Sensing the heavy water concentration in an H_(2)O-D_(2)O mixture by solid-solid phononic crystals

A new method based on phononic crystals is presented to detect the concentration of heavy water(D_(2)O)in an H_(2)O-D_(2)O mixture.Results have been obtained and analyzed in the concentration range of 0%-10%and 90%-100%D_(2)O.A proposed structure of tungsten scatterers in an aluminum host is studied.In order to detect the target material,a cavity region is considered as a sound wave resonator in which the target material with different concentrations of D_(2)O is embedded.By changing the concentration of D_(2)O in the H_(2)O-D_(2)O mixture,the resonance frequency undergoes a frequency shift.Each 1%change in D_(2)O concentration in the H_(2)O-D_(2)O mixture causes a frequency change of about 120 Hz.The finite element method is used as the numerical method to calculate and analyze the natural frequencies and transmission spectra of the proposed sensor.The performance evaluation index shows a high Q factor up to 1475758 and a high sensitivity up to 13075,which are acceptable values for sensing purposes.The other figures of merit related to the detection performance also indicate high-quality performance of the designed sensor.

Localization effect in single crystal of RuAs_(2)

We report the magnetotransport and thermal properties of RuAs_(2) single crystal.RuAs_(2) exhibits semiconductor behavior and localization effect.The crossover from normal state to diffusive transport in the weak localization(WL)state and then to variable range hopping(VRH)transport in the strong localization state has been observed.The transitions can be reflected in the measurement of resistivity and Seebeck coefficient.Negative magnetoresistance(NMR)emerges with the appearance of localization effect and is gradually suppressed in high magnetic field.The temperature dependent phase coherence length extracted from the fittings of NMR also indicates the transition from WL to VRH.The measurement of Hall effect reveals an anomaly of temperature dependent carrier concentration caused by localization effect.Our findings show that RuAs_(2) is a suitable platform to study the localized state.

Crystal structure,phase transitions,and thermodynamic properties of magnesium metavanadate(MgV_(2)O_(6))

As a promising anode material for magnesium ion rechargeable batteries,magnesium metavanadate(MgV_(2)O_(6))has attracted considerable research interest in recent years.A MgV_(2)O_(6)sample was synthesized via a facile solid-state reaction by multistep-firing stoichiometric mixtures of MgO and V2O5 powder under an air atmosphere.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)occurred at 841 K and the enthalpy change was 4.37±0.04 kJ/mol.The endothermic effect at 1014 K and the enthalpy change was 26.54±0.26 kJ/mol,which is related to the incongruent melting ofβ-MgV_(2)O_(6).In situ XRD was performed to investigate phase transition of the as-prepared MgV_(2)O_(6)at high temperatures.The cell parameters obtained by Rietveld refinement indicated that it crystallizes in a monoclinic system with the C2/m space group,and the lattice parameters of a=9.280 A°,b=3.501 A°,c=6.731 A°,β=111.76°.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)was further studied by thermal kinetics,indicating that this process is controlled first by a fibril-like mechanism and then by a spherulitic-type mechanism with an increasing heating rate.Additionally,the enthalpy change of MgV_(2)O_(6)at high temperatures was measured utilizing the drop calorimetry,heat capacity was calculated and given as:Cp=208.3+0.03583T-4809000T^(−2)(298-923 K)(J mol^(−1)K^(−1)),the high-temperature heat capacity can be used to calculate Gibbs free energy of MgV_(2)O_(6)at high temperatures.

