Thermal expansivity of geikielite and ilmenite utilizing in-situ synchrotron X-ray diffraction at high temperature

The unit-cell parameters and volumes of geikielite(MgTiO_(3))and ilmenite(FeTiO_(3))were investigated at high temperatures up to 700 K and ambient pressure,using in-situ angle-dispersive synchrotron X-ray diffraction.No phase transition was detected over the experimental temperature range.Using(Berman in J Petrol29:445-522,1988.10.1093/petrology/29.2.445)equations to fit the temperature-volume data,the volumetric thermal expansion coefficients at ambient conditions(α_(V0))of MgTiO_(3) and FeTiO_(3) were obtained as follows:2.55(6)×10^(-5)K^(-1)and 2.82(10)×10^(-5)K^(-1),respectively.We infer that the larger effective ionic radius of Fe^(2+)(Ⅵ)(0.78 A)than that of Mg^(2+)(Ⅵ)(0.72?)renders FeTiO_(3)has a larger volumetric thermal expansivity than MgTiO_(3).Simultaneously,the refined axial thermal expansion coefficients under ambient conditions areα_(a0)=0.74(3)×10^(-5)K^(-1)andα_(c0)=1.08(5)×10^(-5)K^(-1)for the aaxis and c-axis of MgTiO_(3),respectively,andα_(a0)=0.95(5)×10^(-5)K^(-1)andα_(c0)=0.92(12)×10^(-5)K^(-1)for the aaxis and c-axis of FeTiO_(3),respectively.The axial thermal expansivity of MgTiO_(3) is anisotropic,but that of FeTiO_(3) is nearly isotropic.We infer that the main reason for the different axial thermal expansivity between MgTiO_(3) and FeTiO_(3) is that the thermal expansion mode of the Mg-O bond in MgTiO_(3) is different from that of the Fe-O bonds in FeTiO_(3).

In-Situ High Temperature X-Ray Diffraction Study of Structure and Phase Transformation of Nd-FePt Alloys

The structure and disorder-order transformation of NdxFe60.5-x Pt39.5（x = 0, 0.5, 1.0, 1.5） alloys were investigated in situ by high temperature X-ray diffraction. The results show that the lattice parameter a of disordered γ phase （FCC, Al structure type） and the lattice parameter ratio c/a of ordered γ1 phase （FCT, L10 structure type） increase linearly with increasing Nd concentration, whereas the c/a ratio decreases with increasing temperature. The transition temperature from ordered FCT to disordered FCC decreases with increasing Nd concentration, but for alloys quenched rapidly from γ phase region into ice-water it increases with increasing Nd.

Thermal expansion of kyanite at ambient pressure:An X-ray powder diffraction study up to 1000℃

The thermal expansion coefficients of kyanite at ambient pressure have been investigated by an X-ray powder diffraction technique with temperatures up to 1000 ℃. No phase transition was observed in the experimental temperature range. Data for the unit-cell parameters and temperatures were fitted empirically resulting in the following thermal expansion coefficients： αa = 5.8（3） × 10^-5, αb = 5.8 （1）× 10^-5, αc = 5.2（1）× 10^-5, and αv = 7.4（1） × 10^-3 ℃ 1 in good agreement with a recent neutron powder diffraction study. On the other hand, the variation of the unit-cell angles α, β and γ of kyanite with increase in temperature is very complicated, and the agreement among all studies is poor. The thermal expansion data at ambient pressure reported here and the compression data at ambient temperature from the literature suggest that, for the kyanite lattice, the most and least thermally expandable directions correspond to the most and least compressible directions, respectively.

Novel high-voltage cathode for aqueous zinc ion batteries:Porous K_(0.5)VOPO_(4)·1.5H_(2)O with reversible solid-solution intercalation and conversion storage mechanism

Cathode materials that possess high output voltage,as well as those that can be mass-produced using facile techniques,are crucial for the advancement of aqueous zinc-ion battery(ZIBs)applications,Herein,we present for the first time a new porous K_(0.5)VOPO_(4)·1.5H_(2)O polyanionic cathode(P-KIVP)with high output voltage(above 1.2 V)that can be manufactured at room temperature using straightforward coprecipitation and etching techniques.The P-KVP cathode experiences anisotropic crystal plane expansion via a sequential solid-solution intercalation and phase co nversion pathway throughout the Zn^(2+)storage process,as confirmed by in-situ synchrotron X-ray diffraction and ex-situ X-ray photoelectron spectroscopy.Similar to other layered vanadium-based polyanionic materials,the P-KVP cathode experiences a progressive decline in voltage during the cycle,which is demonstrated to be caused by the irreversible conversion into amorphous VO_(x).By introducing a new electrolyte containing Zn(OTF)_(2) to a mixed triethyl phosphate and water solution,it is possible to impede this irreversible conversion and obtain a high output voltage and longer cycle life by forming a P-rich cathode electrolyte interface layer.As a proof-of-concept,the flexible fiber-shaped ZIBs based on modified electrolyte woven into a fabric watch band can power an electronic watch,highlighting the application potential of P-KVP cathode.

