Etching Mechanism of Ti_(3)C_(2)Cl_(2) MXene Phases by CuCl_(2)-Lewis Molten Salt Method

We described a method for obtaining fluorine-free Ti_(3)C_(2)Cl_(2)MXene phases by melting copper in CuCl_(2)instead of aluminum in Ti_(3)AlC_(2).XRD results show that when molten salt CuCl_(2)etches Ti_(3)AlC_(2),it forms an intermediate product Ti_(3)CuC_(2),and then reacts with Ti_(3)CuC_(2)to obtain Ti_(3)C_(2)Cl_(2).The reaction of Ti_(3)AlC_(2)and CuCl_(2)at a temperature of 800℃for 2 h to obtain Ti_(3)C_(2)Cl_(2)with an optimal lamellar structure is shown in SEM results.The pseudopotential plane-wave(PP-PW)method is used to calculate on the electronic structure.The etching mechanism is investigated by the total energies of each substance.The chemical reaction of Ti_(3)AlC_(2)and CuCl_(2)will first become Ti_(3)CuC_(2)and Cu,and then become Ti_(3)C_(2)Cl_(2)during the Lewis acid etching process,which are consistent with the experimental results.

Electrochemical performances of LiFePO_4/C composites prepared by molten salt method

LiFePO4/C composites were synthesized by a molten salt (MS) method using the mixture of LiCl,LiOH and NaCl.The prepared LiFePO4/C composites are characterized by X-ray diffractometry (XRD),field emission scanning electron microscopy (FESEM) and charge-discharge test.XRD patterns indicate that LiFePO4 prepared in the temperature range of 550-700 ℃ crystallizes well in an olivine-type structure.Through FESEM images,the sphere-like and homogeneous particles of 0.2 μm can be observed.The charge-discharge test shows that the materials prepared at 600 ℃ for 12 h have good electrochemical performance.At the rates of 0.2C (34 mA/g) and 0.5C,the discharge capacities are 144.6 and 122.3 mA·h/g,respectively,together with good cycle performances.

COMPUTERIZED SIMULATION OF MOLTEN SALT SOLUTION OF Li,KF,Cl SYSTEM BY MOLECULAR DYNAMIC METHOD

The structure and properties of molten salt solution o J Li,K|F,Cl system have been investiged by computerized simulation of molecular dynamic method.The partial RDF,the partial molar energy of mixing and the diffusion coeffients of Li^+,K^+,F^- and Cl^- have been calculated. The results are in agreement with the experimental values.The regularities of the distribution of ions and mieroscopic holes are discussed based on the results of computerized simulation.

Structural and Piezoelectric Properties of Sr_(0.6)Ba_(0.4)Nb_2O_6 Micro-rods Synthesized by Molten-Salt Method

Sr0.6 Ba0.4 Nb2 O6 micro-rods are prepared by the molten-salt method with K2 SO4,KCl-K2 SO4,and KCl as fluxes.It reveals that the Sr0.6 Ba0.4 Nb2 O6 synthesized with KCl as a flux exhibits a single phase with tetragonal tungsten bronze structure.The measurement of X-ray diffraction indicates that the Sr0.6 Ba0.4 Nb2 O6 micro-rods synthesized at 1 300℃are anisotropic.The morphology of the powers is examined by transmission electron microscope.It reveals that the length-diameter ratio of Sr0.6 Ba0.4 Nb2 O6 micro-rods increases with increasing annealing temperature from 900℃to 1 300℃.At 1 300℃,the rod possesses a large length-diameter ratio of 8∶1.Moreover,the analysis of the piezoelectric properties of single micro-rods using apiezo-response force microscope indicates that the domains of the material are arranged along its radial direction.

