Synthesis of Mesoporous Chromium Aluminophosphate (CrAlPO) via Solid State Reaction at Low Temperature

Mesoporous chromium aluminophosphate （CrAIPO） was successfully synthesized via solid state reaction （SSR） route at low temperature in the presence of a cationic surfactant cetyltrimethyl ammonium bromide （CTAB） and inorganic sources such as A1C13 · 6H20, CrCI3 · 6H20 and NaH2PO4 · 2H20. Characterizations by means of powder X-ray diffraction （XRD）, N2 adsorption- desorption, high resolution transmission electron microscopy （HR-TEM）, scanning electron micrography （SEM）, energy dispersion spectroscopy （EDS）, thermo-gravimetry （TG）, Fourier transform infrared spectroscopy （FT-IR）, and ultraviolet visible light spectroscopy （UV-Vis） were carried out to understand both the pore characteristics and electron transition route of these obtained materials. The experimental results show that the meso-CrA1PO materials with various Cr/A1 molar ratios possess a mesostructure and a specific surface area of 193 to 310 m2/g corresponding to an average pore size of 5.5 to 2.2 rim, respectively. The maxium content of Cr in meso-CrA1PO materials synthesized via SSR route can achieve 16.7wt%, being significantly higher than that of the meso-CrA1PO prepared via a conventional sol-gel route. Meanwhile, the formation mechanism of the meso-CrA1PO was also proposed.

Preparation of transparent yttrium aluminum garnet ceramics by relatively low temperature solid-state reaction

A new preparation method for a highly sinterable Y 2O 3 powder was developed, using the mixture of the powder with Al 2O 3 powder, a transparent yttrium aluminum garnet(YAG) ceramic was prepared at relatively low temperature by a solid state reaction method. Yttrium nitrate was used as a mother salt, and aqueous ammonia was used as a precipitant reagent, the fine and dendritic precursor crystalline was prepared by adding 0.5% ammonium sulfate into the precipitation reaction system. The highly pure and low agglomerated Y 2O 3 powders were obtained by calcinating the precursor at 1 100 ℃, the primary particles are spherical and 60 nm in diameter. The mixture of Y 2O 3 and Al 2O 3 powders was calcinated, and the resulting mixture compact pressed in mold could be sintered to transparency under vacuum at 1 700 ℃. The sintered transparent YAG polycrystalline exhibits a homogeneous microstructure and its transmittance reaches 45% in the visible light region and 70% in the near infrared wavelength region.

Salt-assisted Low Temperature Solid State Synthesis of High Surface Area CoFe_2O_4 Nanoparticles

A novel salt-assisted low temperature solid state method using CoCl2.6H2O, FeCl3.6H2O and NaOH as precursor and using NaCI as a dispersant to synthesize high surface area CoFe2O4 nanoparticles, has been investigated. The effects of the molar ratio of added salt and calcination temperature on the characteristics of the products were investigated by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, vibrating sample magnetometer （VSM） and Brunauer, Emmett and Teller （BET） surface area analysis. Results showed that the introduction of leachable inert inorganic salt as a hard agglomeration inhibitor in the mixture precursor led to the formation of high dispersive CoFe2O4 nanoparticles; and the increase in specific surface area from 28.28 to 73.97 m^2/g, and the saturation magnetization is 84.6 emu/g.

Preparing Nano-ZnS by Solid State Reaction at Room Temperature

ZnS nanoparticles were prepared by using solid-state reaction method at room temperature in agate mortar for the first time. The average particle size was about 20nm. This reaction is affected by the structure of reactant, crystal water and defects.

