低熔点混合碳酸盐腐蚀特性的研究

熔融盐的腐蚀特性的研究对于太阳能热发电站中的传热蓄热系统的设计非常重要。在三元碳酸盐中加入氢氧化钠后可形成熔点相对低的高温蓄热四元混合盐,本文在520℃空气气氛中对310S和321两种不锈钢分别在三元碳酸盐和四元混合盐中的腐蚀特性进行了研究,并对其腐蚀机理进行了讨论。结果表明,相对于三元碳酸盐,加入氢氧化钠(ω=0.1)后的四元混合盐对其腐蚀性能的影响不大,对于321不锈钢,在三元碳酸盐中加入氢氧化钠后会使其腐蚀性增强,对于310S不锈钢则会使其腐蚀性减弱。     

304不锈钢高温NaNO3/KNO3二元熔盐流动腐蚀机理研究

熔融盐以其优良的性能在太阳能热发电站中常被用作储热和蓄热介质,然而由于蓄热的熔融盐工作温度高达500?600℃,这就使得熔融盐对蓄热系统材料的腐蚀成为一个关键问题。本文以美国新月沙丘塔式熔盐太阳能热电站为原型,针对其运行情况,自主设计并搭建旋转式高温NaNO3/KNO3二元熔盐腐蚀特性模拟实验系统,探究了304不锈钢在特定温度、不同流速、不同时间协同作用下的腐蚀动力学特性,并利用SEM、EDX、XRD等分析测试技术探索材料表面的微观腐蚀形貌和腐蚀产物形态及元素组成,揭示了304不锈钢在高温流动熔融盐中的腐蚀行为规律和腐蚀机理。     

低熔点混合硝酸盐相变传热过程研究

为得到混合熔盐在单罐蓄热系统内的相变传热规律,本文针对具有低熔点的四元混合硝酸盐展开研究,采用VOF与焓-多孔介质耦合模型对底部加热条件下蓄热单元内相变材料(PCM)的相变蓄热过程进行模拟,并利用实验进行验证。结果表明:相变过程中罐内出现明显温度分层现象,固液界面出现波动。蓄热单元中所产生的自然对流强弱直接影响热量传递,同时固液相界面的位置决定自然对流的发展。本文研究结果对相变材料的高效利用与单罐蓄热系统的优化提供理论依据。     

多孔介质中熔融盐流体高温斜温层蓄热的热特性

对熔融盐高温斜温层蓄热过程进行了较深入的理论与实验研究.基于多孔介质局部热平衡理论,建立了多孔介质中熔融盐流体斜温层蓄热的局部热平衡数值模型,研究了熔融盐、多孔介质孔隙结构参数对多孔介质中熔融盐流体传热与流动的影响规律,并在熔融盐传热-蓄热实验平台上进行了试验研究.结果表明:与熔融盐单相流体斜温层(无填充多孔介质)蓄热系统相比,多孔介质填料能够减少斜温层的厚度和改善其形状,采用单位体积热容量(pc)s大于(pc)f,孔隙率(?)小于0.4有利于降低斜温层厚度及其移动速度.揭示了多孔介质中熔融盐流体斜温层蓄热系统的蓄热特性,为熔融盐高温斜温层蓄热的设计和运行控制提供依据.     

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通过失重法结合SEM、金相分析等手段,研究了含焊缝的316L不锈钢试样在350°C、0.15MPa液态锂中500h的静态腐蚀,并采用LIBS结合台阶仪表征液态锂的渗入深度。结果表明,锂对含焊缝的316L不锈钢样式的平均腐蚀速率为99.8mg·m?2·h?1;腐蚀深度为6.4μm;渗入深度在316L不锈钢焊缝处为8.6μm,在母材处为4.8μm。在焊缝处锂对材料有明显的晶间腐蚀。     

液态金属锂对于316L不锈钢焊接件的腐蚀行为研究

通过失重法结合SEM、金相分析等手段,研究了含焊缝的316L 不锈钢试样在350°C、0.15MPa 液态锂中500h 的静态腐蚀,并采用LIBS 结合台阶仪表征液态锂的渗入深度。结果表明,锂对含焊缝的316L 不锈钢样式的平均腐蚀速率为99.8mg·m^-2·h^-1;腐蚀深度为6.4μm;渗入深度在316L 不锈钢焊缝处为8.6μm,在母材处为4.8μm。在焊缝处锂对材料有明显的晶间腐蚀。     

