蓄热技术在聚焦式太阳能热发电系统中的应用现状

从了解聚焦式太阳能热发电（CSP）的发展背景出发,综述了CSP系统中的蓄热技术的应用现状与发展方向,对各种蓄热技术进行了比较,并简要介绍了我国目前技术发展的现状,同时指出经济型的蓄热系统设计是CSP系统成功走向市场化的关键技术,双罐熔融盐直接蓄热塔式系统将是我国发展CSP技术努力的方向。     

Microstructural study and hot corrosion behavior of bimodal thermal barrier coatings under laser heat treatment

In this study, nanostructured YSZ powders were deposited on the Hastalloy X Superalloy substrate coated with a metallic bond coat by plasma spraying to produce a nanostructured thermal barrier coating with bimodal microstructure. After that, the coated samples were heat-treated using a Nd:YAG laser. Then, the microstructures of the conventional and nanostructured TBCs before and after the laser glazing process were examined using a scanning electron microscope (SEM). The coating phases were studied by X-ray diffractometry (XRD). The high-temperature corrosion behavior of the nanostructured plasma sprayed coating in the presence of Vanadium pentoxide and Sodium sulfate molten salt was compared with that of the conventional coatings before and after laser treatment at 1050 °C. The hot corrosion results showed that the coatings had a similar degradation mechanism based on which the corrosive molten salt reacted with the stabilizer of YSZ, producing hot corrosion products such as YVO₄. It led to an unwanted phase transformation from tetragonal (t) to monoclinic (m) Zirconia and the final degradation of the TBC system. However, reducing molten salt penetration, decreasing surface roughness and, reduction of the specific surface area are three important mechanisms that improved hot corrosion resistance, finally extending the lifetime of the glazed samples. The results also showed that the nanostructured TBC had higher hot corrosion resistance in comparison with other samples.     

Thermal and corrosion properties of silicon nitride for copper die casting components

Due to the high melting temperature of copper and copper alloys, conventional die-steel components used in pressure die casting these materials exhibit short service lifetimes and undergo thermal fatigue. Thermal and corrosion properties of silicon nitride were studied to assess the material's applicability in substituting conventional die-steels in casting copper and copper alloys. In this study, experiments were conducted to test the thermal shock resistance and corrosion behaviour of a commercial silicon nitride in contact with molten pure copper. The results did not indicate any corrosive reaction between silicon nitride and pure copper. However, the presence of copper oxides at high temperatures accelerated the oxidation of the ceramic resulting in considerable loss of material. The thermal shock behaviour of silicon nitride proved to be adequate for the application.     

Comparison of hot corrosion behaviors of plasma-sprayed nanostructured and conventional YSZ thermal barrier coatings exposure to molten vanadium pentoxide and sodium sulfate

The purpose of the current study was evaluation and comparison of hot corrosion behaviors of plasma-sprayed conventional and nanostructured yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs). Hot corrosion studies were performed on the surface of coatings in the presence of a molten mixture of V₂O₅+Na₂SO₄ at 1000 °C for 30 h. Results indicated that the hot corrosion mechanisms of conventional and nanostructured YSZ coatings were similar. The reaction between corrosive salt and Y₂O₃ produced YVO₄, leaching Y₂O₃ from YSZ and causing the detrimental phase transformation of zirconia from tetragonal to monoclinic. The nanostructured coating, as compared to its conventional counterpart, in spite of a further reaction with the corrosive salt, showed a higher degradation resistance during the hot corrosion test due to increased compliance capabilities resulting from the presence of an extra source of porosity associated with the nano-zones.     

Surface conductivity and stability of metallic bipolar plate materials for polymer electrolyte fuel cells

Different types of commercial stainless steels, Ni-based alloys and nitride-coated steels were evaluated as metallic bipolar plate in terms of interfacial contact resistance (ICR) and corrosion resistance in conditions typical of PEFC anode and cathode environments. Results show that stainless steel have a high ICR and undergo corrosion in both anode and cathode. Moreover, although Ni-based alloys showed an ICR comparable with graphite, their behaviour was not satisfactory in corrosive acidic medium. Only nitride-coated stainless steel demonstrated to have low ICR and very good corrosion resistance.     

