Ammonia production using iron nitride and water as hydrogen source under mild temperature and pressure

Ammonia generation was studied in the reaction between water and nitrogen-containing iron at 323 K and atmospheric pressure. Similar to metallic Fe, the interstitial compound Fe₃N reduced water through Fe oxidation to produce hydrogen gas, while the N combined with atomic hydrogen to produce ammonia as a byproduct. The addition of carbon dioxide to this system accelerated the reaction with concomitant consumption of carbon dioxide. The promoted ammonia production upon addition of carbon dioxide can be attributed to the generation of atomic hydrogen from the redox reaction of carbonic acid and Fe, as well as removal of used Fe from the reaction system through the formation of a soluble carbonato complex. When carbonate was added to the reaction system, the production rates of ammonia and hydrogen increased further. The results here confirmed that ammonia can be synthesized from iron nitride under mild conditions by utilizing carbon dioxide.     

多晶硅表面金属催化化学腐蚀法制绒研究现状

在多晶硅太阳能电池的生产过程中, 金刚线切割技术(Diamond wire sawn, DWS)具有切割速度快、精度高、原材料损耗少等优点, 受到了广泛关注。金刚线切割多晶硅表面形成的损伤层较浅, 与传统的酸腐蚀制绒技术无法匹配, 金属催化化学腐蚀法应运而生。金属催化化学腐蚀法制绒具有操作简单、结构可控且易形成高深宽比的绒面等优点, 具有广阔的应用前景。本文总结了不同类型的金属催化剂在制绒过程中的腐蚀机理及其形成的绒面结构, 深入分析和讨论了具有代表性的银、铜的单一及复合催化腐蚀过程及绒面结构和电池片性能。最后对金刚线切割多晶硅片表面的金属催化化学腐蚀法存在的问题进行了分析, 并展望了未来的研究方向。     

The corrosion of mild and stainless steel in alkaline anaerobic conditions representing the Belgian “supercontainer” concept and the Swiss L/ILW repository

Deep geological repositories for radioactive waste contain metallic materials, either used to construct disposal canisters or as low-/intermediate-level waste (L/ILW). The safety relevance of corrosion is linked to canister lifetime in the former case and gas generation in the latter. More specifically, the Belgian “supercontainer” concept envisages mild steel for the used fuel disposal canister, and in the case of the Swiss L/ILW repository, mild steels are the largest metallic waste component due to the decommissioning of civilian power-generating facilities. For these circumstances, the corrosion environment is dominated by the chemistry of cement, which is used as buffer or backfill material. The corrosion behaviour of mild steel in anoxic environments was studied through the analysis of the hydrogen end-product. Hydrogen analysis was conducted by periodically purging the cell head-space and analysing the gas using a solid-state hydrogen sensor. While this method is limited to providing only uniform corrosion rates averaged over periods of time, ranging from weeks to months, it provides excellent resolution and sensitivity. The test cell environments were matched against the anticipated Belgian high-level waste and Swiss L/ILW repository environments, and also against experiments that have been conducted by other researchers for comparative purposes. Samples were exposed to synthetic cement pore waters, representing fresh and degraded cement. In young cement waters, the formation of initial corrosion products resulted in steel wire corrosion rates of the order of µm/year, which, at 80°C rapidly declined to ∼10 nm/year. In contrast, SA516 grade 70 steel plate corroded much more slowly under similar conditions. In aged cement waters, initial corrosion rates were higher but declined faster towards a longer-term rate of ∼10 nm/year. 316L stainless steel, embedded in cementitious material, corroded at a rate of <1 nm/year at 50°C.     

Effect of spheroidized microstructure on the impact toughness and electrochemical performance of a high-carbon steel

The influence of cementite spheroidization on the impact toughness and electrochemical properties of a high-carbon steel has been thoroughly investigated in this study. Heavy warm rolling, followed by 2 h of annealing, has resulted in near-complete spheroidization, leading to a microstructure consisting of nano-cementite globules dispersed in the ultrafine-grained ferritic matrix. The Charpy impact test exhibited superior impact toughness with increased spheroidization. It is validated by the presence of abundant dimples in the fractographs of spheroidized specimens, in contrast to the as-received one that experienced a brittle failure due to its lamellar pearlitic structure. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) carried out in a 3.5% NaCl solution revealed that the corrosion resistance of the alloy gets improved with the increase in the degree of spheroidization. This is attributed to the lower susceptibility of the spheroidized specimen to microgalvanic corrosion owing to the minimum area of contact between nano-spheroidized cementite and ferrite, as elucidated with the help of EIS results aided by equivalent electrical circuit model.     

Investigation on thermal conductivity and mechanical properties of Si3N4 ceramics via one-step sintering

High thermal conductivity Si₃N₄ ceramics were fabricated using a one-step method consisting of reaction-bonded Si₃N₄ (RBSN) and post-sintering. The influence of Si content on nitridation rate, β/(α+β) phase rate, thermal conductivity and mechanical properties was investigated in this work. It is of special interest to note that the thermal conductivity showed a tendency to increase first and then decrease with increasing Si content. This experimental result shows that the optimal thermal conductivity and fracture toughness were obtained to be 66 W (m K)^-1 and 12.0 MPa m^1/2, respectively. As a comparison, the nitridation rate and β/(α+β) phase rate in a static pressure nitriding system, i.e., 97% (MS10), 97% (MS15), 97% (MS20) and 8.3% (MS10), 8.3% (MS15), 8.9% (MS20), respectively, have obvious advantages over those in a flowing nitriding system, i.e., 91% (MS10), 91% (MS15), 93% (MS20) and 3.1% (MS10), 3.3% (MS15), 3.3% (MS20), respectively. Moreover, high lattice integrity of the β-Si₃N₄ phase was observed, which can effectively confine O atoms into the β-Si₃N₄ lattice using MgO as a sintering additive. This result indicates that one-step sintering can provide a new route to prepare Si₃N₄ ceramics with a good combination of thermal conductivity and mechanical properties.     

