碳纳米管对中间相炭微球抗氧化性能的影响

通过原位热缩聚、模压成型、高温烧结制备了中间相炭微球/碳纳米管复合块体材料,采用热重分析和恒温氧化方法研究了碳纳米管对中间相炭微球抗氧化性能的影响。结果表明:原位添加适当比例的碳纳米管可以增强中间相炭微球的抗氧化性能。随着碳纳米管含量的增加,碳化处理后的炭材料微晶层间距变小,抗氧化性能增强;当添加5%碳纳米管时,样品初始失重温度提高了40℃,氧化10小时后质量损失仅为8.55%;但过多的碳纳米管会使微球粒径分布变宽,球形度变差,导致块体材料气孔率增加,降低了其抗氧化性能。     

碳纳米管对中间相炭微球制备的影响

以中温煤沥青和碳纳米管为原料进行热缩聚反应,制备出含有碳纳米管的中间相炭微球,采用扫描电子显微镜(SEM)、激光粒度仪和X射线衍射(XRD)等分析手段对其形貌及结构进行了表征。研究了添加碳纳米管对中间相炭微球形貌、粒径、产率、微晶结构及热缩聚工艺的影响。结果表明添加碳纳米管能够促进小球成核,阻止小球的融并长大,使炭微球的粒径减小,分布均匀,但过多的碳纳米管会导致球形度变差及中间相沥青产率的降低;碳纳米管的存在使石墨片层尺寸减小,石墨化程度降低;碳纳米管经过酸煮处理后,可以获得球形度更好、含有更大比例碳纳米管的中间相炭微球。     

中间相炭微球的二次生长

为考察中间相的形成和生长机理,将一种煤沥青制备的中间相炭微球添加到另一种沥青中进行二次热缩聚,结果发现中间相炭微球可以进行二次生长。二次热缩聚中间相炭微球的产率、粒径分布、表面和断面的形貌表明添加的中间相炭微球对于沥青热缩聚过程的物理作用更为主要;二次热缩聚过程包含了添加的中间相炭微球的二次生长过程和原料沥青独立成核生长两个相互竞争的过程,中间相炭微球的添加量对这两个过程有着重要的影响;中间相炭微球的生长是基本构筑单元不断进入相界面的构筑过程。     

不同氧化剂制备的聚苯胺/中间相炭微球复合物电化学性能研究

室温下,以二氧化锰和过硫酸铵为氧化剂,采用原位化学聚合法合成聚苯胺/中间相炭微球(PANI/MCMB)复合物。采用场发射扫描电镜(FE-SEM)和X射线粉末衍射(XRD)对其形貌结构进行表征。以PANI/MCMB复合物为电极活性物质,1.0mol/L H_2SO_4水溶液为电解液组装对称型超级电容器,用循环伏安法(CV)、电化学交流阻抗(EIS)、恒流充放电等测试手段测试超级电容器的电化学性能。结果表明,以二氧化锰为氧化剂制备的聚苯胺/中间相炭微球复合物(MPANI/MCMB),在电流密度为0.1A/g时,单电极比容量为336.4F/g。1 000次循环后比容量保持率为92.3%,比以过硫酸铵为氧化剂制备的聚苯胺/中间相炭微球复合物(NPANI/MCMB)具有更好的循环性能和更高的比容量。     

添加松香对中间相炭微球制备的影响

以中温煤沥青为原料,松香为添加剂,通过热缩聚合法制备中间相炭微球。采用FT-IR、SEM、偏光显微镜等对所得产物进行表征,研究了松香对中间相炭微球制备的影响。研究表明松香的加入能有效限制沥青的过度聚合,不仅促进中间相炭微球的成核和生长,而且在很大程度上防止中间相炭微球的融并;当松香添加量为10%(质量分数)时,改性煤沥青经450℃热解2h可制备出球形度好、粒径均匀的中间相炭微球,其平均粒径为15.3μm,收率达44.1%。     

