A new transition metal diphosphideα-MoP_(2) synthesized by a high-temperature and high-pressure technique

Monoclinicα-MoP_(2),with the OsGe2-type structure(space group C2/m,Z=4)and lattice parameters a=8.7248(11)Å,b=3.2322(4)Å,c=7.4724(9)Å,andβ=119.263°,was synthesized under a pressure of 4~GPa at a temperature between 1100℃and 1200℃.The structure ofα-MoP_(2) and its relationship to other transition metal diphosphides are discussed.Surprisingly,the ambient pressure phase orthorhombicβ-MoP_(2)(space group Cmc21)is denser in structure thanα-MoP_(2).Room-temperature high-pressure x-ray diffraction studies exclude the possibility of phase transition fromβ-MoP_(2) to α-MoP_(2),suggesting thatα-MoP_(2) is a stable phase at ambient conditions;this is also supported by the total energy and phonon calculations.

A study of hydrate plug formation in a subsea natural gas pipeline using a novel high-pressure flow loop

The natural gas pipeline from Platform QKI8-1 in the southwest of Bohai Bay to the onshore processing facility is a subsea wet gas pipeline exposed to high pressure and low temperature for a long distance. Blockages in the pipeline occur occasionally. To maintain the natural gas flow in the pipeline, we proposed a method for analyzing blockages and ascribed them to the hydrate formation and agglomeration. A new high-pressure flow loop was developed to investigate hydrate plug formation and hydrate particle size, using a mixture of diesel oil, water, and natural gas as experimental fluids. The influences of pressure and initial flow rate were also studied. Experimental results indicated that when the flow rate was below 850 kg/h, gas hydrates would form and then plug the pipeline, even at a low water content （10%） of a water/oil emulsion. Furthermore, some practical suggestions were made for daily management of the subsea pipeline.

Thermodynamic Analysis and Synthesis Gas Generation by Chemical-Looping Gasification of Biomass with Nature Hematite as Oxygen Carriers

Thermodynamic parameters of chemical reactions in the system were carried out through thermodynamic analysis. According to the Gibbs free energy minimization principle of the system, equilibrium composition of the reactions of chemical-looping gasification (CLG) of biomass with natural hematite (Fe2O3) as oxygen carrier were analyzed using commercial software of HSC Chemistry 5.1. The feasibility of the CLG of biomass with hematite was experimental verified in a lab-scale bubbling fluidized bed reactor using argon as fluidizing gas. It was indicated the experimental results were consistent with the theoretical analysis. The presence of oxygen carrier gave a significant effect on the biomass conversion and improved the synthesis gas yield obviously. It was observed that the gas content of CO and H2 was over 70% in CLG of biomass. The reduced hematite particles mainly existed in form of FeO. It was showed that the reduction of natural hematite with biomass proceeds in a stepwise manner from Fe2O3 →Fe3O4→ FeO. Reduction product of natural hematite can be restored the lattice oxygen by oxidation with air.

Simultaneous production and utilization of methanol for methyl formate synthesis in a looped heat exchanger reactor configuration

In this investigation, a novel thermally coupled reactor （TCR） containing methyl formate （MF） production in the endothermic side and methanol synthesis in the exothermic side has been investigated. The interesting feature of this TCR is that productive methanol in the exothermic side could be recycled and used as feed of endothermic side for MF synthesis. Other important advantages of the proposed system are high production rates of hydrogen and MF. The configuration consists of two thermally coupled concentric tubular reactors. In these coupled reactors, autothermal system is obtained within the reactor. A steady-state heterogeneous model is used for simulation of the coupled reactor. The proposed model has been utilized to compare the performance of TCR with the conventional methanol reactor （CMR）. Noticeable enhancement can be obtained in the performance of the reactors. The influence of operational parameters is studied on reactor performance. The results show that coupling of these reactions could be feasible and beneficial. Experimental proof-of-concept is required to validate the operation of the novel reactor.