Processing of MAX phases: From synthesis to applications

MAX phases are a large family of materials with more than 150 different compositions that have been extensively investigated during the last 25 years. They present a layered structure and a unique combination of properties, bridging the gap between metallic and ceramic properties. However, despite their excellent response of some compositions at high temperature—excellent oxidation resistance up to 1400°C under corrosive environment, good damage and radiation tolerance, thermal shock resistance, and self-crack healing—their transfer to applications has been limited by three main factors: i) complexity of this large family of materials, ii) unavailability of highly pure commercial powders, and iii) extensive time to license products in strategic fields such as nuclear or aviation. In this article, the main properties and synthesis routes are reviewed, including solid state reaction methods, physical vapor deposition (PVD) techniques and molten salt processes. Emphasis is given to processing routes for developing different structures such as dense bulk samples, ceramic matrix composites, foams with different porosity, coatings by PVD and thermal spray technologies, and near net shaping by slip casting, injection molding, and additive manufacturing. Well-known and novel potential applications are described such as structural materials for high temperature applications, protective coatings and bond-coats for gas turbines, accident tolerant fuel cladding in nuclear power plants, solar receiver in concentrated solar power systems, electrical contacts, catalyst, and joining material. Finally, high impact investigations and future challenges are listed in order to facilitate the transfer of MAX phases to the market.     

HVOF喷涂用于提高锅炉换热面耐磨损耐腐蚀性能综述

火力发电是我国的主要发电方式,在燃用煤、生物质等固体燃料时会面临锅炉换热面的冲蚀磨损或腐蚀问题,导致管道失效停炉,严重影响了电厂的安全稳定运行。超声速火焰（HVOF）喷涂作为热喷涂工艺的一种,可以通过在换热管道表面添加防护涂层来缓解磨损或腐蚀问题。因其制备的涂层具有与基体结合强度高、孔隙率低等优异的特点,在锅炉换热面的耐磨损耐腐蚀方面研究及应用前景广阔。综述了HVOF喷涂的发展、工艺流程以及涂层的特性,并重点总结了用于提升锅炉换热面耐磨损耐腐蚀性能的HVOF涂层材料,以及不同材料应用时需要考虑的环境因素。最后从工艺优化、材料进步以及实验方法创新三个方面对HVOF工艺在锅炉换热面上的应用做出展望。     

ZrO2(f)-NiFe2O4惰性阳极在冰晶石熔盐中的腐蚀行为

以NiO和Fe2O3为原料,采用固相烧结法合成了NiFe2O4尖晶石,通过添加ZrO2纤维[ZrO2(f)]制备了ZrO2(f)-NiFe2O4惰性阳极材料. 采用失重法测量了阳极试样在冰晶石熔盐中的静态热腐蚀率和电解腐蚀率,并对腐蚀机理进行了探讨. 结果表明,ZrO2(f)添加量由0增加至4%(w)时,阳极试样的气孔率从4.9%上升到5.8%,导致其静态热腐蚀率由3.8 mg/(cm2×h)增大到4.3 mg/(cm2×h);在电场作用下,氧化物在冰晶石熔盐中的溶解反应受到抑制,含3%(w) ZrO2(f)阳极试样的电解腐蚀率为2.2 mg/(cm2×h),远小于其静态腐蚀率,腐蚀均为物理化学溶解过程;高温下ZrO2(f)在冰晶石熔盐中稳定性良好,可作为铝电解NiFe2O4基惰性阳极的强韧化材料.     

MnO2添加剂对镍铁尖晶石基惰性阳极耐腐蚀性的影响

以氧化物NiO和Fe2O3为原料,添加氧化物MnO2,采用高温固相烧结法制备了NiFe2O4基惰性阳极材料,采用失重法测量了阳极试样的静态热腐蚀速率,并对其腐蚀机理进行了初步探讨. 实验结果表明,添加2%(ω) MnO2粉末的惰性阳极试样的静态热腐蚀速率最低. 由于掺杂的MnO2在晶界处富集,熔盐对晶粒的腐蚀首先在晶界处发生反应生成Mn2AlO4相,而Mn2AlO4相结构致密,冰晶石熔盐通过该相向NiFe2O4尖晶石晶粒内扩散速度减慢,从而降低了腐蚀速率.     

Corrosion of Borosilicate Sealing Glasses for Molten Carbonate Fuel Cells

The development of a new sealant for molten carbonate fuel cells (MCFC) requires a study of the attack of molten carbonates on selected materials. Silica and Pyrex® glasses have better corrosion resistance against molten carbonates than other glasses, but they have unsuitable thermal expansion coefficients. Comparisons have also been made between borosilicate glasses of suitable thermal expansion for sealants for MCFC and silica and Pyrex® glasses. The corrosion kinetics in molten carbonates follows two limiting relations and involves two corrosion mechanisms. The weight loss varied linearly with time, indicating a dissolution of the glass network at short times. Longer times show corrosion, depending on the square root of time, typical of a diffusion mechanism and indicating formation of a protective layer on the surface of the glass. The main crystalline corrosion product is lithium methasilicate. The glass-corrosion rate follows the well-known Arrhenius law. These studies used scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and chemical analysis. A general corrosion mechanism of borosilicate glasses in molten carbonates is proposed.     