Preparation of nano-sized cerium and titanium pyrophosphates via solid-state reaction at room temperature

Nano-sized cerium-titanium pyrophosphates Ce1-xTixP2O7 （with x = 0, 0.2, 0.5, 0.7, 0.9, and 1.0） were obtained by grinding a mixture of Ce（SO4）2·4H2O, Ti（SO4）2, and Na4P2O7·10H2O in the presence of surfactant PEG-400 at room temperature, washing the mixture with water to remove soluble inorganic salts, and drying at 100℃. The products and their calcined samples were characterized using ultraviolet-visible spectroscopy （UV-vis）, thermogravimetry and differential thermal analyses （TG/DTA）, X-ray powder diffraction （XRD）, and transmission electron microscopy （TEM）. The results show that nano-sized Ce1-xTixP2O7 behave as an excellent UV-shielding material. Thereinto, the CeP2O7 has the most excellent UV-shielding effect, and the amorphous state of Ce0.8Ti0.2P2O7 can keep at a higher temperature than CeP2O7. Therefore, the stabilization of the amorphous state of the cerium pyrophosphates was carded out by doping titanium. This stabilization is a significant improvement, which enables to apply these amorphous pyrophosphates not only to cosmetics and paints, but also plastics and films.

Microstructural evolution of NiFe_2O_4-10NiO powder prepared by high temperature solid state reaction

The NiFe2O4-10NiO powder for inert anode of aluminium electrolysis was prepared by high temperature solid state reaction. The microstructural evolution from the raw materials NiO and Fe2O3 to the NiFe2O4-10NiO powder was studied by SEM. The results show that the domain structure making up of the agglomerate particles of Fe2O3 remains after high temperature solid state reaction, and the diffusion of Ni2+ into Fe2O3 structure is the control step of the reaction process. A microstructure with compact structure and fine grain inside the particle results from the sintering of NiFe2O4-10NiO powder.

Influence of FeO and sulfur on solid state reaction between MnO-SiO_2-FeO oxides and an Fe-Mn-Si solid alloy during heat treatment at 1473 K

To clarify the influence of Fe O and sulfur on solid state reaction between an Fe-Mn-Si alloy and Mn O-Si O2-Fe O oxides under the restricted oxygen diffusion flux, two diffusion couples with different sulfur contents in the oxides were produced and investigated after heat treatment at 1473 K. The experimental results were also compared with previous work in which the oxides contained higher Fe O. It was found that although the Fe O content in the oxides decreased from 3wt% to 1wt% which was lower than the content corresponding to the equilibrium with molten steel at 1873 K, excess oxygen still diffused from the oxides to solid steel during heat treatment at 1473 K and formed oxide particles. In addition, increasing the sulfur content in the oxides was observed to suppress the diffusion of oxygen between the alloy and the oxides.

The Application of Thermomechanical Dynamics (TMD) to the Analysis of Nonequilibrium Irreversible Motion and a Low-Temperature Stirling Engine

We applied the method of Thermomechanical Dynamics (TMD) to a low-temperature Stirling engine, and the dissipative equation of motion and time-evolving physical quantities are self-consistently calculated for the first time in this field. The thermomechanical states of the heat engine are in Nonequilibrium Irreversible States (NISs), and time-dependent thermodynamic work W(t), internal energy E(t), energy dissipation or entropy Qd(t), and temperature T(t), are precisely studied and computed in TMD. We also introduced the new formalism, Q(t)-picture of thermodynamic heat-energy flows, for consistent analyses of NISs. Thermal flows in a long-time uniform heat flow and in a short-time heat flow are numerically studied as examples. In addition to the analysis of time-dependent physical quantities, the TMD analysis suggests that the concept of force and acceleration in Newtonian mechanics should be modified. The acceleration is defined as a continuously differentiable function of Class C2 in Newtonian mechanics, but the thermomechanical dynamics demands piecewise continuity for acceleration and thermal force, required from physical reasons caused by frictional variations and thermal fluctuations. The acceleration has no direct physical meaning associated with force in TMD. The physical implications are fundamental for the concept of the macroscopic phenomena in NISs composed of systems in thermal and mechanical motion.