Low temperature molten salt synthesis of porous La_(1-x)Sr_xMn_(0.8)Fe_(0.2)O_3(0≤x≤0.6) microspheres with high catalytic activity for CO oxidation

A molten salt method was developed to prepare porous La1‐xSrxMn0.8Fe0.2O3 （0≤ x ≤ 0.6） micro‐spheres using hierarchical porous δ‐MnO2 microspheres as a template in eutectic NaNO3‐KNO3. X‐ray diffraction patterns showed that single phase LaMn0.8Fe0.2O3 with good crystallinity was syn‐thesized at 450℃ after 4 h. Transmission electron microscope images exhibited that the LaMn0.8Fe0.2O3 sample obtained at 450？？ after 4 h possessed a porous spherical morphology com‐posed of aggregated nanocrystallites. Field emission scanning electron microscope images indicated that the growth of the porous LaMn0.8Fe0.2O3 microspheres has two stages. SEM pictures showed that a higher calcination temperature than 450？？ had an adverse effect on the formation of a po‐rous spherical structure. The LaMn0.8Fe0.2O3 sample obtained at 450？？ after 4 h displayed a high BET surface area of 55.73 m2/g with a pore size of 9.38 nm. Fourier transform infrared spectra suggested that Sr2＋ions entered the A sites and induced a decrease of the binding energy between Mn and O. The CO conversion with the La1‐xSrxMn0.8Fe0.2O3 （0≤x≤0.6） samples indicated that the La0.4Sr0.6Mn0.8Fe0.2O3 sample had the best catalytic activity and stability. Further analysis by X‐ray photoelectron spectroscopy demonstrated that Sr2＋doping altered the content of Mn4＋ions, oxygen vacancies and adsorbed oxygen species on the surface, which affected the catalytic performance for CO oxidation.

Preparation of titanium dioxide from titania-rich slag by molten NaOH method

Preparing titanium dioxide from titania-rich slag （TiO2 73wt%） by molten NaOH method has been developed. The effects of temperature and reaction time on the titanium conversion were investigated. The results showed that temperature had significant influence on the titanium conversion as well as the structure of the product. About 92% of titanium in the titania-rich slag could be converted after reacting with NaOH at 500℃ for 1 h. Metatitanic acid was formed through the steps of washing treatment, acid dissolution, and hydrolysis. Well-dispersed spherical titanium dioxide particles with an average size of 0.1-0.4μm can be obtained by calcination of metatitanic acid. In addition, the content of titanium dioxide in the product is up to 98.6wt%, which can be used as pigments after further treatment of coating and crushing.

Flow field effect of delayed neutron precursors in liquid-fueled molten salt reactors

In molten salt reactors(MSRs),the liquid fuel salt circulates through the primary loop and a part of the delayed neutron precursors(DNPs)decays outside the reactor core.To model and analyze the flow field effect of DNPs in channel-type liquid-fueled MSRs,a three-dimensional space-time dynamics code,named ThorCORE3D,that couples neutronics,core thermalhydraulics,and a molten salt loop system was developed and validated with the Molten Salt Reactor Experiment(MSRE)benchmarks.The effects of external loop recirculation time,fuel flow rate,and core flow field distribution on the delayed neutron fraction loss of MSRE at steadystate were modeled and simulated using the ThorCORE3D code.Then,the flow field effect of the DNPs on the system responses of the MSRE in the reactivity insertion transient under different initial conditions was analyzed systematically for the channel-type liquid-fueled MSRs.The results indicate that the flow field condition has a significant effect on the steady-state delayed neutron fractions and will further affect the transient power and temperature responses of the reactor system.The analysis results for the effect of the DNP flow field can provide important references for the design optimization and safety analysis of liquid-fueled MSRs.

The protective performance of a molten salt frozen wall in the process of fluoride volatility of uranium

The fluoride volatility method (FVM) is a technique tailored to separate uranium from fuel salt of molten salt reactors. A key challenge in R&D of the FVM is corrosion due to the presence of molten salt and corrosive gases at high temperature. In this work, a frozen-wall technique was proposed to produce a physical barrier between construction materials and corrosive reactants. The protective performance of the frozen wall against molten salt was assessed using FLiNaK molten salt with introduced fluorine gas, which was regarded as a simulation of the FVM process. SS304, SS316L, Inconel 600 and graphite were chosen as the test samples. The extent of corrosion was characterized by an analysis of weight loss and scanning electron microscope studies. All four test samples suffered severe corrosion in the molten salt phase with the corrosion resistance as: Inconel 600>SS316L>graphite>SS304. The presence of the frozen wall could protect materials against corrosion by molten salt and corrosive gases, and compared with materials exposed to molten salt, the corrosion rates of materials protected by the frozen wall were decreased by at least one order of magnitude.