γ-LiAlO_2 Single Crystal Grown by Czochralski Technique and Modified by Vapor Transport Equilibration (VTE) Technique

Large-sized （～2 inch, 50.8 mm） γ-LiAlO2 single crystal has been grown by conventional Czochralski （Cz） method, but the crystal has a milky, dendriform center. The samples taken from transparent and milky parts were ground and examined by X-ray diffraction. All diffraction peaks could be indexed in γ-LiAlO2. The crystal quality was characterized by X-ray rocking curve. The full-width at half-maximum （FWHM） values are 116.9 and 132.0 arcsec for transparent and milky parts, respectively. The vapor transport equilibrium （VTE） technique was introduced to modify the crystal quality. After 1000℃/48 h, 1100℃/48 h, 1200℃/48 h VTE processes, the FWHM values dropped to 44.2 and 55.2 arcsec for transparent and milky part, respectively. The optical transmission of transparent part was greatly enhanced from 85% to 90%, and transmission of milky part from 75% to 80% in the range of 190~1900 nm at room temperature. When the VTE temperature was raised to 1300℃, the sample cracked and FWHM values of transparent and milky parts were increased to 55.2 and 80.9 arcsec, respectively. By combining Cz technique with VTE technique, large-sized and high quality γ-LiAlO2 crystal can be obtained.

NdF_(3)-LiF-Nd_(2)O_(3)-NdF_(2)熔盐体系结晶行为的研究

氟化物体系稀土氧化物熔盐电解过程中,熔盐的结晶析出行为显著影响电解过程,为此本文针对NdF_(3)-LiF-Nd_(2)O_(3)、NdF_(3)-LiF-NdF_(2)以及NdF_(3)-LiF-Nd_(2)O_(3)-NdF_(2)三种熔盐体系(NdF_(3)和LiF质量比固定为85∶15),采用降温黏度曲线测定熔盐的结晶温度,通过X射线衍射分析结晶物相。结果表明:NdF_(3)-LiF-Nd_(2)O_(3)和NdF_(3)-LiF-NdF_(2)熔盐体系中,随着熔盐中Nd_(2)O_(3)或NdF_(2)含量的增加,熔盐的结晶温度升高,熔盐的结晶物相分别为NdOF和NdF_(2);NdF_(3)-LiF-Nd_(2)O_(3)-NdF_(2)熔盐体系中,当Nd_(2)O_(3)含量为2%~3%、NdF_(2)含量为1%~3%时,熔盐结晶温度在981~988℃范围内,且NdOF与NdF_(2)共结晶。适当提高电解槽底部温度、改善底部熔盐的流动性,是抑制稀土熔盐电解过程熔盐结晶析出的有效方法。

Na_(2)O对锂铝硅微晶玻璃析晶及性能的影响

采用熔融法制备了不同Na_(2)O含量的透明锂铝硅微晶玻璃,通过DSC、XRD、FESEM等测试方法研究了不同Na_(2)O含量对玻璃析晶及性能的影响。结果表明:Na_(2)O的引入能显著降低玻璃的转变温度和析晶温度,抑制LiAlSi_(4)O_(10)晶相的析出。但Na_(2)O的引入促使微晶玻璃中析出Li_(2)Si_(2)O_(5)新相,并且随着Na_(2)O引入量的增加,Li_(2)Si_(2)O_(5)转变为主晶相。由于晶体尺寸均为纳米级,主晶相的转变对透过率影响较小,微晶玻璃的可见光透过率均高于85%。主晶相的转变有效增强了微晶玻璃的机械性能,其弯曲强度由300 MPa提升至331 MPa。Na_(2)O的引入有效增强了Na-K交换,Na_(2)O含量为4%(质量分数)的Li 2O-Al_(2)O_(3)-SiO_(2)微晶玻璃在410℃的KNO_(3)熔盐中交换6 h后,维氏硬度由7.108 GPa提升至7.403 GPa,弯曲强度由331 MPa提升至470 MPa。