新型低熔点熔盐黏度的实验研究

熔盐因其具有广泛的使用温度范围,低蒸气压,大热容量,低黏度,良好的稳定性,低成本等诸多特性已成为聚光太阳能热发电中颇有潜力的传热蓄热介质。准确的熔盐热物性对于太阳能发电过程中介质的传热蓄热性能有重要影响。其中熔盐黏度作为重要的热物性之一,对于提高传热效率和降低流动阻力具有决定作用。本文利用研制的高温黏度测量仪对水和HITEC盐的黏度温度特性进行了实验研究,实验结果与文献数据具有较好的一致性,证明了该高温熔盐黏度仪的可靠性。为了降低混合熔盐的熔点,改进其热物性能,本文对Solar Salt进行改性研究,得到两种新型低熔点混合熔盐,并测定得到了黏度温度特性曲线。结果表明,改性后的高温熔融盐黏度有所降低,有利于降低太阳能热发电熔盐传热管路系统的阻力和成本。     

强流脉冲离子束辐照对不锈钢耐腐蚀性能的影响

 利用强流脉冲离子束（HIPIB）对316L不锈钢进行了表面辐照处理，研究了HIPIB辐照对其在0.5mol/L H2SO4溶液中电化学腐蚀性能的影响。极化曲线测量结果表明，HIPIB辐照能够显著提高316L的抗腐蚀性能，自腐蚀电流对辐照次数的依赖性与自腐蚀电位相比明显较强。采用扫描电子显微镜（SEM）、X射线衍射（XRD）和电子探针（EPMA）分析辐照后试样表面形貌、表面层相结构和元素分布的变化。结果表明：HIPIB辐照使试样表面光滑化，表面层产生择优取向，且发生了杂质元素的选择性烧蚀，是316L不锈钢耐电化学腐蚀性能得以提高的主要原因。     

奥氏体不锈钢低温热导率计算方法及验证

不锈钢在低温系统中应用广泛,但各种牌号的不锈钢材料在低温区间的热导率测试数据却很少。文献推荐的计算纯铁低温热导率的经验公式并不适用于不锈钢。在文献公式的基础上,提出了一种针对奥氏体不锈钢材料的低温热导率计算方法,可基于4K~20K温度区间内电阻率或热导率的单点测试数据,估算4K~300K温度区间的热导率,也可根据室温电阻率或热导率的测试数据,但计算精度比前者略低。计算方法通过了美标304、316、317、321牌号不锈钢实测数据的验证。基于该计算方法建立了奥氏体不锈钢低温热导率计算程序,估算了国产牌号1Cr18Ni9Ti不锈钢4~300K温度区间的热导率,并与文献中的测试数据进行了对比验证,相对计算误差能够满足工程设计需要。     

操作参数对熔融盐高温斜温层蓄热性能的影响

首先提出了一种新型熔融盐高温斜温层耦合蓄热单罐系统,然后基于多孔介质局部热平衡理论,建立了熔融盐高温斜温层蓄热的局部热平衡数值模拟模型,研究了熔融盐进口流速、进口温度及工作温差等操作参数对斜温层蓄热单罐热性能的影响,并在熔融盐传热-蓄热实验平台上进行了试验研究。发现:当进口速度为0 001 m/s级及降低工作温差等有利于降低斜温层厚度,模拟得到的蓄热单罐轴向温度分布变化与实验结果趋于一致。因此,合理选取这些参数对蓄热单罐的正常运行是非常必要的,结果可以用于指导蓄热单罐的设计。     

Thermal stability of sodium nitrate–sodium nitrite melts: A Raman spectra study

Abstract

A molten mixture of sodium nitrate–sodium nitrite is an important heat transfer and storage medium. It is important to research the thermal stability of such melts. In the present study, the equilibrium between nitrate and nitrite ion in sodium nitrate–sodium nitrite melts under air atmosphere was studied by Raman spectroscopy and the thermal stability of the melts was analyzed. The results show that when the temperature was greater than 644?K, for melts in which the weighted-in content of sodium nitrate is 90 mass %, the content of nitrate ion decreased slightly with temperature. However, for melts in which the weighted-in content of sodium nitrate was 10–80 mass %, the content of nitrate ion increased with temperature. Melts in which the weighted-in fraction of sodium nitrite were 15.22%, 14.71%, and 14.60% under air atmosphere showed optimal thermal stability at 644?K, 762?K, and 880?K, respectively. The findings of this study have provided a foundation for optimizing the composition of molten salts and for providing molten mixtures applicable to important industrial processes.     

