Thermal Analysis and Optimization of the Phase Diagram of the Cu-Ag Sulfide System

Thermal stabilities of selected ternary phases of industrial interest in the Ag-Cu-S system have been studied by the calorimetric and electromotive force techniques. The ternary compounds Ag1.2Cu0.8S (mineral mackinstryite) and AgCuS (mineral stromeyerite) were equilibrated through high-temperature reaction of the pure Cu2S and Ag2S in an inert atmosphere. The synthesized single solid sample constituting the two ternary phases was ground into fine powders and lightly pressed into pellets before calorimetric measurements. An electrochemical cell incorporating the two equilibrated phase and additional CuS as a cathode material was employed. The measurement results obtained with both techniques were analyzed and thermodynamic properties in the system have been determined and compared with the available literature values. Enthalpy of fusion data of the Ag-richer solid solution (Ag,Cu)2S have also been determined directly from the experimental data for the first time. The thermodynamic quantities determined in this work can be used to calculate thermal energy of processes involving the Ag-Cu-S-ternary phases. By applying the obtained results and the critically evaluated literature data, we have developed a thermodynamic database. The self-developed database was combined with the latest pure substances database of the FactSage software package to model the phase diagram of the Ag2S-Cu2S system.

Preparation of Graphene Oxide/Cellulose Composites with Microcrystalline Cellulose Acid Hydrolysis Using the Waste Acids Generated by the Hummers Method of Graphene Oxide Synthesis

The Hummers method is the most commonly used method to prepare graphene oxide (GO). However, many waste acids remain in the raw reaction mixture after the completion of this reaction. The aim of this study was to reuse these waste acids efficiently. In this study, microcrystalline cellulose (MCC) was directly dissolved in the mixture after the high-temperature reaction of the Hummers method. The residual acid was used to hydrolyze MCC, and the graphene oxide/microcrystalline cellulose (GO/MCC) composites were prepared, while the acid was reused. The effects of MCC addition (0.5 g, 1.0 g, and 1.5 g in 20 mL) on the properties of the composites were discussed. The structure, composition, thermal stability, and hydrophobicity of GO/MCC composites were characterized and tested by SEM, XRD, FTIR, TG, and contact angle tests. The results showed that MCC could be acid hydrolyzed into micron and nano-scale cellulose by using the strong acidity of waste liquid after GO preparation, and it interacted with the prepared GO to form GO/MCC composites. When the addition amount of MCC was 1 g, the thermal stability of the composite was the highest due to the interaction between acid-hydrolyzed MCC and GO sheets. At the same time, the hydrophobic property of the GO/MCC composite is better than that of the GO film. The freeze-dried GO/MCC composites are more easily dispersed in water and have stronger stability.

Calcium-Doped Boron Nitride Aerogel Enables Infrared Stealth at High Temperature Up to 1300 °C

Boron nitride (BN) aerogels, composed of nanoscale BN building units together with plenty of air in between these nanoscale building units, are ultralight ceramic materials with excellent thermal/electrical insulation, great chemical stability and high-temperature oxidation resistance, which offer considerable advantages for various applications under extreme conditions. However, previous BN aerogels cannot resist high temperature above 900 °C in air atmosphere, and high-temperature oxidation resistance enhancement for BN aerogels is still a great challenge. Herein, a calcium-doped BN (Ca-BN) aerogel with enhanced high-temperature stability (up to ~ 1300 °C in air) was synthesized by introducing Ca atoms into crystal structure of BN building blocks via high-temperature reaction between calcium phosphate and melamine diborate architecture. Such Ca-BN aerogels could resist the burning of butane flame (~ 1300 °C) and keep their megashape and microstructure very well. Furthermore, Ca-BN aerogel serves as thermal insulation layer, together with Al foil serving as both low-infrared-emission layer and high-infrared-reflection layer, forming a combination structure that can effectively hide high-temperature target (heated by butane flame). Such successful chemical doping of metal element into crystal structure of BN may be helpful in the future design and fabrication of advanced BN aerogel materials, and further extending their possible applications to extremely high-temperature environments.

