Synthesis of new lead-containing MAX phases of Zr3PbC2 and Hf3PbC2

In this work, two new 312 MAX phases of Zr₃PbC₂ and Hf₃PbC₂ were successfully synthesized by spark plasma sintering. It is the first discovery of lead-containing 312 MAX phases, which together with M₂PbC (M = Ti, Zr, Hf) form the lead-containing MAX phase family. Considering the extremely low electrical conductivity of Hf₂PbC, these two new compounds are of great research value. Based on the Rietveld refinement results, their lattice parameters and atomic positions were well determined, as a = 3.3771(5) Å, c = 20.0070(9) Å for Zr₃PbC₂ and a = 3.3357(1) Å, c = 19.7659(8) Å for Hf₃PbC₂, where M atoms are located at (0, 0, 0) and (1/3, 2/3, 0.1258(6)[Zr]; 0.1255(2)[Hf]), Pb atoms are located at (0, 0, 1/4), and C atoms are located at (1/3, 2/3, 0.0663(2)[Zr]; 0.0641(3)[Hf]), respectively. Additionally, the typical laminar microstructure of Zr₃PbC₂ and Hf₃PbC₂ grains was observed.     

Thermal explosion synthesis of first Te-containing layered ternary Hf2TeB MAX phase

With the new discovery of layered boride compounds M₂AB (M = Zr, Hf, Nb; A = S, Se) with the typical Cr₂AlC-type structure, MAX phases have been successfully expanded from carbides and nitrides to borides. However, only five MAX phase borides have been synthesized at present, which means that the research on MAX phase borides is still in its infancy. Therefore, the exploration of new MAX phase borides is necessary and can provide a solid basis for future research. In this paper, we describe the discovery of the first tellurium (Te)-containing layered ternary compound Hf₂TeB using combinatorial methods of thermal explosion synthesis, XRD, SEM, and HRTEM analyses. This new MAX phase crystallizes with a Cr₂AlC-type structure with the space group of P6₃/mmc, and the lattice parameters are a = 3.60475 Å, c = 13.12663 Å, respectively, and atomic positions are Hf at (1/3, 2/3, 0.57505), Te at (1/3, 2/3, 1/4), and B at (0, 0, 0).     

A new ternary phase in the system CaO–Al2O3–Cr2O3: Crystal structure and thermal expansion of CaAl2Cr2O7

Polycrystalline material of a novel phase in the system CaO–Al₂O₃–Cr₂O₃ has been obtained by solid-state reactions. Chemical analysis indicated the composition CaAl₂Cr₂O₇. Single-crystal growth of the new compound using borax as a mineralizer was successful. Diffraction experiments at ambient conditions on a crystal with composition CaAl_2.13Cr_1.87O₇ yielded the following basic crystallographic data: space group P 3, a = 7.7690(5) Å, c = 7.6463(5) Å, V = 399.68(6) ų, Z = 3. Structure determination and subsequent least-squares refinements resulted in a residual of R(|F|) = 2.3% for 1440 independent observed reflections and 113 parameters. To the best of our knowledge, the structure of CaAl_2.13Cr_1.87O₇ or CaAl₂Cr₂O₇ represents a new structure type. It belongs to the group of double layer structures where individual double layers contain octahedrally and tetrahedrally coordinated cation positions. Linkage between neighboring sheet packages is provided by additional calcium cations. Furthermore, thermal expansion has been studied in the interval between 29 and 790°C using in situ high-temperature single-crystal diffraction. No indications for a structural phase transition were observed. From the evolution of the lattice parameters the thermal expansion tensor has been obtained. A pronounced anisotropy is evident. The response of structural building units to variable temperature has been discussed.     