Li_(2)O/Na_(2)O对YAS微晶玻璃结构、析晶与力学性能的影响

透明微晶玻璃由于优异的力学性能被广泛应用于电子领域。本文采用熔融法制备了不同质量分数Li_(2)O和Na_(2)O的Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)(YAS)微晶玻璃,通过Raman、DSC、XRD、FESEM、UV-VIS-NIR等测试方法研究了其结构特征、析晶与力学性能。结果表明:当碱金属氧化物R_(2)O(R=Li,Na)总量保持不变,随着Li_(2)O取代Na_(2)O含量的增加,YAS微晶玻璃的转变温度、软化温度和结晶峰温度逐渐降低,Q^(4)基团对应的含量逐渐减少,说明Li_(2)O作为网络外体使YAS微晶玻璃结构逐步解聚,玻璃的析晶能力逐渐增强。在同一热处理制度下,随着Li_(2)O取代量的增加,YAS微晶玻璃维氏硬度显著提升,而透过率明显下降。在680℃/10 h+750℃/1 h热处理制度下,可以制备出晶体大小一致且分布均匀的以钇稳定氧化锆为主晶相的透明YAS微晶玻璃,此时2%(质量分数,下同)Na_(2)O+4%Li_(2)O YAS微晶玻璃具有良好的综合性能,如维氏硬度为646 HV,断裂韧性为1.07 MPa·m^(1/2),透过率为85.7%,在诸多领域具有巨大的应用潜力。

Nb_(2)O_(5)对3Y-TZP陶瓷性能影响的研究

研究了Nb_(2)O_(5)的加入对3Y-TZP陶瓷性能的影响,主要包括对硬度、韧性、冲击性的影响,并且结合显微形貌以及XRD物相图谱分析出的晶轴比进行分析。结果表明,随着Nb_(2)O_(5)添加量的增加,陶瓷的韧性呈现提升趋势,硬度呈现降低趋势,强度呈现先上升后下降趋势。这一现象的产生,一方面归因于Nb_(2)O_(5)的加入让陶瓷生成异相小晶粒,进而提供异相颗粒增韧阻碍裂纹扩展;另一方面,由于Nb^(5+)的引入提高了晶轴比,从而让相变更容易发生。综上所述,Nb_(2)O_(5)的最佳添加质量分数为0.5%。

第一性原理研究压力对Fe_(2)B的结构、机械性质的影响

基于密度泛函理论的第一性原理方法,系统研究了0~30 GPa压力下四方相Fe_(2)B的结构,稳定性和力学性质等.随着压力的增加,计算得到的晶格参数逐渐减小,所有结构均满足热力学稳定性,体积模量和剪切模量逐渐增大,韧性得到有效改善.硬度呈现先增大后减小的趋势,并在18 GPa压力时达到最大值,各向异性先增大后减小.德拜温度变化趋势与杨氏模量的变化趋势相同.同时还研究了相变结构——正交相的相关性质,结果表明其结构满足热力学稳定性但不满足力学稳定性,是否稳定存在还需要进行后续实验研究.

Centimeter-sized Cs_(3)Cu_(2)I_(5)single crystals grown by oleic acid assisted inverse temperature crystallization strategy and their films for high-quality X-ray imaging

Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the relatively low detectivity of the lead-free halide perovskites which seriously restrain its commercialization.Here,we developed a solution inverse temperature crystal growth(ITCG)method to bring-up high quality Cs_(3)Cu_(2)I_(5)crystals with large size of centimeter order,in which the oleic acid(OA)is introduced as an antioxidative ligand to inhibit the oxidation of cuprous ions effieiently,as well as to decelerate the crystallization rate remarkalby.Based on these fine crystals,the vapor deposition technique is empolyed to prepare high quality Cs_(3)Cu_(2)I_(5)films for efficient X-ray imaging.Smooth surface morphology,high light yields and short decay time endow the Cs_(3)Cu_(2)I_(5)films with strong radioluminescence,high resolution(12 lp/mm),low detection limits(53 nGyair/s)and desirable stability.Subsequently,the Cs_(3)Cu_(2)I_(5)films have been applied to the practical radiography which exhibit superior X-ray imaging performance.Our work provides a paradigm to fabricate nonpoisonous and chemically stable inorganic halide perovskite for X-ray imaging.