氧化硼-磷酸浸渍对中间相炭微球复合材料抗氧化及力学性能的影响

以原位缩聚法制备的中间相炭微球/碳纳米管(MCMB/CNTs)复合微球为原料, 通过添加氧化硼(B₂O₃)粉体和磷酸浸渍对该复合材料进行了基体和表面改性。采用扫描电子显微镜(SEM)、三点弯曲法、热重分析(TG)以及恒温氧化测试方法对复合材料的表面形貌、弯曲强度以及抗氧化性能进行了表征与测试。结果表明: 添加适量的B₂O₃可以有效提升复合材料的抗氧化性能和弯曲强度, B₂O₃含量超过2%时, 复合材料的弯曲强度逐渐下降。将含有2% B₂O₃的复合材料试样进行磷酸浸渍处理后, 试样的弯曲强度可达66 MPa, 初始氧化温度520℃, 经过500℃恒温氧化60 min后其氧化失重率仅为5%, 弯曲强度仍达到50.3 MPa。     

锂离子电池用中间相炭微球的低温表面修饰

采用CoCl2对中间相炭微球进行低温表面修饰,进行了表征和性能测量,并研究对其性能的影响.结果表明,低温热处理中间相炭微球仍以低温炭结构为主,但是微球表面的碳微晶尺寸比内部的大;低温表面热处理能够明显提高中间相炭微球的可逆容量,在不降低充电容量的情况下将首次库仑效率从52.2%提高到87.2%,并改善了循环性能.低温表面修饰使中间炭微球表面碳结构的有序化程度增强,有效地缓解了碳表面的不可逆电化学反应.     

碳纳米管/微膨石墨复合负极材料的制备及电化学性能研究

通过对两种天然鳞片石墨进行微膨胀处理得到微膨石墨,然后以微膨石墨为基体采用化学气相沉积(CVD)法于微膨石墨的孔洞结构中原位生长碳纳米管,制备了碳纳米管/微膨石墨复合负极材料.电化学测试结果表明两种复合材料分别具有443和477 mAh/g的首次可逆容量.两种复合材料在0.2C倍率下循环充放电30次后容量均能保持95%以上;在1C下循环充放电50次后,可逆容量分别稳定在259和195 mAh/g.微膨胀处理形成的微纳米级孔洞以及原位碳纳米管的网络结构,提供了更多的储锂空间,并能够有效地缓冲电极材料在充放电时的体积变化;电解质溶液浸润在纳米孔洞中,有利于缩短锂离子的扩散路径,提高倍率循环性能;同时原位生长的类似常春藤形的碳纳米管可以起到桥梁的作用,避免"孤岛"的形成,增强了复合材料的导电性能.     

锂离子电池负极材料中间相炭微球的表面镀镍修饰研究

采用化学镀的方法在石墨化中间相炭微球的表面镀覆金属镍,采用扫描电镜对镀覆后的炭微球进行了表面分析,采用X-射线衍射的方法对镀镍炭微球进行了物相分析,将镀覆后的中间相炭微球用于锂离子电池负极材料,并进行了不同倍率的充放电分析及交流阻抗研究。结果表明,在不使用活化剂和敏化剂的情况下,金属镍仍然能够沉积在炭微球的表面;炭微球的大电流放电性能大大提高,在2C放电电流下的放电容量提高了23%,镀镍后交换电流密度增大并且SEI膜电阻减小,炭微球的反应活性大大提高。     

碳纳米管包覆量对天然石墨负极材料的电化学性能的影响

用溶胶-凝胶法将碳纳米管(CNT)包覆到天然石墨的表面,提高其充放电比容量和循环寿命性能,并研究了不同含量的碳纳米管对天然石墨电化学性能的影响。通过扫描电镜(SEM)、X射线衍射(XRD)和电化学测试等对CNT/天然石墨复合材料进行表征。结果表明,碳纳米管能在电极中构建空间三维导电网络,同时保留了天然石墨的晶体结构。随碳纳米管含量增加,复合材料的充放电比容量和循环稳定等电化学性能先升高后降低。碳纳米管包覆的质量分数为7%时,复合材料的综合性能最佳。在0.1C,CNT/天然石墨负极材料放电比容量为427mAh/g,比纯天然石墨(356mAh/g)提高了20%,循环100次后容量保持率仍有93.6%。     

Real gas choked flow conditions at low reduced-temperatures

Real gas choked mass flux is calculated for a frictionless stream expanding isentropically until it reaches the speed of sound and without phase changes. The other parameters associated with the choked state are the pressure, density, temperature ratios, and the speed of sound. Departure of the choked mass flux from the ideal gas model is discussed first in absolute terms and then in relative terms, using the Principle of Corresponding States, for gases with boiling points in the low temperature range. Reduced-stagnation pressures are examined up to values of 30 for hydrogen, neon, nitrogen, argon, methane, krypton, xenon, and R-14 and up to 100 for ⁴He. The corresponding reduced-stagnation temperatures go down to 1.4 and in some cases down to 1.2 for nitrogen and argon. Also discussed are the limiting values of stagnation parameters for which no phase change occurs in the choked state. Compared to the ideal gas, the mass flux may almost double and the critical pressure ratio may decrease by an order of magnitude. The relevance of results is discussed qualitatively and quantitatively for Joule-Thomson cryocooling.     