Compressive Behavior of Ti3AlC2 and Ti3Al0.8Sn0.2C2 MAX Phases at Room Temperature

In this study, we report on the compressive behavior of Ti₃AlC₂ and Ti₃Al_0.8Sn_0.2C₂ MAX phases at room temperature. We found that these two phases could be classified as Kinking Nonlinear Elastic (KNE) solids. The cyclic compressive stress–strain loops for Ti₃AlC₂ and Ti₃Al_0.8Sn_0.2C₂ are typical hysteretic and fully reversible. At failure, both compositions fracture in shear with maximum stresses of 545 MPa for Ti₃AlC₂ and 839 MPa for Ti₃Al_0.8Sn_0.2C₂. Consequently, the macroshear stresses for failure, τ_c, are 185 MPa and 242 MPa for Ti₃AlC₂ and Ti₃Al_0.8Sn_0.2C₂, respectively. In addition to the grain size effects, the presence of a ductile Ti_xAl_y intermetallic distributed in the grain boundaries plays an important role in the enhancement of the ultimate compressive and macroshear stresses for Ti₃Al_0.8Sn_0.2C₂. SEM observations reveal that these two MAX phases exhibit crack deflections, intragranular fractures, kink band formation and delaminations, grain push‐in and pull‐out.     

Experimental synthesis and density functional theory investigation of radiation tolerance of Zr3(Al1‐xSix)C2 MAX phases

Synthesis, characterization and density functional theory calculations have been combined to examine the formation of the Zr₃(Al_1–xSi_x)C₂ quaternary MAX phases and the intrinsic defect processes in Zr₃AlC₂ and Zr₃SiC₂. The MAX phase family is extended by demonstrating that Zr₃(Al_1–xSi_x)C₂, and particularly compositions with x≈0.1, can be formed leading here to a yield of 59 wt%. It has been found that Zr₃AlC₂ ‐ and by extension Zr₃(Al_1–xSi_x)C₂ ‐ formation rates benefit from the presence of traces of Si in the reactant mix, presumably through the in situ formation of Zr_ySi_z phase(s) acting as a nucleation substrate for the MAX phase. To investigate the radiation tolerance of Zr₃(Al_1–xSi_x)C₂, we have also considered the intrinsic defect properties of the end‐members. A‐element Frenkel reaction for both Zr₃AlC₂ (1.71 eV) and Zr₃SiC₂ (1.41 eV) phases are the lowest energy defect reactions. For comparison we consider the defect processes in Ti₃AlC₂ and Ti₃SiC₂ phases. It is concluded that Zr₃AlC₂ and Ti₃AlC₂ MAX phases are more radiation tolerant than Zr₃SiC₂ and Ti₃SiC₂, respectively. Their applicability as cladding materials for nuclear fuel is discussed.     

Reactive spark plasma sintering of Ti3SnC2, Zr3SnC2 and Hf3SnC2 using Fe,Co or Ni additives

This work studied the effect of adding 10 at% Fe, Co or Ni to M-Sn-C mixtures with M = Ti, Zr or Hf on MAX phases synthesis by reactive spark plasma sintering. Adding Fe, Co or Ni assisted the formation of 312 MAX phases, i.e., Ti₃SnC₂, Zr₃SnC₂ and Hf₃SnC₂, while their 211 counterparts Ti₂SnC, Zr₂SnC and Hf₂SnC formed in the undoped M-Sn-C mixtures. The lattice parameters of the newly synthesized Zr₃SnC₂ and Hf₃SnC₂ MAX phases were determined by X-ray diffraction. Binary MC carbides were present in all ceramics, whereas the formation of intermetallics was largely determined by the selected additive. The effect of adding Fe, Co or Ni on the MAX phase crystal structure and the microstructure of the produced ceramics was investigated in greater detail for the case of M = Zr. A mechanism is herein proposed for the formation of M₃SnC₂ MAX phases.     