Cerium Oxide Film Prepared from Molten Salts

Cerium oxide film formed on the nickel electrode at 453 K in LiNO3-KNO3 molten salts. The molten salt background and the cathode process of Leeds on the nickel electrode were studied by using cyclic voltammetry. The cathodic reaction mechanism of the molten salt background was: O-2(-)+e <----> O-2(-2); O-2+2NO(3)(-) --> 2NO(2)(-)+2O(2). According to the results of SEM and XPS, cerium oxide film, which is composed of CeO2, can form on the nickel electrode at - 1.850 V vs. Ag/AgNO3 (0.1 mol/L) reference electrode.

COMPUTERIZED SIMULATION OF THERMODYNAMICS FOR MOLTEN LiF-KF SOLUTION BY MONTE CARLO METHOD

The structure and behaviour of LiF-KF solution,as a typical common-anion system,has been simulated by Monte Carlo method.The calculation of partial radial distribution function of ions,heat of mixing and potential energy distribution shows that the average distance be- tween Li^+ and F^- ions will significantly narrow after mixing of molten LiF and KF.This is very similar to the lean-on-one-side effect in molten LiF-KCl solution.The calculated heat of mixing is in fair agreement with the measured one.The dominant source of the energy of mixing may be that the decrease of the repulsion energy between cations,the decrease of the attraction energy between cations and anions,and the decrease of the repulsion energy be- tween anions.

COMPUTER SIMULATION OF STRUCTURE OF MOLTEN DyF_3－BaF_2－LiF SYSTEM BY MONTE CARLO METHOD

ＣＯＭＰＵＴＥＲＳＩＭＵＬＡＴＩＯＮＯＦＳＴＲＵＣＴＵＲＥＯＦＭＯＬＴＥＮＤｙＦ_３－ＢａＦ_２－ＬｉＦＳＹＳＴＥＭＢＹＭＯＮＴＥＣＡＲＬＯＭＥＴＨＯＤ￥ＸｕＣｈｉ；ＳｕＨａｎｇ；ＣｈｅｎＮｉａｎｙｉ（ＳｈａｎｇｈａｉＩｎｓｔｉｔｕｔｅｏｆＭｅｔａｌｌ...

Computerized Simulation of the Structure of Molten DyF_3-LiF System

The structure of molten DyF_3-LiF system has been simulated by Monte Carlo method.The radial distribution functions(RDFs)and the local structure have been obtained.It is concluded that F^- ions distribute closely around Dy^(3+) ions.There exist some fissures and holes between F^- ions and Li^+ ions. There are mainly two kinds of ionic types:the complex ions like DyF_n^(3-n) clusters with the central Dy^(3+) ions (the main ionic clusters are octahedral complex ions like DyF_6^(3-))and the“free”Li^+ ions.Moreover,some complex ions like DyF_n^(3-n) clusters are connected to one another by flourine-bridge,forming more compli- cated ionic clusters like Dy_m^(3m-n) F_n.By calculating the potential energies of all types of ions,it is concluded that Li^+ ions have the highest potential energy in the molten system,which are current-carrying ions in the electrolytic conductance.

NdF_(3)在LiF熔盐中的溶解及离子结构

LiF-NdF_(3)熔盐体系中离子的构成形式对解析电解钕工艺的电解过程至关重要,本文采用冰点降低法分析LiF-NdF_(3)熔盐体系的离子结构。通过Temkin和Flood模型及热力学计算分析熔盐体系内可能存在的离子团簇,结果表明,NdF_(3)在LiF中的溶解模型符合TemkinⅠ、TemkinⅡ、TemkinⅥ、TemkinⅦ和FloodⅡ、FloodⅥ、FloodⅦ,在LiF-NdF_(3)熔盐体系中主要形成含有1~2个Nd^(3+)的分子团簇,NdF_(3)在LiF内溶解主要形成游离的Nd^(3+)、F-、Li^(+)以及Li^(+)·[NdF_(4)]^(-)、Li^(+)·[Nd2F7]-、2Li^(+)·[Nd_(2)F_(8)]^(2-)分子团簇。

熔盐辅助合成硼化铪工艺研究

这是一篇冶金工程领域的论文。以氧化铪和碳化硼为原料,采用氯化钠为熔盐介质,通过硼/碳热还原法合成了纯度较高的硼化铪粉体。研究了反应温度、保温时间等合成工艺参数以及原料配比对材料晶相组成和显微结构的影响。结果表明,以氯化钠为熔盐介质时,氧化铪在1300℃的合成温度下开始转化为硼化铪,其温度远低于传统的硼化铪合成所需温度。在硼过量20%,反应温度和保温时间分别为1400℃和2 h所制备的硼化铪粉体纯度较高,X射线衍射中可以明显观察到硼化铪结晶峰,且在扫描电镜中可以观察到紧密团聚形貌的硼化铪。