Effects of laser surface remelting on the molten salt corrosion resistance of yttria-stabilized zirconia coatings

In the present study, atmospheric plasma-sprayed yttria-stabilized zirconia coatings were post-remelted by a continuous diode laser to improve the hot corrosion resistance for as-sprayed coatings. The coating surfaces were covered with a salt mixture (V₂O₅ and Na₂SO₄) and then subjected to a hot corrosion test at 1100?°C in air. The influence of laser parameters including power and scanning rate on the coating microstructure and corrosion resistance was investigated. Results showed that the hot corrosion resistance can be improved by producing a dense and smooth surface and reducing the coating permeability to the molten salt. The transformation of the hot corrosion mechanisms was clarified on the basis of the observed corrosion behaviors. A laser power of 1500?W and scanning rate of 9?mm/s can produce minimal surface roughness with few segmented cracks, which can provide improved performance of the hot corrosion resistance.     

The influence of laser treatment on hot corrosion behavior of plasma-sprayed nanostructured yttria stabilized zirconia thermal barrier coatings

In this study, the effect of laser glazing on the hot corrosion behavior of nanostructured thermal barrier coatings (TBCs) was investigated. To this end, the hot corrosion test of plasma-sprayed and laser-glazed thermal barrier coatings conducted against 45 wt.% Na₂SO₄ + 55 wt.% V₂O₅ molten salt at 910 °C for 30 h in open air atmosphere. The results obtained from hot corrosion test showed that the reaction between Y₂O₃ and the corrosive salt produced YVO₄, leached Y₂O₃ from YSZ and led to the progressive destabilization transformation of YSZ from tetragonal to the monoclinic phase. The lifetimes of the plasma-sprayed TBCs were enhanced approximately twofold by laser glazing. Reducing the reactive specific surface area of the dense glazed layer with the molten salts and improving the stress accommodation through network cracks produced by laser glazing were the main enhancement mechanisms accounting for TBC life extension.     

Corrosion of Silicon-Based Ceramics in Combustion Environments

Silicon-based ceramics and composites are prime candidates for heat engine and heat exchanger structural components. In such applications these materials are exposed to combustion gases and deposit-forming corrodents. In this paper combustion environments are defined for various applications. These environments lead to five main types of corrosive degradation: passive oxidation, deposit-induced corrosion, active oxidation, scale/substrate interactions, and scale volatility. Each of these is discussed in detail. The key issues in oxidation mechanisms of high-purity silicon carbide (SiC) and silicon nitride (Si₃N₄) in pure oxygen are discussed. The complicating factors due to the actual combustion environment and commercial materials are discussed. These discussions include secondary elements in the ceramics; additional oxidants, such as water and carbon dioxide (CO₂); combustion environment impurities; long-term oxidation effects; and thermal cycling. Active oxidation is expected in a limited number of combustion situations, and the active-to-passive transition is discussed. At high temperatures the limiting factors are scale melting, scale volatility, and scale/substrate interactions. Deposit-induced corrosion is discussed, primarily for sodium sulfate (Na₂SO₄), but also for vanadate and oxide-slag deposits as well. In applying ceramics in combustion environments it is essential to be aware of these corrosion routes and how they affect the performance of a component.     

NiFe2O4/Ag惰性阳极的熔盐腐蚀性能

以Fe2O3,NiO和Ag粉为主要原料,采用固相烧结工艺制备了NiFe2O4/Ag惰性阳极.采用X射线衍射和扫描电子显微镜对材料的组成和微观结构进行了研究,并测量了样品抗热震性、抗折强度、在冰晶石熔盐中的静态热腐蚀以及电解腐蚀速率,对其腐蚀过程作了初步探讨.结果表明:惰性阳极由NiO,NiFe2O4尖晶石和Ag三相组成.随着金属Ag含量的增多,惰性阳极样品在冰晶石熔盐中的静态热腐蚀速率增加,由于抗热震性和抗折强度有了大幅提高,电解腐蚀速率降低.静态热腐蚀和电解腐蚀呈现出物理化学溶解过程,而且由于金属银对晶界的强化作用,电解腐蚀由晶粒开始.     

Molten Salt Storage for Power Generation

Storage of electrical energy is a key technology for a future climate-neutral energy supply with volatile photovoltaic and wind generation. Besides the well-known technologies of pumped hydro, power-to-gas-to-power and batteries, the contribution of thermal energy storage is rather unknown. At the end of 2019 the worldwide power generation capacity from molten salt storage in concentrating solar power (CSP) plants was 21 GWh_el. This article gives an overview of molten salt storage in CSP and new potential fields for decarbonization such as industrial processes, conventional power plants and electrical energy storage.     