High-temperature synthesis of composite materials based on (Cr,Mn, V)–Al–C MAX phases

Composite materials based on (Cr, Mn, V)–Al–C MAX phases were obtained by self-propagating high-temperature synthesis (SHS). Regularities of synthesis of composite materials from mixtures containing chromium (III) oxide, manganese (IV) oxide, vanadium (V) oxide, calcium (IV) oxide, aluminum, and carbon powders were studied. The synthesis of 30-g blend was carried out in an SHS reactor with a volume of 3 l under Ar pressure (5 MPa). Variation in the amount of the starting reagents markedly affected the process parameters, phase composition, and microstructure of combustion products. The combustion products were characterized by XRD, SEM, and EDS analysis. For Cr–Al–C system, MAX Cr₂AlC phase in addition to chromium aluminide Cr₅Al₈ and chromium carbides (Cr₇C₃, Cr₃C₂) was detected. SEM studies showed that Cr₂AlC has a laminated structure with layer thickness varying from 3 to 20 nm. XRD pattern of Mn–Cr–Al–C composite material were found to have signals belonging (Cr_xMn_1–x)₂AlC solid solution, Mn₃AlC, and Cr₂Al. It was shown that V–Al–C composite material contains nano-layered MAX V₂AlC phase and particles VC_х, VAl₃.     

Sintering behavior of Cr2AlC MAX phase synthesized by Spark plasma sintering

In the current study, the sintering and mechanical properties of the Cr₂AlC MAX phase synthesized by Spark plasma sintering at 1000, 1100, and 1200°C were investigated. The X-ray diffraction (XRD) patterns showed that the synthesis of the Cr₂AlC MAX phase was associated with the presence of impurities such as Cr₇C₃ and Al₂O₃. On the basis of the FESEM images equipped with energy dispersive spectrometer, the MAX phases had been formed successfully and the length of these layers increased by enhancing the sintering temperature. The results of the density showed that by increasing the temperature, the density increases from 5.10 to 5.33 g/cm³ and finally decreases to 5.25 g/cm³. Vickers hardness method applied to determine the hardness of the samples showed that the hardness decreases from 8.52 to 8.07 GPa for the prepared samples.     

Synthesis and Oxidation Testing of MAX Phase Composites in the Cr–Ti–Al–C Quaternary System

According to the properties determined for the ternary end‐members, MAX phases in the quaternary Cr–Ti–Al–C system could be of interest as protective coatings for nuclear fuel cladding in the case of severe accident conditions. In this study, syntheses of 211 and 312 MAX phase compositions were attempted using pressureless reactions starting from Cr, TiH₂, Al, and C (graphite) powders. It was observed that both the Ti substitution by Cr in Ti₃AlC₂ and the mutual solubility of Ti₂AlC and Cr₂AlC are limited to a few atomic percent. In addition, the remarkable stability of the (Cr_2/3Ti_1/3)₃AlC₂ MAX phase composition was confirmed. Due to the low miscibility of MAX phases in the Cr–Ti–Al–C system, most samples contained substantial amounts of TiC_x and Al–Cr alloys as secondary phases, thus forming composite materials. After sintering, all samples were submitted to a single oxidation test (12 h at 1400°C in air) to identify compositions potentially offering high‐temperature oxidation resistance and so warranting further investigation. In addition to (Cr_0.95Ti_0.05)₂AlC, composite samples containing substantial quantities of Al₈Cr₅ and AlCr₂ formed a stable and passivating Al₂O₃ scale, whereas the other samples were fully oxidized.     