(Si_(0.2)Ti_(0.2)Nb_(0.2)Ta_(0.2)V_(0.2))C高熵陶瓷的低温制备及吸波性能

寻求具有良好耐高温及力学性能的新型陶瓷材料是吸波材料领域的研究热点之一。高熵碳化物陶瓷具有高温热稳定性及抗氧化性好等优点,但合成温度高且吸波性能研究较少,限制了其在高温吸波材料领域的应用。本工作采用熔盐法合成了多晶岩盐晶型(Si_(0.2)Ti_(0.2)Nb_(0.2)Ta_(0.2)V_(0.2))C高熵碳化物陶瓷,研究了其物相组成、微观形貌及吸波特性。结果表明:随着反应温度的升高,样品的衍射峰逐渐锐化,吸波性能明显提高。当反应温度为1500℃时,3.72 GHz时最低反射损耗达-34.68 dB;与已报道的高熵碳化物陶瓷相比,在相同的有效吸收带宽(2.3 GHz)下,涂层厚度减少了13.3%(1.5 mm降低到1.3 mm),其介电损耗主要来源于极化损耗和导电损耗。本工作制备的高熵碳化物陶瓷可以为研究制备新型环境适应、耐高温、抗冲击的高性能单相吸波材料提供新途径。

熔盐堆用U型管壳式换热器的传热与流动特性模拟分析

为更好地理解和掌握熔盐换热器的运行特征,并给熔盐堆中换热器的设计和运行累积经验,本文以美国橡树岭国家实验室10 MWt熔盐实验堆(Molten Salt Reactor Experiment,MSRE)用的主换热器为研究对象,基于该换热器的设计参数,应用管壳式换热器的理论计算方法(包括Kern方法和Bell-Delaware方法)、换热器设计软件HTRI Xchanger Suite和计算流体力学方法(Computational Fluid Dynamics,CFD)对换热器的关键性能指标(如换热系数、压降和换热功率)分别进行了计算分析,并与MSRE主换热器的实验数据进行比较分析。结果表明:两种理论计算方法(Kern方法、Bell-Delaware方法)、HTRI软件及CFD仿真模拟的结果与实验结果的差异均在可接受范围内。其中,Kern方法与MSRE实验所得的换热量相差最大,约为15%;HTRI软件模拟与MSRE实验所得的总换热系数相差最小,为0.16%。理论计算方法、换热器设计软件及CFD仿真均在不同程度上适用于熔盐-熔盐换热器设计,且CFD仿真还可以对换热器内部传热和流动细节进行直观描述。

LiF-[CaF_(2)/YbF_(3)]-Yb_(2)O_(3)熔盐及Yb-Ni合金密度特性研究

LiF-[CaF_(2)/YbF_(3)]-Yb_(2)O_(3)熔盐体系的密度是电解法制备稀土Yb合金的重要参数。本文采用阿基米德法测量和分析在1173~1573 K温度范围内LiF-[CaF_(2)/YbF_(3)]-Yb_(2)O_(3)体系的密度及其变化规律,同时,利用数学模型估测Yb-Ni合金密度,分析电解过程中熔盐与合金的分离性,结果表明:在1173~1573 K温度范围内,(LiF-CaF_(2))eut(eut为熔盐体系共晶点)体系与(LiF-YbF_(3))eut体系密度均随温度升高而线性降低,同时,摩尔体积均随温度线性递增;(LiF-YbF_(3))eut体系过剩体积随温度线性递减;在1173~1573 K温度区间和Yb_(2)O_(3)质量分数在0~4%范围内,当Yb_(2)O_(3)含量一定时,(LiF-CaF_(2))eut-Yb_(2)O_(3)和(LiF-YbF_(3))eut-Yb_(2)O_(3)熔盐体系的密度均随温度升高而线性降低,当温度一定时,(LiF-CaF_(2))eut-Yb_(2)O_(3)体系在0≤x(Yb_(2)O_(3))≤2.5%范围内呈线性递增,而((LiF-YbF_(3))eut-Yb_(2)O_(3)体系在0≤x(Yb_(2)O_(3))≤3.5%范围内呈线性递增;Yb-Ni合金的密度要高于LiF-[CaF_(2)/YbF_(3)]-Yb_(2)O_(3)熔盐体系的密度,在电解过程中易于分离。