Dramatic improvement of NO reduction activity via reversible re-dispersion of CeO2 nanoparticles into Ce+3 atoms on alumina under high temperature reactive treatment

Ceria nanoparticles supported on gamma-alumina prepared via wet impregnation and sourced commercially have low activity for industrially relevant NO reduction by CO in the presence of steam. These supports contain ceria nanoparticles as well as small (~1%) amount of Ce atomically dispersed and anchored by penta-Al sites. We discovered that treatment of these catalysts at temperatures ~750-950 ºC under the flow of CO and NO in the presence of steam, which typically leads to catalyst deterioration and sintering, in fact, leads to dispersion of ceria nanoparticles into isolated Ce+3 atoms. We extensively characterize them with XPS, FTIR and HAADF-STEM imaging. Their presence changes the alumina surface, as evidenced by XPS and FTIR with probe molecules. Ce+3 ions show dramatically enhanced NO reduction ability in the presence of CO and steam. Infra-red studies reveal close interaction of NO molecules on Ce+3/Alumina surfaces with the formation of N2O species. Heating these samples in oxygen (in wet or dry streams) at 800 ºC and above leads to coalescence of Ce+3 into CeO2 nanoparticles, resulting in reversible loss of activity. Further, reactive treatment of CeO2/Al2O3 under high temperature reaction conditions restores Ce+3 cations as well as catalytic activity. Our study shows reversible redispersion of ceria into isolated Ce+3 cations under conditions where typical catalyst sintering is generally assumed to occur and suggests a pathway to utilize these materials as supports for more effective catalysis. Indeed, supporting only 0.1-0.5 wt% Rh on these CeAl supports, shows synergies between Rh and atomically dispersed Ce ions with excellent activity and stability for NO reduction with CO.

On the extraordinary low quench sensitivity of an AlZnMg alloy

The scope of this work was to investigate the quench sensitivity of a high-purity wrought aluminum alloy Al6Zn0.75 Mg (in this work called 7003pure). This is compared to a similar alloy with the additions of Fe, Si, and Zr at a sum less than 0.3 at.% (in this work called 7003Fe,Si,Zr). Differential scanning calorimetry (DSC) was used for an in situ analysis of quench induced precipitation in a wide range of cooling rates varying between 0.0003 and 3 K/s. In 7003pure, three main precipitation reactions were observed during cooling, a medium temperature reaction with a distinct double peak between 325 and 175 °C and a very low temperature reaction starting at about 100 °C. An additional high temperature reaction related to the precipitation of Mg2Si starting at 425 °C has been observed for 7003Fe,Si,Zr. In terms of hardness after natural as well as artificial aging, alloy 7003pure shows a very low quench sensitivity. Hardness values on the saturation level of about 120 HV1 are seen down to cooling rates of 0.003 K/s. The as-quenched hardness (5 min of natural aging) shows a maximum at a cooling rate of 0.003 K/s, while slower and faster cooling results in a lower hardness. In terms of hardness after aging, 0.003 K/s could be defined as the technological critical cooling rate, which is much higher for 7003Fe,Si,Zr (0.3–1 K/s). The physical critical cooling rates for the suppression of any precipitation during cooling were found to be about 10 K/s for both variants.

Acid dissolution behavior of ferritic FeCrAl tubes candidates for nuclear fuel cladding.