Carbonation Reaction of Lithium Hydroxide during Low Temperature Thermal Energy Storage Process

In order to apply lithium hydroxide(LiOH)as a low temperature chemical heat storage material,the carbonation reaction of LiOH and the prevention method are focused in this research.The carbonation of raw LiOH at storage and hydration condition is experimentally investigated.The results show that the carbonation reaction of LiOH with carbon dioxide(CO_(2))is confirmed during the hydration reaction.The carbonation of LiOH can be easily carried out with CO_(2) at room temperature and humidity.LiOH can be carbonated at a humidity range of 10%to 20%,a normal humidity region that air can easily be reached.Furthermore,the carbonation reaction rate has not nearly affected by the increase of reaction temperature.An improved storage method by storing LiOH at a low humidity less than 1.0%can be effectively prevented the carbonation of LiOH.The hydration reaction ratio of LiOH at the improved storage method shows a better result compared to the ordinary storage method.Therefore,the humidity should be carefully controlled during the storage of LiOH before hydration and dehydration reaction when apply LiOH as a low heat chemical storage material.

Solid-state synthesis of Sr-and Co-doped LaMnO_3 perovskites

The synthesis process for La 1- x Sr x Mn 1- y Co y O 3- δ ( x = 0.2, 0.3; y = 0.2, 0.8, designated as LSMC below) perovskite oxides prepared by solid state reaction was investigated using DSC/TG, XRD, EPMA and particle size analysis methods. It was found that LSMCs were all of single phase and the synthesis process might be divided into three stages: the decomposition of reactants, the formation of LaMn(Co)O 3 based oxides, and the formation of LSMC solid solution. Typical average and the peak value of particle size, and the specific surface area are 14.65?μm, 16.4?μm and 1.38?m 2/mL, respectively, for mixed reactants and are 23.81?μm, 32.11?μm and 0.5?m 2/mL, respectively, for powder synthesized at 1?200?℃ for 8?h in air.

Low Temperature Heat Capacities and Thermodynamic Properties of Zinc L-Threonate Zn(C_4H_7O_5)_2(s) by Adiabatic Calorimetry

Low-temperature heat capacities of the solid compound Zn（C4H7O5）2（s） were measured in a temperature range from 78 to 374 K, with an automated adiabatic calorimeter. A solid-to-solid phase transition occurred in the temperature range of 295？322 K. The peak temperature, the enthalpy, and entropy of the phase transition were determined to be （316.269±1.039） K, （11.194±0.335） kJ？mol-1, and （35.391±0.654） J？K-1？mol-1, respectively. The experimental values of the molar heat capacities in the temperature regions of 78？295 K and 322？374 K were fitted to two polynomial equations of heat capacities（Cp,m） with reduced temperatures（X） and [X = f（T）], with the help of the least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound, relative to that of the standard reference temperature 293.15 K, were calculated on the basis of the fitted polynomials and tabulated with an interval of 5 K. In addition, the possible mechanism of thermal decomposition of the compound was inferred by the result of TG-DTG analysis.

Planck’s Oscillators at Low Temperatures and Haken’s Perturbation Approach to the Quantum Oscillators Reconsidered

In the first step the extremal values of the vibrational specific heat and entropy represented by the Planck oscillators at the low temperatures could be calculated. The positions of the extrema are defined by the dimensionless ratios between the quanta of the vibrational energy and products of the actual temperature multiplied by the Boltzmann constant. It became evident that position of a local maximum obtained for the Planck’s average energy of a vibration mode and position of a local maximum of entropy are the same. In the next step the Haken’s time-dependent perturbation approach to the pair of quantum non-degenerate Schr?dinger eigenstates of energy is re-examined. An averaging process done on the time variable leads to a very simple formula for the coefficients entering the perturbation terms.

基于Smith模糊PID控制的固体电蓄热供热温控系统研究

固体电蓄热供热的温控系统存在滞后性,导致系统响应缓慢,抗干扰能力和能源利用率大大降低。为了解决这一问题,以某高校的固体储能供热示范工程为基础,提出了采用基于Smith模糊PID控制的方法对温控系统进行控制。实验结果显示,该温控系统的控温精度可达到±0.8℃,调节时间缩短了5 min。分析结果表明,与传统的PID控制方法相比,这种控制方法能够更有效地减小控制过程中的扰动影响,显著缩短调节时间,使系统更快进入稳定状态,有效克服了传统大滞后系统对稳定性的不利影响,温控效果优于传统PID控制。

Low-heating solid state synthetic reactions of cyclopeantadienyl organolanthanide complexes

A novel and simple one-step, solid state reaction of multicomponent systems has been developed to synthesize cyclopentadienyl-containing organolanthanide complexes, in which the effects of the coordinated solvent molecules and the nature of the reactants were also studied. We also studied the solid state decomposition reaction of Cp2YbPz(HPz), and the formation of [CpYb(Pz)2]2 may indicate that the constrained environment in solid state can lead to a novel chemical transformation, with product selectivity possibly different from that in the liquid phase.