Large Deformation Analysis and Synthesis of Elastic Closed-loop Mechanism Made of a Certain Spring Wire Described by Free Curves

Recently novel mechanisms with compact size and without many mechanical elements such as bearing are strongly required for medical devices such as surgical operation devices. This paper describes analysis and synthesis of elastic link mechanisms of a single spring beam which can be manufactured by NC coiling machines. These mechanisms are expected as disposable micro forceps. Smooth Curvature Model（SCM） with 3rd order Legendre polynomial curvature functions is applied to calculate large deformation of a curved cantilever beam by taking account of the balance between external and internal elastic forces and moments. SCM is then extended to analyze large deformation of a closed-loop curved elastic beam which is composed of multiple free curved beams. A closed-loop elastic link is divided into two free curved cantilever beams each of which is assumed as serially connected free curved cantilever beams described with SCM. The sets of coefficients of Legendre polynomials of SCM in all free curved cantilever beams are determined by taking account of the force and moment balance at connecting point where external input force is applied. The sets of coefficients of Legendre polynomials of a nonleaded closed-loop elastic link are optimized to design a link mechanism which can generate specified output motion due to input force applied at the assumed dividing point. For example, two planar micro grippers with a single pulling input force are analyzed and designed. The elastic deformation analyzed with proposed method agrees very well with that calculated with FEM. The designed micro gripper can generate the desired pinching motion. The proposed method can contribute to design compact and simple elastic mechanisms without high calculation costs.

Synthesis identification analysis for closed loop system

The existing theories for closed loop identification with the linear feedback controller are very mature.To apply the existed theories directly in the control field,we propose a new idea about replacing the original unknown and nonlinear feedback controller with one approximated linear controller,while guaranteeing the equivalent property for the obtained closed loop system.Based on some statistical correlation functions,one condition is derived to show the equivalent property between the approximated linear controller and the original nonlinear controller.The detailed explicit form,corresponding to the approximated linear controller,is also constructed.Furthermore,to give a complete analysis for closed loop identification,the cost function is rewritten as one extended expression,being convenient to understand.Then spectral estimation is introduced to identify the unknown plant in the closed loop system.Finally,the proposed theories are verified by one simulation example.

Crystal structure and catalytic performance for direst oxidation of propylene to acrylic acid of MoVTeNbO_(x) prepared by high-pressure hydrothermal synthesis

MoVTeNbO_(x) catalysts were prepared through a high-pressure hydrothermal method,in which the crystalline structure and properties of the catalysts were tuned by varying the system pressure(0-12.0 MPa).Results showed that the system pressure had a significant influence on the structure and catalytic performance of MoVTeNbO_(x).Under 3.0 MPa,MoVTeNbO_(x) prepared possessed the highest content of M1 phase(90.6%)and V5+content(60.7%),exhibiting a uniform short and thick needle-like morphology.Also,it showed excellent selectivity(79.1%)and yield(52.8%)to acrylic acid at the catalytic temperature of 380℃.However,under 4.4 and 11.6 MPa,the characteristic peaks of M1 shifted to a certain extent and the morphology changed from short and thick to slender.As a result,the V5+content of M1(001)plane decreased,resulting in a remarkable decline of the selectivity to acrylic acid.Moreover,DFT simulation results showed that the anti-bond orbital energy of V-O bond is the highest under 3.0 MPa,while further increase of pressure leads to obvious extrusion between atoms in the internal structure of MoVTeNbO_(x).Moreover,it was clear that the lower the anti-bond orbital energy of V-O bond,the lower the selectivity to acrylic acid.

Recent progress towards mild-condition ammonia synthesis

Ammonia is essential for food and energy.Industrial ammonia synthesis via Haber–Bosch process is energy-intensive and releases large amount of CO2.Increasing research efforts are devoted to "green"ammonia synthesis.The present article reviews the recent progress in the fields of thermocatalytic, electrocatalytic, photocatalytic and chemical looping processes for dinitrogen reduction towards ammonia formation and discusses the challenges borne for mild-condition synthesis.