Potential influence of microorganisms on the corrosion of carbon steel in the French high- and intermediate-level long-lived radioactive waste disposal context

In the context of the high-level radioactive waste disposal CIGEO, the corrosion rate due to microbially influenced corrosion (MIC) has to be evaluated. In France, it is envisaged to dispose of high- and intermediate-level long-lived radioactive waste at a depth of 500 m in a deep geological disposal, drilled in the Callovo-Oxfordian claystone (Cox) formation. To do so, a carbon steel casing will be inserted inside disposal cells, which are horizontal tunnels drilled in the Cox. A specific cement grout will be injected between the carbon steel casing and the claystone. A study was conducted to evaluate the possibility of MIC on carbon steel in the foreseeable high radioactive waste disposal. The corrosiveness of various environments was investigated at 50°C and 80°C with or without microorganisms enriched from samples of Andra's underground research laboratory. The monitoring of corrosion during the experiments was ensured using gravimetric method and real-time corrosion monitoring using sensors based on the measurements of the electrical resistance. The corrosion data were completed with microbiological analyses including cultural and molecular characterizations.     

Corrosion behavior of T24, T92, VM12, and AISI 304 steels exposed to KCl–NaCl–K2SO4–Na2SO4 salt mixtures

The corrosion mechanisms of T24, T92, VM12, and AISI 304 steels are studied under the influence of NaCl–KCl, NaCl–Na₂SO₄, and KCl–K₂SO₄ salt mixtures in a dry air atmosphere at 650°C for 15 days. NaCl–KCl was the most aggressive deposit and AISI 304 stainless steel exhibited the highest corrosion resistance. There was no relation between the Cr content of the ferritic steels and their corrosion resistance in NaCl–KCl. In contrast, the resistance of high-Cr steels was better when exposed to NaCl–Na₂SO₄ and KCl–K₂SO₄. The high-Cr and the low-Cr steels were more susceptible to NaCl–Na₂SO₄ and to KCl–K₂SO₄, respectively.     

基于材料力学性能的最低设计金属温度曲线分析

铁素体钢在低温条件下存在明显的韧脆转变现象。为防止脆断事故的发生,需要确定铁素体钢制压力容器的最低使用温度。针对ASME中的A^D四条冲击豁免曲线,对应地选取了4种材料,基于材料实际的屈服强度和参考温度,按照ASME中豁免曲线的计算方法,计算得到4种材料的最低设计金属温度曲线,并与对应的A^D曲线对比,定量地分析ASME中豁免曲线的保守性。结果表明,ASME中的豁免曲线相对于材料自身的最低设计金属温度曲线保守性较大;韧性相近的材料被划分到不同的豁免曲线,使得韧性富裕量差异较大,对于某些材料,其断裂韧性被低估。     

复杂炼油塔模拟的改进联立方程内外层算法

在内外层算法的基础上，采用联立方程思想将主塔、侧线汽提塔视为一个整体进行建模，并针对复杂炼油塔的特点对算法提出了改进。首先，由于传统内外层法简化的K值模型对组成的变化不敏感，在处理带有石油的体系时，容易出现迭代次数较多，甚至部分塔板温度更新异常的问题，因此采用了汽相分数加和式推导了简化的K值模型加权因子。其次，借鉴流量加和法思想，规定侧线汽提塔的塔底产品流量作为设计变量，增强了算法收敛的稳定性。为验证改进后算法的有效性，采用不同的算法对实际的常压塔进行了模拟，结果显示改进后的算法适合应用于复杂炼油塔的模拟计算。     

钢管套筒灌浆连接轴向受拉性能模拟试验研究

为研究钢管套筒灌浆连接轴向受拉破坏过程及破坏机理，试验中设计了16组48个钢管套筒灌浆连接试件，试件采用钢板代替圆钢管，并进行静载试验。分析了灌浆料裂缝扩展过程、荷载-相对位移曲线，并对抗剪键高距比、灌浆料厚度、侧向力等因素对破坏过程及承载力的影响进行分析。结果表明：对于不设置抗剪键的套筒灌浆连接试件，斜裂缝随机产生，裂缝分布不均匀；对于设置抗剪键的套筒灌浆连接试件，裂缝首先出现在底部抗剪键位置处，与水平方向夹角约为30°，随后在中部和上部抗剪键位置处分别出现斜裂缝。由于每个抗剪键上荷载分担并不均匀，与抗剪键接触的灌浆料逐渐达到极限压应力，达到极限状态时，承载力全部由抗剪键间的机械咬合力承担，在连接承载力中，可忽略摩擦力和胶结力作用。随着抗剪键高距比h/s增大，各试件初始剪切刚度相差不大，承载力增大，但增幅逐渐减小，建议抗剪键高距比0.06g/s>0.3，同时需要满足灌浆料灌注的施工要求。