Crystallization thermodynamics of 2,4(5)-dinitroimidazole in binary solvents

2,4(5)-Dinitroimidazole(2,4(5)-DNI)is an important organic intermediate,and itself can also be used for energetic material.In this work,the solubility of 2,4(5)-DNI in(methanol+water,acetonitrile+water,acetone+water)binary solvents were measured by using a dynamic test method from 278.15 K to 323.15 K under 101.1 k Pa.The Jouyban–Acree model,van't Hoff–Jouyban–Acree model,Apelblat–Jouyb an–Acree model,Ma model,and Sun model were used to correlate the experimental data.The values of relative average deviation(RAD)and root-mean-square deviation(RMSD)were very small,indicating that the error between the experimental value and the correlated value was very small.The thermodynamic parameters such as dissolution enthalpy,dissolution entropy and Gibbs energy were calculated based on solubility data.High-purity of 2,4(5)-DNI was efficiently obtained by using cooling and dilution crystallization method.

Li(Sc,M)Si_(2)O_(6)∶Cr^(3+)(M=Ga^(3+)/Lu^(3+)/Y^(3+)/Gd^(3+))的近红外发光性能

荧光转换型近红外发光二极管(NIR pc-LED)具有体积小、谱带宽、峰位易调谐等优点,是新一代NIR光源发展的前沿,其关键在于研发可被蓝光有效激发的高效率宽带近红外荧光粉。LiScSi_(2)O_(6)∶Cr^(3+)荧光材料的激发波长为460 nm,发射峰位在845 nm,光谱带宽为156 nm,内量子效率为64.4%。基于该体系,本文通过M离子(M=Ga^(3+),Lu^(3+),Y^(3+),Gd^(3+))取代Sc^(3+)的方式对其性能进行调控。结果表明,引入M离子易生成杂相或发生相变,降低了材料的发光性能。本文从晶体结构出发对其调控过程进行了分析。

高光产额SrI_(2)Eu^(2+)晶体制备及其闪烁性能研究

SrI_(2)Eu^(2+)晶体因其极高的光产额和优良的能量分辨率,在伽马射线高分辨测量中呈现出良好的应用前景。采用改进的坩埚下降法制备出掺杂浓度为5.0%的SrI_(2)Eu^(2+)晶体,加工制成了直径为25 mm,厚度分别为3,6,9,12 mm的单透光防潮封装SrI_(2)Eu^(2+)闪烁体。研究了4种不同尺寸闪烁体对^(241)Am,^(137)Cs,^(60)Co放射源伽马射线的响应,测试了SrI_(2):Eu^(2+)晶体的荧光光谱、能量分辨率、发光产额及衰减时间等闪烁性能。实验结果表明:SrI_(2)Eu^(2+)晶体的发光光谱峰值位于436 nm,SrI_(2)Eu^(2+)晶体闪烁性能随晶体厚度减薄或伽马射线能量的提高而提升。3 mm厚度SrI_(2)Eu^(2+)闪烁体对1.173 MeV^(60)Co伽马射线的能量分辨率达到了2.74%,在^(137)Cs源伽马射线激发下,光产额达到1.23×10^(5)MeV^(-1),是传统NaI:Tl闪烁体光产额的3倍以上,与当前国际上报道的最好的实验结果相当。

CO_(2)间接矿化工业固废制备多晶型碳酸钙研究进展

CO_(2)和工业固体废弃物的排放量逐年上升,威胁人类的生存和发展,世界各国迫切寻求降碳减排的解决路径。研究人员基于钙、镁元素与CO_(2)反应生成稳定的碳酸盐反应,开发出一系列CO_(2)矿化工艺,实现CO_(2)的永久封存。为实现CO_(2)的大规模封存和含钙固废的高值化利用,降低矿化成本,选取廉价易得的含钙工业固体废弃物为矿化原料,从多晶型微纳米碳酸钙的制备入手,总结了含钙工业固废浸取和CO_(2)间接矿化的最新研究进展,介绍了含钙工业固废间接矿化常用的浸取剂,并着重分析了间接矿化制备微纳米碳酸钙时反应条件和晶型控制剂对碳酸钙晶型和形貌产生的影响,对其控制原理进行了解释说明,总结了CO_(2)间接矿化含钙固废当前存在的技术难点,展望了未来的研究重点。国内外结果表明,调变温度、pH、搅拌速率以及CO_(2)通气速率等矿化反应条件或添加晶型控制剂能有效控制碳酸钙的晶型、形貌和尺寸。利用含钙工业固体废弃物间接矿化CO_(2)制备微纳米碳酸钙能够满足不同领域对碳酸钙的使用要求,能带来经济效益和环境效益,具有广阔的发展前景。