As-cast microstructures and behavior at high temperature of chromium-rich cobalt-based alloys containing hafnium carbides

Hafnium is often used to improve the high temperature oxidation resistance of superalloys but not to form carbides for strengthen them against creep. In this work hafnium was added in cobalt-based alloys for verifying that HfC can be obtained in cobalt-based alloys and for characterizing their behavior at a very temperature. Three Co–25Cr–0.25 and 0.50C alloys containing 3.7 and 7.4 Hf to promote HfC carbides, and four Co–25Cr– 0 to 1C alloys for comparison (all contents in wt.%), were cast and exposed at 1200 °C for 50 h in synthetic air. The HfC carbides formed instead chromium carbides during solidification, in eutectic with matrix and as dispersed compact particles. During the stage at 1200 °C the HfC carbides did not significantly evolve, even near the oxidation front despite oxidation early become very fast and generalized. At the same time the chromium carbides present in the Co–Cr–C alloys totally disappeared in the same conditions. Such HfC-alloys potentially bring efficient and sustainable mechanical strengthening at high temperature, but their hot oxidation resistance must be significantly improved.     

Chitosan-collagen/organomontmorillonite scaffold for bone tissue engineering

A novel composite scaffold based on chitosan-collagen/organomontmo-rillonite (CS-COL/OMMT) was prepared to improve swelling ratio, biodegradation ratio, biomineralization and mechanical properties for use in tissue engineering applications. In order to expend the basal spacing, montmorillonite (MMT) was modified with sodium dodecyl sulfate (SDS) and was characterized by XRD, TGA and FTIR. The results indicated that the anionic surfactants entered into interlayer of MMT and the basal spacing of MMT was expanded to 3.85 nm. The prepared composite scaffolds were characterized by FTIR, XRD and SEM. The swelling ratio, biodegradation ratio and mechanical properties of composite scaffolds were also studied. The results demonstrated that the scaffold decreased swelling ratio, degradation ratio and improved mechanical and biomineralization properties because of OMMT.     

Capacitance based mass metering for cryogenic fluids

This paper describes a method for measuring the mass of cryogenic fluids in on-board rocket propellant tanks or ground storage tanks. Linear approximations to the Clausius-Mossotti relationship serve as the foundation for a capacitance based mass sensor, regardless of fluid density stratification or tank shape. Sensor design considerations are presented along with the experimental results for a capacitance based mass gage tested in liquid nitrogen. This test data is shown to be consistent with theory resulting in a demonstrated mass measurement accuracy of ±0.75% and a deviation from linearity of less than ±0.30% of full scale mass. Theoretical accuracies are also shown to be ±0.73% for hydrogen and ±1.39% for oxygen for a select range of pressures and temperatures.     

Equipment using a “static-analytic” method for solubility measurements in potentially hazardous binary mixtures under cryogenic temperatures

A new apparatus designed to study, at cryogenic temperatures, thermodynamic equilibria of potentially explosive binary systems such as hydrocarbon-oxygen mixtures is described herein. This equipment has an equilibrium cell which was especially designed to minimize hazards while allowing accurate phase equilibrium measurements. Reliability of results, obtained with this equipment has been verified by working on the nitrogen-propane system, for which data are already available in literature, over a large range of compositions and at various temperatures. Four isothermal curves describing liquid phase compositions at 109.98, 113.77, 119.75 and 125.63 K have been determined. Our experimental data are represented within 2% in compositions and in pressures through the Peng-Robinson equation of state implying Mathias-Copeman alpha function and Huron-Vidal mixing rule. Comparisons to literature allow pointing out: good agreement is observed with Kremer and Knapp data (1983) while the three sets of Poon and Lu data (1974) presenting systematic positive deviation are consequently judged as suspicious.     