基于热量平衡模型的大曲发酵升温机理研究

中国白酒产业正面临产业转型升级,包括制曲在内的关键工艺采用基于经验式的直接改造,关键工程学机理的缺乏导致无法进行理性设计。该研究从大曲升温机理角度,对曲房固态发酵热量的产生与流动进行了定量分析,跟踪记录大曲发酵过程参数,简化大曲发酵过程生化反应,构建大曲热量平衡模型。通过模型计算,整个曲房发酵过程产生的热量,经水分蒸发途径散热占比54.22%,墙壁和微弱气体流动散热占比42.00%,由室内空气升温引起的热量变化可以忽略,剩余3.77%为累积热量部分,其与大曲升温呈正相关(R^(2)=0.85)。经验证,大曲温度变化模型的平均误差为5.05%,R^(2)=0.94。基于模型探讨了调控水分参数对大曲温度产生的影响,表明了水分控制对于调控大曲温度的重要性。初步探讨从数学建模的角度为未来大曲生产的调控与优化的可行性,研究结果可为智能曲房的构建提供理论支撑。

钾离子电池低温电解质的研究进展

钾离子电池因其能量密度高、廉价易得等特点,已成为有潜力的储能设备,尤其钾离子更小的斯托克斯半径,使超低温钾离子电池成为可能。然而,传统电解质会使钾离子电池在低温下生长枝晶,导致电池失效并造成安全隐患。因此,改善电解质的低温特性对提高钾离子电池低温性能至关重要。本文综述了近些年钾离子电池低温电解质的研究进展,其大致可分为三类,即非水系电解液、水系电解液和固态电解质。其中,非水系电解液大多含弱溶剂化醚类溶剂和添加剂,提高界面去溶剂化过程的同时使电极表面形成良好的界面膜,以提高电池的低温性能;水系电解液通过引入特定的添加剂分子降低电解液凝固点的同时破坏H2O分子间氢键网络,实现电池低温性能;固态电解质以准固态电解质为主,使聚合物骨架孔道中保留少量液态电解液以提高电解质体相离子传输,并降低电解质与电极界面接触阻抗,最终提高电池的低温性能。

NaYSiO_(4)∶Ce^(3+)蓝色荧光粉的发光性质及其在白光发光二极管上的应用

采用高温固相法合成了NaYSiO_(4)∶xCe^(3+)(0.01≤x≤0.05)系列蓝色荧光粉。NaYSiO_(4)∶xCe^(3+)荧光粉在250~360 nm之间的宽带吸收能与紫外LED芯片很好地匹配。NaYSiO_(4)∶xCe^(3+)荧光粉中存在多个Ce^(3+)离子荧光中心,且在紫外光激发下表现出峰值波长位于414 nm附近的宽带蓝光发射。NaYSiO_(4)∶0.02Ce^(3+)荧光粉在300~350 nm紫外光激发下量子效率在25%以上。NaYSiO_(4)∶0.02Ce^(3+)荧光粉表现出优良的化学稳定性,在水中浸泡14 d后荧光强度和量子效率几乎不变。将NaYSiO_(4)∶0.02Ce^(3+)蓝色荧光粉、商用(Sr,Ba)_2SiO_(4)∶Eu^(2+)绿色荧光粉和商用(Ca,Sr)AlSiN_(3)∶Eu^(2+)红色荧光粉涂覆于310 nm紫外LED芯片上制备得到了显色指数高达95的LED器件。当驱动电流从50 mA逐渐增大到300 mA时,制备的LED器件表现出稳定的暖白光发射,其色坐标几乎不变。上述结果说明,本研究报道的NaYSiO_(4)∶0.02Ce^(3+)蓝色荧光粉在紫外LED芯片驱动的白光发光二极管照明上有着潜在应用价值。