Crystal facet engineering coexposed CuIn(200)and In(101)in CuIn alloy nanocatalysts enabling selective and stable CO_(2)electroreduction

The electrocatalytic carbon dioxide reduction reaction(eCO_(2)RR)into high-value-added chemicals and fuels is a promising strategy to mitigate global warming.However,it remains a significant stumbling block to the rationally tuning lattice plane of the catalyst with high activity to produce the target product in the eCO_(2)RR process.To attempt to solve this problem,the Culn bimetallic alloy nanocatalyst with specifically exposed lattice planes is modulated and electrodeposited on the nitrogen-doped porous carbon cloth by a simple two-step electrodeposition method,which induces high Faraday efficiency of 80%towards HCOO-(FEHCOO-)with a partial current density of 13.84 mA cm-2at-1.05 V(vs.RHE).Systematic characterizations and theoretical modeling reveal that the specific coexposed Culn(200)and In(101)lattice facets selectively adsorbed the key intermediate of OCHO*,reducing the overpotential of HCOOH and boosting the FEHCOO-in a wide potential window(-0.65--1.25 V).Moreover,a homogeneous distribution of Culn nanoparticles with an average diameter of merely~3.19 nm affords exposure to abundant active sites,meanwhile prohibiting detachment and agglomeration of nanoparticles during eCO_(2)RR for enhanced stability attributing to the self-assembly electrode strategy.This study highlights the synergistic effect between catalytic activity and facet effect,which opens a new route in surface engineering to tune their electrocatalytic performance.

Effect of ZnO,La_(2)O_(3),and YF_(3)on Crystallization and Rehological Behavior of Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)Glass

The effect of substitution La_(2)O_(3)and YF_(3)as network modifiers respectively for Y_(2)O_(3),and ZnO as intermediate oxide for Al_(2)O_(3)on crystallization and viscous behavior of Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)glass was studied.La_(2)O_(3)and YF_(3)substitution for Y_(2)O_(3)decreases the melting temperature of studied glass from 1402 to 1346 and 1379℃,and the activation energy of viscous flow decreases from 340 to 250 and 265 kJ/mol.Meanwhile,ZnO substitution for Al_(2)O_(3)decreases the melting temperature to 1379℃while increases the activation energy of viscous flow to 542 kJ/mol,due to their different role in glass structure.Substitution ZnO for Al_(2)O_(3)refines and homogenizes the crystals size and lowers crystallinity because the nucleation and crystal growth are depressed by higher activation energy of crystallization and change of crystallization mechanism from bulk crystallization to surface crystallization.Replacement of Y_(2)O_(3)by La_(2)O_(3)and YF_(3)respectively also decreases the crystallinity of Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)glass ceramic due to competitive and hindering effect on the rearranged atoms,structural units and groups required by precipitated two crystals.Besides,y-Y2Si2O7,precipitation of Y4.67(SiO4)3O,ZnAl_(2)O_(4),and Y3Si3O10F were observed respectively due to incorporation of La_(2)O_(3),ZnO,and YF_(3).