Study of Oxidation Kinetics in Air of Zircaloy-4 by <i>in Situ</i>X-Ray Diffraction

The zircaloy-4 is an alloy of zirconium, which has a very weak thermal neutron absorption, satisfactory mechanical properties and good corrosion resistance at high temperature. For these reasons, zircaloy-4 is used as a material of cladding fuel rod of nuclear reactors. In this environment, it is submitted to different severe conditions of temperature and pressure. The objective of this work is to study the oxidation kinetics of zircaloy-4 in air by the X-ray diffraction technique. The experiments were realized in a “HTK1200” furnace installed as a sample holder in the diffractometer at different temperatures;25°C, 350°C, 500°C, 830°C and 1000°C. The results show that the monoclinic and the tetragonal phases are formed at 350°C temperature. The volume fraction of these phases increased with the temperature until 1000°C where the α phase disappears completely. For simulating the case of loss-of-coolant-accident (LOCA), we have done x-ray diffraction of Zry-4 samples water quenched at 1050°C with different ageing times at this temperature. At 10 seconds and more, there is an important evolution of monoclinic and tetragonal zirconias, which leads to the degradation of zircaloy-4 properties.

Behaviors of Zn2GeO4 under high pressure and high temperature

The structural stability of Zn2GeO4 was investigated by in-situ synchrotron radiation angle dispersive x-ray diffraction. The pressure-induced amorphization is observed up to 10 GPa at room temperature. The high-pressure and hightemperature sintering experiments and the Raman spectrum measurement firstly were performed to suggest that the amorphization is caused by insufficient thermal energy and tilting Zn–O–Ge and Ge–O–Ge bond angles with increasing pressure,respectively. The calculated bulk modulus of Zn2GeO4 is 117.8 GPa from the pressure-volume data. In general, insights into the mechanical behavior and structure evolution of Zn2GeO4 will shed light on the micro-mechanism of the materials variation under high pressure and high temperature.

Plasma assisted synthesis of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2) cathode materials with good cyclic stability at subzero temperatures

Layered Ni-rich cathode materials,LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622),are synthesized via solid reaction assisted with a plasma milling pretreatment,which is resulted in lowering sintering temperatures for solid precursors.The plasma milling pretreated NCM622 cathode material sintered at 780℃(named as PM-780)demonstrates good cycling stability at both room and subzero temperatures.Specifically,the PM-780 cathode delivers an initial discharge capacity of 171.2 mAh g^(-1) and a high capacity retention of 99.7%after 300 cycles with current rate of 90 mA g^(-1) at 30℃,while stable capacities of 120.3 and 94.0 m Ah g^(-1) can be remained at-10℃and-20℃in propylene carbonate contained electrolyte,respectively.In-situ XRD together with XPS and SEM reveal that the NCM622 cycled at-10℃presented better structural stability and more intact interface than that of cathodes cycled at 30℃.It is also found that subzero temperatures only limit the discharge potential of NCM622 without destroying its structure during cycling since it still exhibits high discharge capacity at 30℃after cycled at subzero temperatures.This work may expand the knowledge about the low-temperature characteristics of layered cathode materials for Li-ion batteries and lay the foundation for its further applications.

Measurement of integral diffraction coefficients of crystals on beamline 4B7 of Beijing Synchrotron Radiation Facility

Integral diffraction coefficients of the crystal are the essential data of a crystal spectrometer which is extensively used to measure quantitative x-ray spectra of high temperature plasmas in kilo-electron-volt region. An experimental method has been developed to measure the integral diffraction coefficients of crystals on beamline 4B7 of Beijing Synchrotron Radiation Facility. The integral diffraction coefficients of several crystals including polyethylene terephthalate （PET）, thallium acid phthalate （T1AP） and rubidium acid phthalate （RAP） crystals have been measured in the x-ray energy range 2100-5600 eV and compared with the calculations of the ＇Darwin Prins＇ and the ＇Mosaic＇ models. It is shown that the integral diffraction coefficients of these crystals are between the calculations of the ＇Darwin Prins＇ and the ＇Mosaic＇ models, but more close to the ＇Darwin Prins＇ model calculations.