Preparation and Application of the Sol–Gel Combustion Synthesis-Made CaO/CaZrO_3 Sorbent for Cyclic CO_2 Capture Through the Severe Calcination Condition

Calcium looping method has been considered as one of the efficient options to capture C02 in the combustion Ilue gas. CaO-based sorbent is the basis for application of calcium looping and should be subjected to the severe calcination condition so as to obtain the concentrated C02 stream. In this research, CaO/CaZrO3 sorbents were synthesized using the sol-gel combustion synthesis （SGCS） method with urea as fuel. The cyclic reaction performance of the synthesized sorbents was evaluated on a lab-scaled reactor system through calcination at 950 ℃ in a pure C02 atmosphere and carbonation at 650 ℃ in the 15% （by volume） C02. The mass ratio of CaO to CaZr03 as 8：2 （designated as CasZr2） was screened as the best option among all the synthesized CaO sorbents for its high CO2 capture capacity and carbonation conversion at the initial cycle. And then a gradual decay in the C02 capture capacity was observed at the following 10 successive cycles, but hereafter stabilized throughout the later cycles. Furthermore, structural evolution of the carbonated CasZr2 over the looping cycles was investigated. With increasing looping cycles, the pore peak and mean grain size of the carbonated CasZr2 sorbent shifted to the bigger direction but both the surface area （SA） ratio and surface fractal dimension Ds decreased. Finally, morphological transformation of the carbonated CasZr2 was observed. Agglomeration and edge rounding of the newly formed CaC03 grains were found as aggravated at the cyclic carbonation stage. As a result, carbonation of CasZr2 with C02 was observed only confined to the external active CaO by the fast formation of the CaC03 shell outside, which occluded the further carbonation of the unreacted CaO inside. Therefore, enough attention should be paid to the carbonation stage and more effective activation measures should be explored to ensure the unreacted active CaO fully carbonatPd river the extended Ioonin cycles.

Autopilot Control Synthesis for Path Tracking Maneuvers of Underwater Vehicles

This paper is concerned with the robust control synthesis of autonomous underwater vehicle （AUV） for general path following maneuvers. First, we present maneuvering kinematics and vehicle dynamics in a unified framework. Based on H∞ loop-shaping procedure, the 2-DOF autopilot controller has been presented to enhance stability and path tracking. By use of model reduction, the high-order control system is reduced to one with reasonable order, and further the scaled low-order controller has been analyzed in both the frequency and the time domains. Finally, it is shown that the autopilot control system provides robust performance and stability against prescribed levels of uncertainty.

Chemical Synthesis of C3N and BC2N Compounds

A chemical reaction for the preparation of B-C-N compounds by using carbon tetrachloride （CC14）, boron tribromide （BBr3）, lithium nitride （Li3N） and sodium as reactants has been carried out at the temperature of 400℃. Measurements of FTIR, XRD, TEM and EELS show that two kinds of compounds have been formed in the prepared sample. One is hollow sphere-like C-N with an amorphous, structure; the other is piece-like polycrystalline B-C-N with the hexagonal structure. Their determined compositions are close to C3N and BC2N, respectively.

High pressure synthesis and characterization of the pyrochlore Dy2Pt2O7:A new spin ice material

The cubic pyrochlore Dy2Pt2O7 was synthesized under 4 GPa and 1000℃ and its magnetic and thermodynamic properties were characterized by DC and AC magnetic susceptibility and specific heat down to 0.1 K.We found that Dy2Pt2O7 does not form long-range magnetic order,but displays characteristics of canonical spin ice such as Dy2Pt2O7,including(1)a large effective moment 9.64μB close to the theoretical value and a small positive Curie-Weiss temperatureθCW=+0.77 K signaling a dominant ferromagnetic interaction among the Ising spins;(2)a saturation moment ~4.5μB being half of the total moment due to the local<111>Ising anisotropy;(3)thermally activated spin relaxation behaviors in the low(~1 K)and high(~20 K)temperature regions with different energy barriers and characteristic relaxation time;and most importantly,(4)the presence of a residual entropy close to Pauling’s estimation for water ice.

