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).

Molar volume, thermal expansivity and isothermal compressibility of trans-decahydronaphthalene up to 200MPa and 446K

The molar volume isotherms of trans-decahydronaphthalene （C10H18） between 293 and 446 K and at pressures from 10 to 200 MPa have been determined. A modified Tait equation of state is used to fit each experimental molar volume isotherm with a maximum average deviation of 0.029%. The thermal expansivity （cubic expansion coefficient） α and isothermal compressibility κ were determined by fitting the slopes of the isobaric curves and isotherms, respectively. The coefficients in the equation Vm=C1＋C2T＋C3T^2-C4p-C5pT have been fitted with an average deviation of 1.03%.

Improvement strategy on thermophysical properties of A_(2)B_(2)O_(7)-type rare earth zirconates for thermal barrier coatings applications:A review

The A_(2)B_(2)O_(7)-type rare earth zirconate compounds have been considered as promising candidates for thermal barrier coating(TBC) materials because of their low sintering rate,improved phase stability,and reduced thermal conductivity in contrast with the currently used yttria-partially stabilized zirconia (YSZ) in high operating temperature environments.This review summarizes the recent progress on rare earth zirconates for TBCs that insulate high-temperature gas from hot-section components in gas turbines.Based on the first principles,molecular dynamics,and new data-driven calculation approaches,doping and high-entropy strategies have now been adopted in advanced TBC materials design.In this paper,the solid-state heat transfer mechanism of TBCs is explained from two aspects,including heat conduction over the full operating temperature range and thermal radiation at medium and high temperature.This paper also provides new insights into design considerations of adaptive TBC materials,and the challenges and potential breakthroughs are further highlighted for extreme environmental applications.Strategies for improving thermophysical performance are proposed in two approaches:defect engineering and material compositing.

The Negative Thermal Expansion Property of NdMnO_(3) Based on Pores Effect and Phase Transition

A novel negative thermal expansion(NTE) material NdMnO_(3) was synthesized by solid-state method at 1 523 K. The crystal structure, phase transition, pores effect and negative expansion properties of NdMnO_(3) were investigated by variable temperature X-ray diffraction(XRD), scanning electron microscope(SEM) and variable temperature Raman spectra. The compound exhibits NTE properties in the orderly O' phase crystal structure. When the temperature is from 293 to 759 K, the ceramic NdMnO_(3) shows negative thermal expansion of-4.7×10^(-6)/K. As temperature increases, the ceramic NdMnO_(3) presents NTE property range from 759 to 1 007 K. The average linear expansion coefficient is-18.88×10^(-6)/K. The physical mechanism of NTE is discussed and clarified through experiments.

Modification of streamer-to-leader transition model based on radial thermal expansion in the sphere-plane gap discharge at high altitude

Historically,streamer-to-leader transition studies mainly focused on the rod-plane gap and low altitude analysis,with limited attention paid to the sphere-plane gap at high altitude analysis.In this work,sphere-plane gap discharge tests were carried out under the gap distance of 5 m at the Qinghai Ultra High Voltage(UHV)test base at an altitude of 2200 m.The experiments measured the physical parameters such as the discharge current,electric field intensity and instantaneous optical power.The duration of the dark period and the critical charge of streamer-toleader transition were obtained at high altitude.Based on radial thermal expansion of the streamer stem,we established a modified streamer-to-leader transition model of the sphere-plane gap discharge at high altitude,and calculated the stem temperature,stem radii and the duration of streamer-to-leader transition.Compared with the measured duration of sphere-plane electrode discharge at an altitude of 2200 m,the error rate of the modified model was 0.94%,while the classical model was 6.97%,demonstrating the effectiveness of the modified model.From the comparisons and analysis,several suggestions are proposed to improve the numerical model for further quantitative investigations of the leader inception.

Properties of Ultra-low Thermal Expansion LAS Transparent Glass-ceramics Prepared by Spodumene

The glass-ceramics were prepared with the spodumene mineral as the main raw material,and the effects of ZrO_(2)replacing TiO_(2)on the samples were systematically investigated.The results show that the substitution of ZrO_(2)for TiO_(2)is not conductive to precipitate𝛽β-quartz solid solution phase,but can improve the transparency and flexural strength of glass-ceramics.And the glass-ceramic with the highest visible light transmittance(87%)and flexural strength(231.80 MPa)exhibits an ultra-low thermal expansion of-0.028×10^(-7)K^(-1)in the region of 30-700℃.