利用电子顺磁共振和紫外/可见吸收光谱研究熔融KNO3-NaNO2-NaNO3盐分解过程中的超氧负离子

On account of excellent thermal physical properties, molten nitrates/nitrites salt has been widely employed in heat transfer and thermal storage industry, especially in concentrated solar power system. The thermal stability study of molten nitrate/nitrite salt is of great importance for this system, and the decomposition mechanism is the most complicated part of it. The oxide species O₂^2- and O₂^- were considered as intermediates in molten KNO₃-NaNO₃ while hard to been detected in high temperature molten salt due to their trace concentration and low stability. In this work, the homemade in situ high temperature UVVis instrument and a commercial electron paramagnetic resonance were utilized to supply evidence for the formation of superoxide during a slow decomposition process of heat transfer salt (HTS, 53 wt% KNO₃/40 wt% NaNO₂/7 wt% NaNO₃). It is found that the superoxide is more easily generated from molten NaNO₂ compared to NaNO₃, and it has an absorption band at 420-440 nm in HTS which red shifts as temperature increases. The band is assigned to charge-transfer transition in NaO₂ or KO₂, responsible for the yellow color of the molten nitrate/nitrite salt. Furthermore, the UV absorption bands of molten NaNO₂ and NaNO₃ are also obtained and compared with that of HTS.     

常压下固态KNO2热力学性质的密度泛函理论研究

采用密度泛函理论结合准谐德拜模型研究常压下300~725 K间KNO₂立方结构的热力学性质,重点分析常压下定压热容、定容热容、熵、德拜温度、体膨胀系数、平衡体积和体弹模量随温度的变化.结果显示,常压下计算的定压热容随温度的变化与实验数据符合较好,而计算的熵与实验数据相差较大.计算得到KNO₂的平均体膨胀系数约为1.837 8×10^-5K^-1,常温下(300 K)KNO₂的德拜温度约为667.13K.     

高温熔盐横纹管传热特性与强化机理研究

本文对以熔融盐为传热工质的横纹管传热过程进行了实验研究。研究温度、热流密度对横纹管传热性能的影响,并与光管的传热性能进行比较,探讨了强化传热的机理,确定了强化传热的范围和途径。实验结果表明:横纹管比光管具有更好的传热性能。     

Optimization of a New Design of Molten Salt-to-CO2 Heat Exchanger Using Exergy Destruction Minimization

One of the ways to make cost-competitive electricity, from concentrated solar thermal energy, is increasing the thermoelectric conversion efficiency. To achieve this objective, the most promising scheme is a molten salt central receiver, coupled to a supercritical carbon dioxide cycle. A key element to be developed in this scheme is the molten salt-to-CO₂ heat exchanger. This paper presents a heat exchanger design that avoids the molten salt plugging and the mechanical stress due to the high pressure of the CO₂, while improving the heat transfer of the supercritical phase, due to its compactness with a high heat transfer area. This design is based on a honeycomb-like configuration, in which a thermal unit consists of a circular channel for the molten salt surrounded by six smaller trapezoidal ducts for the CO₂. Further, an optimization based on the exergy destruction minimization has been accomplished, obtained the best working conditions of this heat exchanger: a temperature approach of 50 °C between both streams and a CO₂ pressure drop of 2.7 bar.     

High-Temperature Corrosion Behavior of Superalloys in Molten Salts – A Review

The use of molten salts based on fluorides/chlorides/nitrates/sulfates or carbonates is now an accepted practice in energy conversion technologies and many other industrial processes. However, compatibility of molten salts with the structural alloys and materials corrosion has been of real concern at such temperatures (600–900°C). Hence, the material development and corrosion studies turn out to be an essential part of research. The results of recent studies are reviewed to understand the developments that have occurred in the latter part of the last decade. The corrosion kinetics of modern materials in variety of molten salts with focus on reaction mechanisms and corrosion products is investigated by scientists around the globe. Emphasis has also been given on the composition of the oxide films/corrosion products on alloys of interest in wide a range of melts. By and large, molten salt corrosion has been predominantly studied by gravimetric, electrochemical techniques and, morphology and chemical analysis of corrosion products by means of XRD, SEM/EDX, ICP/AAS, etc. This article gives in-depth insight into the composition of materials, the molten salt mixtures, and various aggressive environments mainly high temperatures and long exposures.     

Composition and corrosion resistance of cerium conversion films on the AZ31 magnesium alloy and its relation to the salt anion

Pre-treatments based on different cerium salts were applied to the AZ31 Mg alloy. The pre-treatments were performed by immersion in solutions of various Ce(III) salts: cerium chloride, cerium nitrate, cerium sulphate and cerium phosphate. The chemical composition of the treated surfaces was investigated by X-ray photoelectron spectroscopy and Auger electron spectroscopy, whereas the corrosion behaviour of the pre-treated AZ31 substrates was investigated in 0.005 M NaCl solutions using potentiodynamic polarisation and open circuit potential monitoring. The surface film contained a mixture of Ce(IV) and Ce(III) salts. The film thickness depends upon the cerium salt used. The electrochemical results show that all the conversion pre-treatments reduced the corrosion activity of the AZ31 Mg alloy substrates in the presence of chloride ions. The corrosion protection efficiency is related with the anion present in the cerium salt.