A New Synthesis Method for Sum and Difference Beam Pattern with Low Sidelobe

A new method for sum and difference beam pattern synthesis with low sidelobe is proposed.In the situation of phase taper weighting,it makes use of Fourier transform pair relationship existing between the array factor and the element excitations and uses a loop iterative way to derive the array element excitations according to given array factor.The iteration does not stop until the array element excitations meet the initial sidelobe requirements.The method overcomes the defects of traditional methods,such as more searching times,larger amount of calculation and poor robustness.In addition,it can also synthesize the low sidelobe pattern in case of element failures.Simulation verifies the effectiveness of the method.

化学链合成氨中载氮体的设计与应用研究进展

氨不仅是氮肥生产的主要原料,也是可再生能源储存与转化过程中的能源载体之一。因此,开发温和条件下的合成氨技术是近年来重要的研究课题。化学链合成氨技术通过载氮体的传递作用,将合成氨反应解耦为固氮与释氨等多步反应,具有操作简便、反应温和、能耗低等优点。载氮体作为化学链合成氨的关键,起到传递能量及氮物种的作用,目前,载氮体固氮效率低,极大地限制了化学链合成氨技术的发展。基于此,本工作对化学链合成氨中载氮体的设计与应用研究进行综述。首先,对载氮体的设计理论进行了归纳与总结;其次,介绍了载氮体的研究现状,重点对如何提高载氮体的产氨速率以及如何提升晶格氮利用率等问题进行了综述;最后,对化学链合成氨技术所面临的机遇与挑战进行了研究,为今后载氮体的设计与开发提供了参考依据。

化学链合成氨研究进展与展望

氨主要被用作生产氮肥的原料,近年来被认为是一种具有重要应用前景的能源载体。目前工业合成氨主要采用Haber-Bosch工艺,该过程严重依赖化石能源,是高能耗、高碳排放过程,为生态环境带来巨大压力。因此,开发温和条件下可再生能源驱动的绿色合成氨过程具有重要的实用意义和社会价值。化学链合成氨过程是将合成氨反应解耦为两步或多步反应,具有规避催化中普遍存在的Scaling relations关系、避免氮气和氢气竞争吸附、可常压操作等特点,被认为是一种具有应用前景的合成氨技术。此外,该过程适合于分布式、小型化的生产模式,便于与可再生能源利用过程相耦合。因此,近年来化学链合成氨受到广泛关注。本综述首先简述了化学链过程的定义及其在化石能源转化领域的研究概况,随后重点介绍化学链合成氨的发展历史、载氮体分类及近期研究进展,最后对载氮体材料的设计思路及化学链合成氨过程的前景进行展望。根据载氮体不同,分别介绍了二元金属氮化物、多元金属氮化物、亚氨基化物及氮氧化物等载氮体材料在分别以N_(2)-H_(2)和N_(2)-H_(2)O为原料的化学链合成氨过程中材料种类、反应热力学及动力学、合成氨速率等方面研究成果。此外,由于近期外场驱动合成氨取得了较好进展,根据外场驱动力不同,分别介绍了以电、光、等离子体、微波等为外加能量形式的化学链合成氨过程。并从热力学及动力学两方面分别介绍了载氮体材料的改进策略。最后,对化学链合成氨技术存在的问题及外来研究方向进行展望。