Crystal Structure,Thermal Expansivity and High-Temperature Vibrational Spectra on Natural Hydrous Rutile

A natural rutle sample was measured by in situ high-temperature X-ray diffraction(XRD)patterns,as well as Raman and Fourier transform infrared(FTIR).Crystal structure is refined on the sample with 1.4 mol.%Fe and 510±120 ppmw.H2 O.The unit-cell and Ti O6 octahedral volumes are expanded by 0.7%–0.8%for Fe3+incorporation,as compared with the reported Ti-pure samples.The volumetric thermal expansion coefficient(α,K-1)could be approximated as a linear function of T(K):4.95(3)×10-9×T+21.54(5)×10-6,with the averaged valueα0=30.48(5)×10-6 K-1,in the temperature range of 300–1500 K.The internal Ti-O stretching(A1 g and B2 g)and O-Ti-O bending(Eg)modes show‘red shift',whereas the multi-phonon process exhibits‘blue shift'at elevated temperature.The rotational mode(B1 g)for Ti O6 octahedra is nearly insensitive to temperature variations.The OH-stretching bands at 3279 and 3297 cm-1 are measured by high-temperature spectroscopy experiments.Both the IR-active and Raman-active OH-stretching modes shift to lower frequencies at higher temperature,with the signal intensities decreasing.And after quenching,we expect about 43%dehydration around 873 K,and 85%dehydration at 1273 K for this hydrous sample.

Statics, vibration, and buckling of sandwich plates with metamaterial cores characterized by negative thermal expansion and negative Poisson's ratio

This paper proposes a three-dimensional(3D)Maltese cross metamaterial with negative Poisson’s ratio(NPR)and negative thermal expansion(NTE)adopted as the core layers in sandwich plates,and aims to explore the relations between the mechanical responses of sandwich composites and the NPR or NTE of the metamaterial.First,the NPR and NTE of the metamaterial are derived analytically based on energy conservation.The effective elastic modulus and mass density of the 3D metamaterial are obtained and validated by the finite element method(FEM).Subsequently,the general governing equation of the 3D sandwich plate under thermal environments is established based on Hamilton’s principle with the consideration of the von Kármán nonlinearity.The differential quadrature(DQ)FEM(DQFEM)is utilized to obtain the numerical solutions.It is shown that NPR and NTE can enhance the global stiffness of sandwich structures.The geometric parameters of the Maltese cross metamaterial significantly affect the responses of the thermal stress,natural frequency,and critical buckling load.

Anisotropic thermal expansion in high-entropy multicomponent AlB_(2)-type diboride solid solutions

High-entropy(HE)ultra-high temperature ceramics have the chance to pave the way for future applications propelling technology advantages in the fields of energy conversion and extreme environmental shielding.Among others,HE diborides stand out owing to their intrinsic anisotropic layered structure and ability to withstand ultra-high temperatures.Herein,we employed in-situ high-resolution synchrotron diffraction over a plethora of multicomponent compositions,with four to seven transition metals,with the intent of understanding the thermal lattice expansion following different composition or synthesis process.As a result,we were able to control the average thermal expansion(TE)from 1.3×10^(−6)to 6.9×10^(−6)K^(−1)depending on the combination of metals,with a variation of in-plane to out-of-plane TE ratio ranging from 1.5 to 2.8.

Tailoring of thermal expansion and phase transition temperature of ZrW_(2)O_8 with phosphorus and enhancement of negative thermal expansion of ZrW_(1.5)P_(0.5)O_(7.75)

ZrW_(2)O_(8)is a typical isotropic negative thermal expansion material with cubic structure.However,quenching preparation,pressure phase transition and metastable structure influence its practical applications.Adopting P to part-substitute W for ZrW_(2-x)P_(x)O_(8-0.5x)has decreased the sintering temperature and avoided the quenching process.When x=0.1,ZrW_(1.9)P_(0.1)O_(7.95)with a stable cubic structure can be obtained at 1150℃.The thermal expansion coefficient is tailored with the P content,and phase transition temperature is lowered.When x=0.5,thermal expansion coefficient attains-13.6×10^(-6)℃^(-1),ZrW_(1.5)P_(0.5)O_(7.75)exhibits enhance negative thermal expansion property.The difference of electronegativity leads to the decrease of phase transition temperature with the increase of P content.The different radii of ions lead to new structure of materials when P substitutes more.The results suggest that the P atom plays the stabilization role in the crystal structure of ZrW_(2-x)P_(x)O_(8-0.5x).