Combined use of fly ash and silica to prevent the long-term strength retrogression of oil well cement set and cured at HPHT conditions

The long-term strength retrogression of silica-enriched oil well cement poses a significant threat to wellbore integrity in deep and ultra-deep wells, which is a major obstacle for deep petroleum and geothermal energy development. Previous attempts to address this problem has been unsatisfactory because they can only reduce the strength decline rate. This study presents a new solution to this problem by incorporating fly ash to the traditional silica-cement systems. The influences of fly ash and silica on the strength retrogression behavior of oil well cement systems directly set and cured under the condition of 200°C and 50 MPa are investigated. Test results indicate that the slurries containing only silica or fly ash experience severe strength retrogression from 2 to 30 d curing, while the slurries containing both fly ash and silica experience strength enhancement from 2 to 90 d. The strength test results are corroborated by further evidences from permeability tests as well as microstructure analysis of set cement. Composition of set cement evaluated by quantitative X-ray diffraction analyses with partial or no known crystal structure(PONKCS) method and thermogravimetry analyses revealed that the conversion of amorphous C-(A)-S-H to crystalline phases is the primary cause of long-term strength retrogression.The addition of fly ash can reduce the initial amount of C-(A)-S-H in the set cement, and its combined use with silica can prevent the crystallization of C-(A)-S-H, which is believed to be the working mechanism of this new admixture in improving long-term strength stability of oil well cement systems.

High-temperature phase relations of ZrN–ZrO_2–Y_2O_3 ternary system

Zirconium nitride(ZrN) ceramics were prepared via hot pressed sintering(HP) at 1750 ℃ in N_2 atmosphere with ZrO_2–Y_2O_3 as sintering additive. X-ray diffraction was applied to analyze the phase composition of the as-prepared ceramics to study the high temperature phase relation in ZrN –ZrO_2–Y_2O_3 ternary system and establish ZrN –ZrO_2–Y_2O_3 ternary phase diagrams. The results show that ZrN and tetragonal ZrO_2(t-ZrO_2) solid solution, face-centered cubic ZrO_2(c-ZrO_2) solid solution, body-centered cubic Y_2O_3(c-Y_2O_3) solid solution coexist in the system of ZrN –ZrO_2–Y_2O_3.

DYNAMIC PROCESS OF VALENCE CHANGE OF EUROPIUM ION IN EUROPIUM DIFLUORIDE AT HIGH TEMPERATURE

The dynamic process of the ionic valence changing from Eu^(2+) to Eu^(3+) in EuF_2 at high temperature has been investigated by ESCA, high,temperature X-ray diffraction, high temperature spectrum, high temperature magnetic Isusceptibility and Mssbauer spectrum. It has been shown that the formed Eu^(3+) exists in different compounds when EuF_2 is heated to high temperature in different atmospheres. In air, Eu^(3+) exists in the form of hexagonal EuOF, in nitrogen, in the form of orthogonal EuF_3 and non-hexagon EuOF. This is because decomposition or disproportionation of EuF_2 is different with different atmospheres. The magnetic susceptibility measurement showed quantitatively that the change rate from Eu^(2+) to Eu^(3+) is about 95% in air, and about 75% in nitrogen when it is heated to 900℃. A small amount of Eu^(2+) coexists with Eu^(3+) in the final product.

Operando Observation of Structural Evolution and Kinetics of Li[Ni0.6Co0.2Mn0.2]O2 at Elevated Temperature

Li[Ni0.6Co0.2Mn0.2]O2(NCM622)is one of the best commercialized cathodes in the battery field.However,poor cyclability at relatively high temperature hinders its multiple usages.Here,operando tests were performed to investigate the phase transitions and electron/ion transfer process of lavered NCM622 at 25 and 55℃.The identified spinel structure resulting in the poor cyclability at 55℃ guides the commercialization of batteries at high temperature.

Relating microstructure to magnetocaloric properties in RE_(36)Tb_(20)Co_(20)Al_(24)(RE=Gd,Dy or Ho)high-entropy metallic-glass microwires designed by binary eutectic clusters method

The new high-entropy metallic-glasses(HE-MGs)are designed by using Dy and Ho to replace Gd in Gd_(36)Tb_(20)Co_(20)Al_(24)alloy based on the binary eutectic clusters method.Compared with the equiatomic Gd 25 Tb 25 Co 25 Al 25 HE-MG,the non-equiatomic RE_(36)Tb_(20)Co_(20)Al_(24)(RE=Gd,Dy,or Ho)alloys show bet-ter glass-forming ability,which is attributed to the deep binary eutectic compositions used for alloy de-sign.All RE_(36)Tb_(20)Co_(20)Al_(24)alloys undergo second-order magnetic transition.An extreme peak value of magnetic entropy change is obtained as 10.3 J kg^(-1) K-1(5 T)for the Ho_(36)Tb_(20)Co_(20)Al_(24)alloy.In-situ high-energy synchrotron X-ray diffraction was conducted to observe the microstructural difference among non-equiatomic samples at cryogenic temperatures.The results indicate that Gd_(36)Tb_(20)Co_(20)Al_(24)alloy possesses a relatively large average value of the dispersion of local clusters at a low-temperature range.This,com-bined with the critical exponentβclose to 0.5 of Gd_(36)Tb_(20)Co_(20)Al_(24)alloy,leads to its widest working temperature span among non-equiatomic samples.This work successfully establishes the connection be-tween microstructure and magnetocaloric properties of HE-MGs,which is beneficial for understanding the physical mechanism of the magnetocaloric behaviors of HE-MGs.