火电厂铜合金凝汽器氯离子腐蚀及缓蚀剂研究综述

目前我国火力发电厂凝汽器材质以铜合金为主,而氯离子对铜合金凝汽器的腐蚀是火电厂循环冷却水系统的主要腐蚀性因素,直接关系到生产的安全运行.作者首先针对铜合金材质氯离子腐蚀评价方法及腐蚀机理进行了综述,然后对该类缓蚀剂的研究进展进行了系统归纳,涉及BTA及其衍生物以及MBT的论述,亦包括了其他唑类及非唑类缓蚀剂情况,同时对部分缓蚀剂的腐蚀控制机理进行了描述,旨在对铜合金材质氯离子的腐蚀及控制的现状及发展方向有一个系统的把握.     

Acceleration of thermal decomposition of molten nitrates by Cr in steel and promotion of this effect by halogens

Molten salts have been widely studied as the most common heat storage medium for concentrated solar power (CSP) plants. However, most studies have focused on the corrosiveness of molten salts, while this study innovatively reveals the role of stainless steel in promoting the decomposition of molten salts and the mechanism by which the halogen ions accelerate this process. Considering commercial Solar Salt as an example, the thermal stability, composition, and thermophysical properties of Solar Salt adding Cl⁻, Br⁻, and I⁻ after contacting different stainless steel were analyzed. The results showed that Cr was the main reason for the decomposition of the molten salt, and Cl⁻, Br⁻, and I⁻, all accelerated the decomposition. Meanwhile, different halogen ions promoted the decomposition of molten salts through different mechanisms: oxide layer destruction and chain oxidation.     

Thermodynamics of reaction between gas-turbine ceramic coatings and ingested CMAS corrodents

The thermodynamic stability of ceramic coatings with respect to their reaction products is crucial to develop more durable coating materials for gas-turbine engines. Here, we report direct measurements using high-temperature solution calorimetry of the enthalpies of reaction between some relevant ceramic coatings and a corrosive molten silicate. We also report the enthalpy of mixing between the coatings and molten silicate after combining the results measured by high-temperature solution calorimetry with enthalpies of fusion measured by drop-and-catch calorimetry and differential thermal analysis. The enthalpies of solution of selected silicate and zirconia-based coatings and apatite reaction products are moderately positive except for 7YSZ, yttria-stabilized zirconia. Apatite formation is only favorable over coating dissolution in terms of enthalpy for 7YSZ. The enthalpies of mixing between the coatings and the molten silicate are less exothermic for Yb₂Si₂O₇ and CaYb₄Si₃O₁₃ than for 7YSZ, indicating lower energetic stability of the latter against molten silicate corrosion. The thermochemical results explain and support the very corrosive nature of CMAS melts in contact with ceramic coatings.     

氟化物熔盐的制备及其应用进展

氟化物熔盐具有高温稳定性好、热导率高、比热容大、电化学窗口宽、饱和蒸汽压低和中子吸收截面小等一系列优点,是一种具有广阔应用前景的重要功能材料。本文介绍了氟化物熔盐的典型制备及净化方法（如真空除水法、氟氢化铵法、H₂-HF净化法、电化学净化法、添加还原剂法）,分析了不同方法去除熔盐中杂质离子的作用机制和技术特点。总结了氟化物熔盐在核能、冶金、功能材料制备、先进储能介质、表面处理技术、电子化学品、精细化工及熔盐电池材料等领域的应用及最新进展。突出了氟化物熔盐作为核反应堆冷却剂、熔盐电解质、高温储能材料及反应介质等方面的应用优势。指出了氟化物熔盐在制备及应用过程中存在的问题及发展趋势,并就其发展前景进行了展望。文章指出开展氟化物熔盐制备与纯化机制研究、探索氟化物熔盐净化过程中杂质的存在形式与迁移规律、阐明氟化物熔盐制备与净化机理、发展新的熔盐净化方法以减小熔盐的腐蚀性和降低成本对熔盐的工业化生产和应用至关重要。     

C/C-SiC component for metallic phase change materials

Thanks to their high energy density and thermal conductivity, metallic Phase Change Materials (mPCM) have shown great potential to improve the performance of thermal energy storage systems. However, the commercial application of mPCM is still limited due to their corrosion behavior with conventional container materials. This work first addresses on a fundamental level, whether carbon-based composite-ceramics are suitable for corrosion critical components in a thermal storage system. The compatibility between the mPCM AlSi₁₂ and the Liquid Silicon Infiltration (LSI)-based carbon fiber reinforced silicon carbide (C/C-SiC) composite is then investigated via contact angle measurements, microstructure analysis, and mechanical testing after exposure. The results reveal that the C/C-SiC composite maintains its mechanical properties and microstructure after exposure in the strongly corrosive mPCM. Based on these results, efforts were made to design and manufacture a container out of C/C-SiC for the housing of mPCM in vehicle application. The stability of the component filled with mPCM was proven nondestructively via computer tomography (CT). Successful thermal input- and output as well as thermal storage ability were demonstrated using a system calorimeter under conditions similar to the application. The investigated C/C-SiC composite has significant application potential as a structural material for thermal energy storage systems with mPCM.