Ba_(3)(VO_(4))_(2):Sm^(3+)荧光粉的熔盐法合成及其温度传感特性

采用熔盐法成功合成了Ba_(3-x)(VO_(4))_(2):xSm^(3+)(x=0.02~0.16)一系列荧光粉,探讨了合成条件、Sm^(3+)掺杂对样品结构和发光性能的影响,并探究了样品的温度传感性能。结果表明:合成样品的适宜反应条件是煅烧温度为900℃、煅烧时间为1 h、原料与熔盐质量比为1∶3,所得样品相纯度和结晶度均较高。样品微观形貌呈片状,厚度约1.5~3 mm。在318 nm激发下,Ba_(3-x)(VO_(4))_(2):xSm^(3+)的发射光谱中可同时观察到VO_(4)^(3-)基团的宽带发射和Sm^(3+)的特征发射,样品的发光颜色集中在黄白光区域。随着Sm^(3+)掺杂浓度(x)从0.02增大到0.16,Sm^(3+)的特征发射峰强度呈现出先升后降的变化趋势,当x=0.10时,发射峰强度达到最高值。导致其浓度猝灭的主要原因是电偶极-电偶极(d-d)相互作用。在298~473 K的温度范围内,Ba_(2.9)(VO_(4))_(2):0.10Sm^(3+)荧光粉中Sm^(3+)(652 nm)和VO_(4)^(3-)基团(504 nm)发射的荧光强度比呈现明显的温度依赖性,其最大绝对灵敏度为0.36 K^(-1),最大相对灵敏度为1.99%K^(-1)。因此,Sm^(3+)掺杂Ba_(3)(VO_(4))_(2)的荧光粉具有优异的温度传感性能,在非接触式光学测温中具有潜在的应用价值。

铝-空气电池废电解液制备片状氧化铝的研究

以铝-空气电池废电解液为原材料,用硫酸铝调节pH值,用硫酸钾作为熔盐制备片状氧化铝(α-Al_(2)O_(3)),研究了合成温度、晶种添加量对α-Al_(2)O_(3)粉体体积分数、粒度大小及粒度分布的影响规律。通过X射线衍射仪、扫描电子显微镜和激光粒度仪等,对加入不同晶种量的α-Al_(2)O_(3)粉体的结构和形貌进行表征。结果表明,添加晶种后可以提高α-Al_(2)O_(3)粉体的体积分数,减小α-Al_(2)O_(3)粉体的粒度,使α-Al_(2)O_(3)粉体的粒度分布更集中,同时使α-Al_(2)O_(3)粉体更分散。此外,当晶种添加量为5%(质量分数)时,制备出的片状α-Al_(2)O_(3)的体积分数可达97.0%,平均粒度约为7.24μm。

颗粒团聚对太阳盐纳米流体导热性能的影响特性研究

【目的】纳米流体技术是提升太阳能光热电站熔盐储热材料导热性能的重要手段。然而实际熔盐基纳米流体中纳米粒子通常会自发聚集并沉降,进而显著影响储能介质的热导率。为了深入探究熔盐基纳米流体热物性的调控规律,在太阳盐相变介质中分别构建了具有不同分散形态的二氧化硅纳米颗粒。【方法】基于分子动力学和格子玻尔兹曼方法,重点探讨了体系温度、纳米颗粒的质量分数以及聚集体微观形貌对太阳盐-二氧化硅纳米流体热导率的影响特性。【结果】添加纳米颗粒能有效提升基液的导热性能。相较于均匀分散的纳米流体,聚集型纳米流体的热导率更高,并且随着团聚颗粒分形维数的增加而降低。此外,纳米流体的热导率与温度、团聚尺寸呈负相关,而与纳米粒子的质量分数、聚集体主链的粒子数量以及其团聚程度呈正相关。【结论】研究成果揭示了纳米颗粒聚集对相变材料内热输运的作用机制,并为熔盐基纳米流体热物性的设计提供了参考。