Structure and Microwave Dielectric Properties of Low Firing Bi2Te2W3O16 Ceramics

Dense Bi₂Te₂W₃O₁₆ ceramics were prepared by the conventional solid‐state reaction route. X‐ray diffraction data show the room‐temperature (RT) crystal symmetry of Bi₂Te₂W₃O₁₆ to be well described by the centrosymmetric monoclinic C2/c space group [a = 21.280(5) Å, b = 5.5663(16) Å, c = 12.831(3) Å and β = 124.014(19)° and Z = 4]. Raman spectroscopy analyses are in broad agreement with space group assignment, but also revealed the presence of Bi₂W₂O₉ as a secondary phase. This phase is present as plate‐like grains embedded on a fine‐grained equiaxed matrix, as revealed by scanning electron microscopy. From the fitting of infrared reflectivity data the relative permittivity, ε_r, was estimated as 34.2, and the intrinsic quality factor, Q_u × f as 57 500 GHz. At RT and microwave frequencies, Bi₂Te₂W₃O₁₆ ceramics sintered at 720°C for 6 h exhibit ε_r ~ 34.5, Q_u × f = 3173 GHz (at 7.5 GHz), and temperature coefficient of resonant frequency, τ_f = ?92 ppm/°C. This shows a good agreement between the estimated and measured ε_r values, but also shows that, in principle, the dielectric losses of the ceramics are of extrinsic origin.     

Eu2+‐doped strontium aluminum silicon nitrides having α‐SiAlON and polytypoid structures

Yellow single crystals of aluminum silicon nitrides containing strontium and europium were prepared by heating starting mixtures of Sr₃N₂, Si₃N₄, AlN, and EuN at 2050°C and 0.85 MPa of N₂ for 8 hours. Single‐crystal X‐ray diffraction revealed that prismatic crystals 20‐100 μm in size were Sr_0.31Al_0.62Si_11.38N₁₆:Eu (trigonal, a=7.7937(2) Å, c=5.6519(2) Å, space group P31c), which are isotypic with Sr‐α‐SiAlON, Sr_m/2Al_m+nSi_12?m?nN_16?nO_n, with m=0.62 and n=0. The Eu²⁺ content was approximately 1 at.% of Sr contained in the framework of corner‐sharing (Al/Si)N₄ tetrahedra with an occupancy of 0.154(2). Block‐shaped crystals with a side length of 50‐300 μm were a new polytypoid of Sr‐α‐SiAlON, Sr_2.97Eu_0.03Al₆Si₂₄N₄₀. Streak lines were observed in the direction of the c* axis in the X‐ray oscillation photographs, indicating stacking faults of the structure. The fundamental X‐ray reflections were indexed with a hexagonal cell (a=7.9489(3) Å, c=14.3941(6) Å). The structure was analyzed with a model of space group P in which one of the six Al/Si sites was statistically split into two sites with occupancies of 0.673(5) and 0.227(5). The atomic arrangements in the layers of the structure were similar to those of Sr‐α‐SiAlON, but the stacking sequences of the layers were different. The peak wavelengths and full widths at half maximum of emission spectra measured for the single crystals of Sr_0.31Al_0.62Si_11.38N₁₆:Eu and Sr_2.97Eu_0.03Al₆Si₂₄N₄₀ were 583 nm and 87 nm, and 584 nm and 91 nm, respectively, under 400 nm wavelength light excitation at room temperature.     

Accommodation,Accumulation, and Migration of Defects in Ti3SiC2 and Ti3AlC2 MAX Phases

We have determined the energetics of defect formation and migration in M_n+1AX_n phases with M = Ti, A = Si or Al, X = C, and n = 3 using density functional theory calculations. In the Ti₃SiC₂ structure, the resulting Frenkel defect formation energies are 6.5 eV for Ti, 2.6 eV for Si, and 2.9 eV for C. All three interstitial species reside within the Si layer of the structure, the C interstitial in particular is coordinated to three Si atoms in a triangular configuration (C–Si = 1.889 Å) and to two apical Ti atoms (C–Ti = 2.057 Å). This carbon–metal bonding is typical of the bonding in the SiC and TiC binary carbides. Antisite defects were also considered, giving formation energies of 4.1 eV for Ti–Si, 17.3 eV for Ti–C, and 6.1 eV for Si–C. Broadly similar behavior was found for Frenkel and antisite defect energies in the Ti₃AlC₂ structure, with interstitial atoms preferentially lying in the analogous Al layer. Although the population of residual defects in both structures is expected to be dominated by C interstitials, the defect migration and Frenkel recombination mechanism in Ti₃AlC₂ is different and the energy is lower compared with the Ti₃SiC₂ structure. This effect, together with the observation of a stable C interstitial defect coordinated by three silicon species and two titanium species in Ti₃SiC₂, will have important implications for radiation damage response in these materials.     