Understand anisotropy dependence of damage evolution and material removal during nanoscratch of MgF_(2) single crystals

To understand the anisotropy dependence of the damage evolution and material removal during the machining process of MgF_(2) single crystals,nanoscratch tests of MgF_(2) single crystals with different crystal planes and directions were systematically performed,and surface morphologies of the scratched grooves under different conditions were analyzed.The experimental results indicated that anisotropy considerably affected the damage evolution in the machining process of MgF_(2) single crystals.A stress field model induced by the scratch was developed by considering the anisotropy,which indicated that during the loading process,median cracks induced by the tensile stress initiated and propagated at the front of the indenter.Lateral cracks induced by tensile stress initiated and propagated on the subsurface during the unloading process.In addition,surface radial cracks induced by the tensile stress were easily generated during the unloading process.The stress change led to the deflection of the propagation direction of lateral cracks.Therefore,the lateral cracks propagated to the workpiece surface,resulting in brittle removal in the form of chunk chips.The plastic deformation parameter indicated that the more the slip systems were activated,the more easily the plastic deformation occurred.The cleavage fracture parameter indicated that the cracks propagated along the activated cleavage planes,and the brittle chunk removal was owing to the subsurface cleavage cracks propagating to the crystal surface.Under the same processing parameters,the scratch of the(001)crystal plane along the[100]crystal-orientation was found to be the most conducive to achieving plastic machining of MgF_(2) single crystals.The theoretical results agreed well with the experimental results,which will not only enhance the understanding of the anisotropy dependence of the damage evolution and removal process during the machining of MgF_(2) crystals,but also provide a theoretical foundation for achieving the high-efficiency and low-damage processing of anisotropic single crystals.

钼片上少层MoS_(2)薄膜制备及其结构性能研究

采用气-固法在Mo基片制备高结晶质量的少层MoS_(2)薄膜。通过X射线衍射仪(XRD)、拉曼光谱仪和光学显微镜(OM)对样品的结构和形貌进行表征,研究生长温度对薄膜结构、形貌和光致发光性能的影响。结果表明:在温度为800,900,1000℃生长的大面积薄膜呈现枝状晶结构;随着生长温度的增加制备的薄膜结晶性能越来越好;所有样品特征拉曼峰均位于385.7 cm^(-1)和410.8 cm^(-1)附近,这两个特征峰的差值为25.1 cm^(-1),表明生长的薄膜为少层MoS_(2)膜;所有样品在693 nm处出现发光峰,对应带隙1.789 eV属于直接带隙半导体。该方法制备的薄膜在实现具有宽波段吸收和高光响应度的光电探测器件方面具有重要的应用价值。

Extremely fast vortex dynamics in Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrip

The maximum velocity of a mobile vortex in movement is generally limited by the phenomenon of flux-flow instability(FFI),which necessitates weak vortex pinning and fast heat removal from non-equilibrium electrons.We here demonstrate exfoliations and nano-fabrications of Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips,which possess a rather weak pinning volume of vortices,relatively low resistivity,and large normal electron diffusion coefficient.The deduced vortex velocity in Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips can be up to 300 km/s near the superconducting transition temperature,well above the speed of sound.The observed vortex velocity is an order of magnitude faster than that of conventional superconducting systems,representing a perfect platform for exploration of ultra-fast vortex matter and a good candidate for fabrications of superconducting nanowire single photon detectors or superconducting THz modulator.

1,1’-磺酰基双(2-甲基-1H-咪唑)对宽带隙钙钛矿太阳电池性能的影响

对倒置结构,带隙为1.68 eV的钙钛矿太阳电池光吸收层掺杂1,1’-磺酰基双(2-甲基-1H-咪唑),以改善钙钛矿薄膜质量,提高太阳电池性能。空间电荷限制电流(SCLC)测试结果表明,掺杂后的钙钛矿薄膜的缺陷密度明显降低;稳态光致发光光谱(PL)结果表明,掺杂后的钙钛矿薄膜的非辐射复合被显著抑制;最终太阳电池的开路电压达到1.17 V,光电转换效率达到21.42%,在氮气环境下储存1000 h后,未封装的太阳电池仍能保持初始效率的96%,稳定性显著提高。