LOOP环改良法全自动化制备^(11)C-胆碱

为研究国产^(11)C-多功能合成模块经LOOP环法合成放射性药物[N-甲基-^(11)C]胆碱(^(11)C-Choline,^(11)C-CH)的合成方法,对碱当量、溶剂效应及前体量等影响因素进行研究,优化LOOP环法合成^(11)C-CH的合成工艺。^(11)C-CH的优化条件:前体量为60~150 uL,无碱无溶剂,室温与^(11)C-CH 3I反应。此条件下^(11)C-CH的合成效率为(72.16±2.96)%(n=19,^(11)C-CH 3I未校正效率),产品的放化纯度均大于95%,产量为(7.59±1.54)GBq(n=19)。国产^(11)C-多功能合成模块LOOP环法合成^(11)C-CH与C18柱固相法进行比较表明,LOOP环可以多次重复利用,降低生产成本,提高合成效率,实现稳定、全自动化合成^(11)C-CH,产品满足临床需求。

激光陀螺机抖控制的DDS锁相频率合成方法及其国产化设计

激光陀螺通常采用数模转换器(DAC)配合模拟乘法器产生正弦自激振荡的机抖控制方式,乘法器模块现阶段没有国产化替代方案,存在自激振荡在高低温条件下偶发不起振问题。因此,选用国产化微处理器MCU配合DAC替换乘法器模块,采用捕获抖动过零信号快速获得控制相位,使用PI控制器进行相位-频率差运算,采取查找表方式实现频率合成,输出周期驱动信号(正弦信号或三角波信号),实现抖动偏频闭环控制。所提方案在某三轴一体小型化三自惯组产品50型陀螺控制系统中应用,实现了关键器件的国产化替代设计,且陀螺系统固定位置百秒计数均值的标准方差优于5‰。

一种低附加相位噪声的频率合成方法

频率源的相位噪声水平直接制约雷达的性能上限,因而低相噪频率合成技术是高性能雷达系统的一项关键技术。现有低相噪频率合成方法常用高次倍频实现,整体性能上严重依赖于低相噪晶振,成本一直居高不下。对此,提出一种低附加相位噪声频率合成方法,即采用最小化链路上附加相位噪声的技术,用普通恒温晶振级联低相噪放大器、梳状谱发生器和锁相环,最终实现低相位噪声的频率合成。实测数据表明,本文方法以100 MHz普通恒温晶振为参考,积分区间[1 kHz,30 MHz]的时间抖动为11 fs,频率合成在5.8 GHz载波的相位噪声为-119 dBc/Hz@1 kHz,积分区间[1 kHz,30 MHz]的时间抖动为13.7 fs,总附加时间抖动为8.17 fs,附加相位噪声仅1.9 dB,达到了业界领先水平,能够有效提升毫米波雷达系统的成像性能,优于传统频率合成方法。

TDTL Based Frequency Synthesizers with Auto Sensing Technique

This paper presents a frequency synthesizer architecture based on the time delay digital tanlock loop (TDTL). The loop is of the first order type. The synthesizer architecture includes an adaptation mechanism to keep the complete system in lock. The mechanism uses a frequency sensing structure to control critical TDTL parameters responsible for locking. Both integer and fractional multiples of the loop reference frequency are synthesized by the new architecture. The ability of the TDTL based frequency synthesizer to respond to sudden variations in the system input frequency is studied. The results obtained indicate the proposed synthesizer has a robust performance and is capable of responding to those changes provided that they are within the bounds of its locking region.

基于ADF4106锁相环的频率源设计与实现

频率源普遍应用于日常生活中,生活中的各类电子设备都有频率源的参与,尤其是无线电技术与电子系统的各个领域应用最为广泛。该文采用锁相环芯片ADF4106构成锁相频率合成电路,该电路从ADF4106锁相环芯片引出,接入环路滤波器、压控振荡器,然后接回ADF4106锁相环芯片,最终形成回路。其中的环路滤波器通过ADIsimPLL软件进行设计,采用STC15W4K56S4单片机控制ADF4106内部的分频器参数,设计输出频率范围为515~805 MHz的频率源,该频率源具有输出信号频率范围宽、控制灵活等特点。