Gas gap thermal switches using neon or hydrogen and sorption pump

The very low pressure obtained thanks to adsorption phenomenon at low temperature can be used to build cryogenic heat switches, which offer the possibility to make or break thermal contact between two parts of a cryogenic system. The ON (conducting) and OFF (insulating) states of the switch are obtained by varying the gas pressure between two copper blocks separated by a gap of 100 μm. This pressure is controlled by acting upon the temperature of a small sorption pump (activated charcoal) connected to the gap space. For a “high” sorption pump temperature, the gas previously adsorbed in the sorption pump is released to the gap between the two blocks, allowing a good thermal conduction through the gas (ON state). On the opposite, cooling the sorption pump allows a very good vacuum between the copper blocks, which efficiently break the thermal contact (OFF state). Experimental thermal characteristics (Conductance in the ON and OFF state, ON-OFF switching temperature) of such a “Gas Gap Heat Switch” are described using hydrogen or neon as exchange gas and are compared with theoretical calculations.     

Development of No-Vent™ liquid hydrogen storage system for space applications

A number of technological advances required to store and maintain normal-boiling-point and densified cryogenic liquids, including liquid hydrogen, under zero boil-off conditions in-space, for long periods of time, have been developed. These technologies include (1) thermally optimized compact cryogen storage systems that reduce environmental heat leak to the lowest-temperature cryogen, which minimizes cryocooler size and input power, and (2) actively-cooled shields that surround the storage systems and intercept heat leak. The processes and tools used to develop these technologies are discussed. A zero boil-off liquid hydrogen storage system technology demonstrator for validating the actively-cooled shield technology is presented.     

Development of a miniature cryogenic fluid circuit and a cryogenic micropump

This article presents the development of a miniaturized cryogenic fluid circuit for distributed cooling of low-temperature tracking detectors in high-energy physics (HEP). The heart of the circuit is a prototype cryogenic micropump. This volumetric pump is compatible with cooling powers of about 10-100 W, and capable of producing pressure heads of up to around 0.3 MPa. Besides detector and electronics cooling in HEP, potential applications are found in the field of superconductor technology.     

Integrated Resonant Self-Pumped Loop and pulse tube cryocooler for cryogenic cooling distribution

Cooling distribution is a vital technology concerning cryogenic thermal management systems for many future space applications, such as in-space, zero boil-off, long-term propellant storage, cooling infrared sensors at multiple locations or at a distance from the cryocooler, and focal-plane arrays in telescopes. These applications require a cooling distribution technology that is able to efficiently and reliably deliver cooling power (generated by a cryocooler) to remote locations and uniformly distribute it over a large-surface area. On-going efforts by others under this technology development area have not shown any promising results.This paper introduces the concept of using a Resonant Self-Pumped Loop (RSPL) integrated with the proven, highly efficient pulse tube cryocooler. The RSPL and pulse tube cryocooler combination generates cooling power and provides a distributive cooling loop that can be extended long distances, has no moving parts, and is driven by a single linear compressor. The RSPL is fully coupled with the oscillating flow of the pulse tube working fluid and utilizes gas diodes to convert the oscillating flow to one-directional (DC) steady flow that circulates through the cooling loop. The proposed RSPL is extremely simple, lightweight, reliable, and flexible for packaging. There are several requirements for the RSPL to operate efficiently. These requirements will be presented in this paper. Compared to other distributive cooling technologies currently under development, the RSPL technology is unique.     

Helium liquefaction with a commercial 4 K Gifford-McMahon cryocooler

This paper describes helium liquefaction using a commercial cryocooler with 1.5 W cooling power at 4.2 K (Sumitomo model RDK415D with compressor CSW-71D, consuming 6.5 kW electrical power), equipped with heat exchangers for precooling the incoming gas. No additional cooling power of cryoliquids or additional Joule-Thomson stages were utilized. Measurements of the pressure dependence of the liquefaction rate were performed. A maximum value of 83.9 g/h was obtained for 2.25 bar stabilized input pressure. Including the time needed to cool the liquefied helium to 4.2 K at 1 bar after filling the bottle connected to the cold head, and correcting for heat screen influences, this results in a net liquefaction rate of 67.7 g/h. Maintaining a pressure close to 1 bar above the bath during liquefaction, a rate of 55.7 g/h was obtained. The simple design enables many applications of the apparatus.