聚合物基电解质在低温固态锂电池中的应用与挑战

由于其良好的柔韧性、与电极兼容性好、易加工等特点,聚合物基电解质在固态锂电池中极具应用前景。聚合物基固态电池可在室温下稳定工作,在低温下(≤0℃),聚合物电解质离子电导率的降低和缓慢的锂离子传输动力学导致电池极化增大,放电容量急剧衰减,且低温下枝晶生长更加严重,极大限制了固态电池在低温环境中的应用。本文通过对近期相关文献进行探讨,首先介绍了聚合物基电解质在低温下应用面临的挑战和局限,接着阐述了聚合物基电解质的离子传导机制,通过实例重点阐述了低温聚合物基电解质的设计策略及应用,包括添加无机/有机填料、引入液体塑化剂、分子结构工程等优化聚合物基电解质体相离子传导的方法,以及原位聚合和构建良好的固体电解质界面/正极电解质界面等优化聚合物基电解质和电极间界面离子传输的方法。最后,评估并展望了低温聚合物基电解质的传输机制、设计原则、制备方法的不足及创新。本文有望促进聚合物基电解质及其固态锂电池在低温下的应用。

纳米SiO_(2)包覆Na_(2)Ca_(2.93)Si_(6)O_(16):7% Eu^(3+)荧光粉的制备及性能研究

采用传统高温固相法在1050℃烧结下制备了Na_(2)Ca_(3-x)Si_(6)O_(16)∶xEu^(3+)红色荧光粉,其中Na_(2)Ca_(2.93)Si_(6)O_(16)∶7%Eu^(3+)荧光粉的发光性能最好。采用溶胶-凝胶法制备出纳米SiO_(2)并包覆在Na_(2)Ca_(2.93)Si_(6)O_(16)∶7%Eu^(3+)荧光粉表面,包覆量为2%~10%(wt,质量分数,下同)。通过X射线衍射仪、激发-发射光谱分别对荧光粉物相结构和发光性能进行表征,采用CIE色度坐标分析软件对样品的色度图进行绘制。结果表明纳米SiO_(2)包覆量不同的荧光粉其基质结构未发生改变,纳米SiO_(2)包覆膜是无定型的,样品的发射峰位置没有变化,但发射强度不同;当纳米SiO_(2)包覆量为8%时,荧光粉发射强度最高,比Na_(2)Ca_(2.93)Si_(6)O_(16)∶7%Eu^(3+)荧光粉的发光强度明显提高,且此时色纯度更高,更接近正红色,CIE色度坐标为(0.5282,0.3210)。

红色荧光粉CaWO_(4)∶Eu^(3+),Bi^(3+)的制备和光学性能的研究

本文采用高温固相法合成了一系列红色荧光粉CaWO_(4)∶Eu^(3+),Bi^(3+)。通过X射线衍射仪、扫描电子显微镜和荧光分光光度计等手段,对样品的晶体结构、微观形貌、光学性能、能量传递方式、荧光寿命和热稳定性进行了表征。结果表明,当Eu^(3+)和Bi^(3+)的掺杂浓度分别为7%和2%时(摩尔分数),荧光粉红色发光(615 nm)最强,理论计算得到荧光粉的平均颗粒尺寸为50.27 nm,这与电子显微镜观察结果相符合。能量传递方式以电偶极-电四极相互作用为主,对CaWO_(4)∶7%Eu^(3+),yBi^(3+)(y=0~6%)系列荧光粉进行了荧光寿命测量,发现它们荧光寿命基本相同,都在0.56 ms左右。对CaWO_(4)∶7%Eu^(3+),2%Bi^(3+)荧光粉在不同温度下的光谱进行比较,并且计算相应的色度坐标,当温度升高时,色度坐标整体左移,发光强度有所变弱,但整体来说热稳定性较好。较好的热稳定性和明亮红光发射表明该荧光粉可以作为潜在商用红光荧光粉。