Oxidation-induced crack healing and erosion life assessment of Ni–Mo–Al–Cr7C3–Al2O3 composite coating

The present investigation focuses on the effect of Cr₂AlC MAX phase addition on erosion and oxidation-induced crack healing behavior of Ni–Mo–Al alloy. For this, Ni–Mo–Al and 20 wt% Cr₂AlC-blended Ni–Mo–Al powders were coated by Air Plasma Spray (APS). For oxidation-induced crack healing studies, the samples were heat treated at 500, 800, and 1100°C in the air for 5 hours. The heat-treated samples were analyzed by X-Ray Diffraction (XRD) analysis, Scanning Electron Microscopy (SEM), and Energy Dispersive Spectroscopy (EDS) for the phases, morphology, and composition. Erosion behavior studies were carried out at 30, 250, 500, 800, and 1000°C temperatures. The average hardness was obtained to be 400 ± 10 HV for Ni–Mo–Al coating and 580 ± 10 HV for 20 wt% Cr₂AlC-blended Ni–Mo–Al coating. The addition of Cr₂AlC MAX into Ni–Mo–Al matrix reduces the overall erosion rate and improved the crack healing ability. This was attributed to the presence of in-situ-formed Cr₇C₃ and Al₂O₃ phases.     

Oxidation Behavior of MAX Phase Ti2Al(1−x)SnxC Solid Solution

MAX phase Ti₂Al_(1?x)Sn_xC solid solution with x = 0, 0.32, 0.57, 0.82, and 1 was synthesized by pressureless sintering of uniaxially pressed Ti, Al, Sn, and TiC powder mixtures. Annealing in air atmosphere at 200°C–1000°C triggered a sequence of oxidation reactions which reveal a distinct influence of solid solution composition on the oxidation process. With decreasing Al/Sn ratio, the characteristic temperature of accelerated oxidation reaction of A‐element was reduced from 900°C (x = 0) to 460°C (x = 1). SnO₂ was formed at temperatures significantly lower than TiO₂ (rutile) and Al₂O₃. Substitution of A‐element in MAX phase solid solution by low‐melting elements such as Sn may offer potential for reducing oxidation‐induced crack healing temperatures.     

Oxidation and hot corrosion behaviors of MAX-phase Ti3SiC2, Ti2AlC,Cr2AlC

Oxidation and hot corrosion behaviours of Ti₃SiC₂, Ti₂AlC and Cr₂AlC at 750 °C were investigated in this work. Ti₃SiC₂ and Ti₂AlC showed a linear increase in mass gain and a relatively poor oxidation resistance. This might be attributed to the porous TiO₂ scale. A dense α-Al₂O₃ layer was formed during the oxidation test. Cr₂AlC exhibited the best oxidation resistance. This dense oxide scale can effectively isolate the substrate from contact with oxygen leading to excellent oxidation resistance. In contrast to the oxidation test, Ti₃SiC₂ and Ti₂AlC showed relatively better resistance to hot corrosion, while Cr₂AlC showed inferior resistance to NaCl introduced hot corrosion. The hot corrosion mechanism of the MAX phases was analyzed. Due to the formation of Na₂TiO₃, Ti containing MAX phases showed a continuous increase in the mass gain. The corrosion products of Cr₂AlC were Al₂O₃, Cr₂O₃ and Na₂CrO₄. However, due to the volatilization of Na₂CrO₄, Cr₂AlC showed a mass loss during the hot corrosion test. The chemical reaction process of the MAX phase was also analyzed.     

