sandia National Laboratories' Intelligent Systems and Robotics Center (ISRC), where the "rubber meets the road" is in the ISRC'S delivered systems. The ISRC has delivered several systems over the last few years that handle hazardous materials on a daily basis, and allow human workers to move to a safer, supervisory role than the "hands-on" operations that they used to perform. The ISRC at Sandia performs a large range of research and development activities, including development and delivery of one-of-a-kind robotic systems for use with hazardous materials. Our mission is to create systems for operations where people can't or don't want to perform the operations by hand, and the systems described in this article are several of our first-of-a-kind deliveries to achieve that mission

Elevated Temperature Thermal Properties of ZrB2-B4C Ceramics

The elevated temperature thermal properties of zirconium diboride ceramics containing boron carbide additions of up to 15 vol% were investigated using a combined experimental and modeling approach. The addition of B4C led to a decrease in the ZrB2 grain size from 22 µm for nominally pure ZrB2 to 5.4 µm for ZrB2 containing 15 vol% B4C. The measured room temperature thermal conductivity decreased from 93 W/m·K for nominally pure ZrB2 to 80 W/m·K for ZrB2 containing 15 vol% B4C. The thermal conductivity also decreased as temperature increased. For nominally pure ZrB2, the thermal conductivity was 67 W/m·K at 2000 °C compared to 55 W/m·K for ZrB2 containing 15 vol% B4C. A model was developed to describe the effects of grain size and the second phase additions on thermal conductivity from room temperature to 2000 °C. Differences between model predictions and measured values were less than 2 W/m·K at 25 °C for nominally pure ZrB2 and less than 6 W/m·K when 15 vol% B4C was added

Relating Detonation Parameters to the Detonation Synthesis of Silicon Carbide

Detonation synthesis of silicon carbide (SiC) nanoparticles from carbon liberated by negatively oxygen balanced explosives was evaluated in a 23 factorial design to determine the effects of three categorical experimental factors: (1) cyclotrimethylene-trinitramine (RDX)/2,4,6-trinitrotoluene (TNT) ratio, (2) silicon (Si) additive concentration, and (3) Si particle size. These factors were evaluated at low and high levels as they relate to the detonation performance of the explosive and the solid Si-containing phases produced. Detonation velocity and Chapman-Jouguet (C-J) detonation pressure, which were measured using rate stick plate dent tests, were evaluated. Solid detonation product mass, silicon carbide product concentration, and residual silicon concentration were evaluated using the x-ray diffraction analysis. The factors of Si concentration and the RDX:TNT ratio were shown to affect detonation performance in terms of detonation velocity and C-J pressure by up to 10% and 22%, respectively. Increased concentration of Si in the reactants improved the average SiC concentration in the detonation products from 1.9 to 2.8 wt. %. Similarly, increasing the ratio of RDX to TNT further oxidized detonation products and reduced the average residual Si remaining after detonation from 8.6 to 2.8 wt. %. A 70:30 mass ratio mixture of RDX to TNT loaded with 10 wt. % \u3c 44 μm silicon powder produced an estimated 1.33 g of nanocrystalline cubic silicon carbide from a 150-g test charge. Using a lower concentration of added silicon with a finer particle size reduced SiC yield in the residue to 0.38 g yet improved the SiC to residual Si ratio to 1.64:1

Synthesis, densification, and cation inversion in high entropy (Co,Cu,Mg,Ni,Zn)Al2O4 spinel

The synthesis, densification behavior, and crystallographic site occupancy were investigated for four different spinel-based ceramics, including a high-entropy spinel (Co0.2Cu0.2Mg0.2Ni0.2 Zn0.2)Al2O4. Each composition was reacted to form a single phase, but analysis of X-ray diffraction patterns revealed differences in cation site occupancy with the high-entropy spinel being nearly fully normal. Densification behavior was investigated and showed that fully dense ceramics could be produced by hot pressing at temperatures as low as 1375°C for all compositions. Vickers’ hardness values were at least 10 GPa for all compositions. The cations present in the high-entropy spinel appear to have a stabilizing effect that led to nearly normal site occupancy compared to full cation inversion behavior of nickel aluminate spinel. This is the first report that compares cation site occupancy of a high-entropy spinel to conventional spinel ceramics

Carbothermal reaction of mechanically activated ZrC powders followed by DSC-TGA

Mixtures of ZrO2 and C were prepared by high-energy ball milling. Powders were milled for times from 0 to 120 minutes in air atmosphere. As milling time increased, surface area of powders increased, indicating significant particle size reduction. The thermal treatment cycle included heating at 10 °C/min to 1600 °C followed by an isothermal hold for 2 hours under the vacuum (~20 Pa) in a resistance-heated graphite element furnace. This first step of the process promoted carbothermal reaction of the starting materials. DSC-TGA was used to follow the carbothermal reaction. The onset temperature does not seem to change for non-activated and activated powders. The change in peak area may be related to the amount of the powder that reacts at this temperature. The catbothermal reaction was split into two parts for powders activated 60 and 120 minutes. Only part of the powder reacts at the initial reaction, and then higher temperatures are required for full reaction

Disordered enthalpy–entropy descriptor for high-entropy ceramics discovery

The need for improved functionalities in extreme environments is fuelling interest in high-entropy ceramics1,2,3. Except for the computational discovery of high-entropy carbides, performed with the entropy-forming-ability descriptor4, most innovation has been slowly driven by experimental means1,2,3. Hence, advancement in the field needs more theoretical contributions. Here we introduce disordered enthalpy–entropy descriptor (DEED), a descriptor that captures the balance between entropy gains and enthalpy costs, allowing the correct classification of functional synthesizability of multicomponent ceramics, regardless of chemistry and structure. To make our calculations possible, we have developed a convolutional algorithm that drastically reduces computational resources. Moreover, DEED guides the experimental discovery of new single-phase high-entropy carbonitrides and borides. This work, integrated into the AFLOW computational ecosystem, provides an array of potential new candidates, ripe for experimental discoveries

Blumenzwiebel-Treiberei auf Gläsern

Von W. Fahrenholt

Elevated Temperature Strength Enhancement of ZrB₂-30 vol% SiC Ceramics by Postsintering Thermal Annealing

The mechanical properties of dense, hot-pressed ZrB2-30 vol% SiC ceramics were characterized from room temperature up to 1600⁰C in air. Specimens were tested as hot-pressed or after hot-pressing followed by heat treatment at 1400⁰C, 1500⁰C, 1600⁰C, or 1800⁰C for 10 h. Annealing at 1400⁰C resulted in the largest increases in flexure strengths at the highest test temperatures, with strengths of 470 MPa at 1400⁰C, 385 MPa at 1500⁰C, and 425 MPa at 1600⁰C, corresponding to increases of 7%, 8%, and 12% compared to as hot-pressed ZrB2-SiC tested at the same temperatures. Thermal treatment at 1500⁰C resulted in the largest increase in elastic modulus, with values of 270 GPa at 1400⁰C, 240 GPa at 1500⁰C, and 120 GPa at 1600⁰C, which were increases of 6%, 12%, and 18% compared to as hot-pressed ZrB2-SiC. Neither ZrB2 grain size nor SiC cluster size changed for these heat-treatment temperatures. Microstructural analysis suggested additional phases may have formed during heat treatment and/or dislocation density may have changed. This study demonstrated that thermal annealing may be a useful method for improving the elevated temperature mechanical properties of ZrB2-based ceramics