Thermal expansion of lattice parameter of (powder) silicon up to 1473 K

The XRPD (X-ray powder diffxactometry) patterns of silicon powder with a unit cell structure of diamond were determined from 298 to 1473 K. Lattice parameters of Si linearly increase with temperature. The thermal shifts of the positions of all reflection peaks are linearly correlated with the temperature. The coefficients of the intrinsic linear thermal expansion and volumetric thermal expansion were determined as 3.87×10-6/K and 1.16×10-5/K respectively. It indicates that Si is still a suitable standard in the XRPD method at high temperatures.

Effect of Glass Composition on the Thermal Expansion of Relict Crystals of RuO₂in Doped Lead-Silicate Glasses (Thick Film Resistors)

The thermal expansion coefficients (TEC) of RuO2 crystallits in thick film resistor (TFR) composites, consisting of RuO2 dispersed in lead-silicate glass of various compositions, were evaluated from X-ray diffraction patterns at temperatures 298;773;973 and 1123 K corresponding to characteristic temperatures of resistivity and thermopower anomalies of the TFRs. It has been found that TEC of free RuO2 powder along a-axis has an anomaly at T > 973 K (expansion is replaced by constriction), whereas constriction along c-axes remains for all temperatures. This anomaly disappears in doped glass of simplest composition (2SiO2.PbO) but occurs in glasses of some complex compositions. Symmetry of unit cell of RuO2 is not changed in the temperature range investigated.

Synthesis and Characterization of Methanesulfonate and Ethanesulfonate Intercalated Lithium Aluminum LDHs

LDH-phases become increasingly interesting due to their broad ability to be able to incorporate many different cations and anions. The intercalation of methanesulfonate and ethanesulfonate into a Li-LDH as well as the behavior of the interlayer structure as a function of the temperature is presented. A hexagonal P63/m [LiAl2(OH)6][Cl?1.5H2O] (Li-Al-Cl) precursor LDH was synthesized by hydrothermal treating of a LiCl solution with γ-Al(OH)3. This precursor was used to intercalate methanesulfonate (CH3O3S?) and ethanesulfonate (C2H5O3S?) through anion exchange by stirring Li-Al-Cl in a solution of the respective organic Li-salt (90?C, 12 h). X-ray diffraction pattern showed an increase of the interlayer space c' (d001) of Li-Al-methanesulfonate (Li-Al-MS) with 1.2886 nm and Li-Al-ethanesulfonate (Li-Al-ES) with 1.3816 nm compared to the precursor with 0.7630 nm. Further investigations with Fourier-transform infrared spectroscopy and scanning electron microscopy confirmed a complete anion exchange of the organic molecules with the precursor Cl?. Both synthesized LDH compounds [LiAl2(OH)6]CH3SO3?nH2O (n = 2.24-3.72 (Li-Al-MS) and [LiAl2(OH)6]C2H5SO3}?nH2O (n = 1.5) (Li-Al-ES) showed a monomolecular interlayer structure with additional interlayer water at room temperature. By increasing the temperature, the interlayer water was removed and the interlayer space c' of Li-Al-MS decreased to 0.87735 nm (at 55?C). Calculations showed that a slight displacement of the organic molecules is necessary to achieve this interlayer space. Different behavior of Li-Al-ES could be observed during thermal treatment. Two phases coexisted at 75?C - 85?C, one with a reduced c' (0.9015 nm, 75?C) and one with increased c' (1.5643 nm, 85?C) compared to the LDH compound at room temperature. The increase of c' is due to the formation of a bimolecular interlayer structure.

Valency and Its Change Process of Samarium Ion in Samarium Fluoride System

Nonstoichiometric series SmF_x (2.0≤x≤3.0) have been synthesized by reduction of samarium trifluoride with hydrogen for several times, and the stoichiometric samarium difluoride has been obtained. The structure of nonstoichiometric samarium fluoride series and the valency of samarium ion are briefly discussed. The valent change process of samarium ion at high temperatures in different atmospheres is investigated.