Pulse Electric Current–Aided Reactive Sintering of High‐Purity Zr3Al3C5

Herein, we report on the in situ reactive synthesis and simultaneous densification of a high‐purity ternary Zr₃Al₃C₅ phase via pulse electric current sintering (PECS) of Zr/Al/graphite powder mixtures with a molar ratio of 3:3.2:4.8. The phases and microstructure evolution in the 580°C–1800°C temperature range were characterized by X‐ray diffraction, real‐time sintering curves, and a scanning electron microscope equipped with an energy dispersive spectroscope. An additive‐free, fully dense Zr₃Al₃C₅ compound was obtained at 1800°C using a load corresponding to a stress of 35 MPa for 20 min. The final product was comprised of 96.61 wt% Zr₃Al₃C₅, 3.14 wt% ZrC, and 0.25 wt% Zr₂Al₃C₄; the relative density was 97%.     

Structure of a new bulk Ti5Al2C3 MAX phase produced by the topotactic transformation of Ti2AlC

Upon annealing cold-pressed Ti₂AlC, ?325 mesh powders, at 1500 °C for 8 h in argon, the resulting partially sintered sample contained 43(±2) wt.% of the layered ternary carbide Ti₅Al₂C₃. Herein, the X-ray powder diffraction pattern of Ti₅Al₂C₃ is reported for the first time and its structure and stoichiometry are confirmed through high-resolution transmission electron microscopy. This phase has a trigonal structure (space group P3m1) with a unit cell consisting of 3 formula units and cell parameters of a = 3.064 Å, c = 48.23 Å. The lattice parameters determined through first principles calculations agree reasonably well with the experimentally determined values. At 147.1 GPa, the calculated bulk modulus falls between the bulk moduli of Ti₂AlC and Ti₃AlC₂. The transformation from Ti₂AlC to Ti₅Al₂C₃ is topotactic.     

Thermal evolution of Al2O3–CaO–Cr2O3 castables in different atmospheres

Al₂O₃–CaO–Cr₂O₃ castables are required for various furnaces linings due to their excellent corrosion resistance. However, toxic and water-soluble Cr(VI) could be generated in these linings during service. In this study Al₂O₃–CaO–Cr₂O₃ castables were prepared and heated at 300–1500 °C in air and coke bed to simulate actual service conditions. The formations of various phases were investigated by XRD and SEM-EDS. The Cr(VI) compounds CaCrO₄ and Ca₄Al₆CrO₁₆ formed in air at 300–900 °C and 900–1300 °C respectively, while C₁₂A₇ and CA₂ were generated rather than forming Cr(VI) compounds in coke bed at 700–1300 °C. However, at 1500 °C, nearly all the chromium existed in the form of (Al_1-xCr_x)₂O₃ solid solution in both atmosphere. As a result, the specimens treated in air contained 185.0–1697.8 mg/kg of Cr(VI) at 500–1300 °C but only 17.2 mg/kg of Cr(VI) at 1500 °C, whereas specimens treated in coke bed exhibited extremely low Cr(VI) concentration in the whole temperature range studied. Moreover, in coke bed, the mutual diffusion between Cr₂O₃ and Al₂O₃ was suppressed and a trace of Cr₂O₃ would even be reduced to form chromium-containing carbides on its surface, which would hindered the sintering process and hence lower the density as well as strength of the castables.     

Elastic constants of polycrystalline Ti3AlC2 and Ti3SiC2 measured using coherent inelastic neutron scattering

The magnitude of the single‐crystal elastic constant c₄₄ in the MAX phase Ti₃SiC₂ is under debate. In this paper, estimates for the magnitude of c₄₄ for MAX phases Ti₃AlC₂ and Ti₃SiC₂ are determined from a partially oriented polycrystalline sample via coherent inelastic neutron scattering. The largely quasi‐isotropic nature of these M_n+1AX_n phase elastic constants as previously predicted by density functional theory calculations is confirmed experimentally for Ti₃AlC₂ to be c₄₄=115.3 ± 30.7 GPa. In contrast, Ti₃SiC₂ is confirmed to be shear stiff with c₄₄=402.7 ± 78.3 GPa supporting results obtained by earlier elastic neutron diffraction experiments.