The international materials community is engaged in finding safer alternatives to zirconium alloys for the cladding of fuel in light water reactors. One solution is to replace the zirconium cladding using ferritic iron-chromium-aluminum -FeCrAl- alloys, which offer extraordinary resistance to high temperature reaction with air or steam due to the formation of a protective alumina layer on the external surface. It is important to characterize the behavior of FeCrAl not only during accident conditions but in the entire fuel cycle, which may include reprocessing of the used fuel after it is removed from the power reactors. The reprocessing may involve the dissolution of the fuel rods in mineral acids. Little or nothing is known on the dissolution of FeCrAl alloys in common mineral acids, therefore the objective of this research was to study the dissolution of typical cladding tubing having two compositions of FeCrAl (APMT & C26M) in three acids (H2SO4, HNO3 & HCl) as a function of the temperature using both standard ASTM immersion tests as well as electrochemical tests. The dissolution behavior of the FeCrAl alloys is compared to the dissolution capability of other traditional nuclear materials such as austenitic stainless steels (304SS & 316SS) and austenitic nickel alloys (Alloy 600 and Hastelloy C-276). Results show that both C26M and APMT have a higher dissolution capability in the studied mineral acids, which will be beneficial for reprocessing procedures.

Reduction Characteristic of CaSO4-CuO Combined Oxygen Carrier Under CO Atmosphere

CaSO4 oxygen carrier is considered to be a potential oxygen carrier (OC) for Chemical Looping Combustion because of its high oxygen capacity and low price. But its reactivity is lower than the main metal oxide oxygen carriers, and it deactivates due to sulfur loss as well as sintering at high reaction temperatures above 920 ℃. To improve the performance of CaSO4-based oxygen carrier, small amounts of CuO particles were mixed mechanistically with CaSO4 particles to use as combined oxygen carrier in this work. The reduction reactions of CaSO4 oxygen carrier, CuO oxygen carrier and CaSO4-CuO combined oxygen carrier under CO atmosphere were investigated. The effects of reaction factors including reaction temperature, the oxygen-carrying ratio of CuO to CaSO4 and mass of oxygen carrier, on the reductions have been investigated in this study. XRD, SEM-EDS, BET and gas analyses were performed to investigate the variations of solid phase, element compositions in solid residual and sulfur release with reaction time. The results show that the addition of CuO increases the reactivity of the CaSO4-based oxygen carrier while also suppressing the release of the gas sulfur. For the individual reduction of CaSO4 by CO, with the increase of CaSO4 mass (500 - 1200 mg), CO2 yield also increases until 1000 mg stops and SO2 released rises remarkably; An increase in the reaction temperature aggravated the SO2 emission. The carbon dioxide generation efficiency also increases with an increase in temperature, but decreases when the temperature exceeds 950 ℃ due to sintering of the oxygen carrier particles; With respect to the reaction of CuO with CO, CO2 yield does not change significantly with increasing temperature, due to the sintering of the CuO oxygen carrier in a high temperature reaction environment;For the combined oxygen carrier: a.As the reduction reaction temperature increases, the reduction reaction performance of the combined oxygen carrier is enhanced within the reaction temperature range of 750~900℃. b. CaO the use of CuO additives not only improves the CO conversion rate, but also inhibits the release of gas sulfide. As the oxygen carrying fraction of CuO increases, SO2 released is reduced and the SO2 release time is delayed. What� more, the solid products after reduction reaction mainly contain CaS, CaO, CuO, Cu2O and CaSO4, and no copper sulfide is detected. c. When the oxygen-carrying ratio of CuO to CaSO4 is increasing from 15% to 20%, CO2 yield increases greatly.

The structure of Ce2Al3Ge4 refined for the first time from single-crystal X-ray diffraction data

Single crystals of dicerium trialuminium tetragermanide, Ce2Al3Ge4, have been synthesized from a high-temperature reaction using an eutectic mixture of Al and Ge as a metal flux. Through single-crystal X-ray diffraction it was established that Ce2Al3Ge4 crystallizes in the centrosymmetric space group Cmce (No. 64) with the Ba2Cd3Bi4 structure type (Pearson code oC36). Five atoms compose the asymmetric unit, i.e. one Ce, two Al, and two Ge atoms, all in special positions with Wyckoff symbols 8f (Ce), 4a and 8e (Al), and 8e and 8f (Ge). The structure can be described as a three-dimensional network of Al and Ge atoms, with Ce atoms occupying the cavities of the framework.