Evaluating thermal expansion in fluorides and oxides:Machine learning predictions with connectivity descriptors

Open framework structures(e.g.,ScF_(3),Sc_(2)W_(3O)_(12),etc.)exhibit significant potential for thermal expansion tailoring owing to their high atomic vibrational degrees of freedom and diverse connectivity between polyhedral units,displaying positive/negative thermal expansion(PTE/NTE)coefficients at a certain temperature.Despite the proposal of several physical mechanisms to explain the origin of NTE,an accurate mapping relationship between the structural–compositional properties and thermal expansion behavior is still lacking.This deficiency impedes the rapid evaluation of thermal expansion properties and hinders the design and development of such materials.We developed an algorithm for identifying and characterizing the connection patterns of structural units in open-framework structures and constructed a descriptor set for the thermal expansion properties of this system,which is composed of connectivity and elemental information.Our developed descriptor,aided by machine learning(ML)algorithms,can effectively learn the thermal expansion behavior in small sample datasets collected from literature-reported experimental data(246 samples).The trained model can accurately distinguish the thermal expansion behavior(PTE/NTE),achieving an accuracy of 92%.Additionally,our model predicted six new thermodynamically stable NTE materials,which were validated through first-principles calculations.Our results demonstrate that developing effective descriptors closely related to thermal expansion properties enables ML models to make accurate predictions even on small sample datasets,providing a new perspective for understanding the relationship between connectivity and thermal expansion properties in the open framework structure.The datasets that were used to support these results are available on Science Data Bank,accessible via the link https://doi.org/10.57760/sciencedb.j00113.00100.

Thermal expansion behavior of sintered Nd–Fe–B magnets with different Co contents and orientations

The thermal expansion behavior of sintered Nd–Fe–B magnets is a crucial parameter for production and application.However, this aspect has not been thoroughly investigated. In this study, three different sintered Nd–Fe–B magnets with varying Co content(Co = 0, 6, 12 wt%) were prepared using the conventional powder metallurgy method, and four magnets oriented under different magnetic fields were prepared to compare. The thermal expansion behavior for the magnets was investigated using a linear thermal dilatometry in the temperature range of 20℃–500℃. It was found that, the coefficient of thermal expansion(CTE) increases with the increase of Co contents, while the anisotropy of thermal expansion decreases.The introduction of Co leads to continuous changes from negative to positive thermal expansion in the vertically oriented direction, which is important for the development of zero thermal expansion magnets. The thermal expansion of nonoriented magnets was found to be isotropic. Additionally, the anisotropy of thermal expansion increases with the increase of orientation degree. These results have important implications for the development of sintered Nd–Fe–B with controllable CTE.

Negative thermal expansion and phase transition of low-temperature Mg_(2)NiH_(4)

The negative thermal expansion(NTE) phenomenon is of great significance in fabricating zero thermal expansion(ZTE) materials to avoid thermal shock during heating and cooling. NTE is observed in limited groups of materials, e.g., metal cyanides, oxometallates, and metalorganic frameworks, but has not been reported in the family of metal hydrides. Herein, a colossal and continuous negative thermal expansion is firstly developed in the low-temperature phases of LT1-and LT2-Mg_(2)NiH_(4) between 488 K and 733 K from in-situ transmission electron microscope(TEM) video, with the volume contraction reaching 18.7% and 11.3%, respectively. The mechanisms for volume contraction of LT1 and LT2 phases are elucidated from the viewpoints of phase transformation, magnetic transition, and dehydrogenation, which is different from common NTE materials containing flexible polyhedra units in the structure. The linear volume shrinkage of LT2 in the temperature of 488-553 K corresponds to the phase transition of LT2→HT with a thermal expansion coefficient of -799.7 × 10^(-6) K^(-1) revealed by in-situ synchrotron powder X-ray diffraction. The sudden volume contraction in LT1 between 488 and 493 K may be caused by the rapid dehydrogenation of LT1 to Mg_(2)Ni. The revealed phenomenon in single composite material with different structures would be significant for preparing zero thermal expansion materials by tuning the fraction of LT1 and LT2 phases.

Magneto-volume effect in Fe_(n)Ti_(13-n)clusters during thermal expansion

Ab initio molecular dynamics calculations have been carried out to search for the ground state structure of Fe_(n)Ti_(13-n)clusters and measure the thermal expansion of Fe_(n)Ti_(13-n).The volume of Fe_(n)Ti_(13-n)clusters during thermal expansion is jointly determined by anharmonic interaction and magneto-volume effect.It has been found that Fe_(6)Ti_(7),Fe_9Ti_(4),Fe_(11)Ti_(2),and Fe_(13)clusters can exhibit the remarkable magneto-volume effect with abnormal volume behaviors and magnetic moment behaviors during thermal expansion.A prerequisite for the magneto-volume effect of Fe_(n)Ti_(13-n)clusters during thermal expansion has been revealed and the magnitude of the magneto-volume is also approximately determined.Furthermore,the magneto-volume behaviors of Fe_(n)Ti_(13-n)clusters are qualitatively characterized by the energy contour map.Our results shed light on the mechanism of the magneto-volume effect in Fe_(n)Ti_(13-n)clusters during thermal expansion,which can guide the design of nanomaterials with zero expansion or even controllable expansion properties.

Microstructure evolution and thermal expansion of Cu-Zn alloy after high pressure heat treatment

The thermal expansion coefficients of Cu-Zn alloy before and after high pressure treatment were measured by thermal expansion instrument in the temperature range of 25？700 ℃,and the microstructure and phase transformation of the alloy were examined by optical microscope,X-ray diffractometer（XRD） and differential scanning calorimeter（DSC）.Based on the experimental results,the effects of high pressure treatment on the microstructure and thermal expansion of Cu-Zn alloy were investigated.The results show that the high pressure treatment can refine the grain and increase the thermal expansion coefficient of the Cu-Zn alloy,resulting in that the thermal expansion coefficient exhibits a high peak value on the α-T curve,and the peak value decreases with increasing the pressure.

Effects of cooling rate on thermal expansion of Cu_(49)Hf_(42)Al_9 metallic glass

Effects of cooling rate on thermal expansion of Cu49Hf42Al9 metallic glass were studied. Five types of amorphous samples with different sizes were prepared in order to get a broad range of cooling rates （from 102 to 107 K/s）. The average thermal expansion coefficients （αaver） of as-quenched samples range from 6.14×10-6 to 9.20×10-6 K-1. When the temperature is below the glass transformation temperature （Tg）, αaver of as-quenched samples has a negative correlation with cooling rate; the values of αaver of annealed and crystallized samples are closed to each other. The results indicate that the amount and motion of free volume play important roles in thermal expansion of metallic glasses.

Anisotropy of Thermal-expansion for β-Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine： Quantum Chemistry Calculation and Molecular Dynamics Simulation

Molecular dynamics simulations on octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine （HMX） at 303-383 K and atmospheric pressure are carried out under NPT ensemble and COMPASS force field, the equilibrium structures at elevated temperatures were obtained and showed that the stacking style of molecules don＇t change. The coefficient of thermal expansion （CTE） values were calculated by linear fitting method. The results show that the CTE values are close to the experimental results and show anisotropy. The total energies of HMX cells with separately increasing expansion rates （100%-105%） along each crystallographic axis was calculated by periodic density functional theory method, the results of the energy change rates are anisotropic, and the correlation equations of energy change-CTE values are established. Thus the hypostasis of the anisotropy of HMX crystal＇s thermal expansion, the determinate molecular packing style, is elucidated.

Linear magnetoresistance and structural distortion in layered SrCu_(4-x)P_(2) single crystals

We report a systematic study on layered metal SrCu_(4-x)P_(2) single crystals via transport, magnetization, thermodynamic measurements and structural characterization. We find that the crystals show large linear magnetoresistance without any sign of saturation with a magnetic field up to 30T. We also observe a phase transition with significant anomalies in resistivity and heat capacity at T_(p)~140 K. Thermal expansion measurement reveals a subtle lattice parameter variation near Tp, i.e.,?L_(c)/L_(c)~0.062%. The structural characterization confines that there is no structure transition below and above T_(p). All these results suggest that the nonmagnetic transition of SrCu_(4-x)P_(2) could be associated with structural distortion.

CFD modeling of gas−liquid flow phenomenon in lead smelting oxygen-enriched side-blown furnace

A validated numerical model was established to simulate gas−liquid flow behaviors in the oxygen-enriched side-blown bath furnace.This model included the slip velocity between phases and the gas thermal expansion effect.Its modeling results were verified with theoretical correlations and experiments,and the nozzle-eroded states in practice were also involved in the analysis.Through comparison,it is confirmed that the thermal expansion effect influences the flow pattern significantly,which may lead to the backward motion of airflow and create a potential risk to production safety.Consequently,the influences of air injection velocity and furnace width on airflow behavior were investigated to provide operating and design guidance.It is found that the thin layer melt,which avoids high-rate oxygen airflow eroding nozzles,shrinks as the injection velocity increases,but safety can be guaranteed when the velocity ranges from 175 to 275 m/s.Moreover,the isoline patterns and heights of thin layers change slightly when the furnace width increases from 2.2 to 2.8 m,indicating that the furnace width shows a limited influence on production safety.

Mixed Alkali-zinc Effects on Thermo-mechanical Properties in Borosilicate Glasses

A series of mixed alkali-zinc borosilicate glasses with various r values(r=molar ratio of[ZnO]/([R^(2)O]+[ZnO]))from 0.00 to 1.00 were fabricated to probe the mixed alkali-zinc effects on thermo-mechanical properties.The nonlinear evolution of glass transition temperature(T_(g))with the addition of ZnO is ascribed to the competition of two converse factors,i e,the T_(g)depression as one of the colligative properties for a solution,on the one hand,and the enhancement of T_(g)due to the higher field strength of zinc cations compared to that of alkali ions.However,the nonlinear evolution of elastic moduli and coefficients of thermal expansion with r is attributed to the variance of intermediate-range clusters,which is confirmed by infrared and Raman scattering spectra.These findings are very helpful in tailoring the performance of borosilicate glasses.