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Effects of iron oxide on crystallization behavior and spatial distribution of spinel in stainless steel slag
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作者 Zihang Yan Qing Zhao +3 位作者 Chengzhi Han Xiaohui Mei Chengjun Liu Maofa Jiang 《International Journal of Minerals,Metallurgy and Materials》 SCIE EI CAS CSCD 2024年第2期292-300,共9页
Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimen... Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimental environmental issues.To prevent chromium pollution,the effects of iron oxide on crystallization behavior and spatial distribution of spinel were investigated in this work.The results revealed that FeO was more conducive to the growth of spinels compared with Fe2O3 and Fe3O4.Spinels were found to be mainly distrib-uted at the top and bottom of slag.The amount of spinel phase at the bottom decreased with the increasing FeO content,while that at the top increased.The average particle size of spinel in the slag with 18wt%FeO content was 12.8μm.Meanwhile,no notable structural changes were observed with a further increase in FeO content.In other words,the spatial distribution of spinel changed when the content of iron oxide varied in the range of 8wt%to 18wt%.Finally,less spinel was found at the bottom of slag with a FeO content of 23wt%. 展开更多
关键词 stainless steel slag spinel CHROMIUM waste remediation ferrous oxide
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Microwave-assisted exploration of the electron configuration-dependent electrocatalytic urea oxidation activity of 2D porous NiCo_(2)O_(4) spinel
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作者 Jun Wan Zhiao Wu +11 位作者 Guangyu Fang Jinglin Xian Jiao Dai Jiayue Guo Qingxiang Li Yongfei You Kaisi Liu Huimin Yu Weilin Xu Huiyu Jiang Minggui Xia Huanyu Jin 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第4期226-235,共10页
Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spine... Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spinel synthesis methods with prolonged high-temperature reactions lack kinetic precision,hindering the balance between controlled doping and highly active two-dimensional(2D)porous structures design.This significantly impedes the identification of electron configuration-dependent active sites in doped 2D nickel-based spinels.Herein,we present a microwave shock method for the preparation of 2D porous NiCo_(2)O_(4)spinel.Utilizing the transient on-off property of microwave pulses for precise heteroatom doping and 2D porous structural design,non-metal doping(boron,phosphorus,and sulfur)with distinct extranuclear electron disparities serves as straightforward examples for investigation.Precise tuning of lattice parameter reveals the impact of covalent bond strength on NiCo_(2)O_(4)structural stability.The introduced defect levels induce unpaired d-electrons in transition metals,enhancing the adsorption of electron-donating amino groups in urea molecules.Simultaneously,Bode plots confirm the impact mechanism of rapid electron migration caused by reduced band gaps on UOR activity.The prepared phosphorus-doped 2D porous NiCo_(2)O_(4),with optimal electron configuration control,outperforms most reported spinels.This controlled modification strategy advances understanding theoretical structure-activity mechanisms of high-performance 2D spinels in UOR. 展开更多
关键词 2D materials spinel Microwave ELECTROCATALYSIS Urea oxidation reaction
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Unveiling the geometric site dependent activity of spinel Co_(3)O_(4)for electrocatalytic chlorine evolution reaction
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作者 Linke Cai Yao Liu +5 位作者 Jingfang Zhang Qiqi Jia Jiacheng Guan Hongwei Sun Yu Yu Yi Huang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第5期95-103,共9页
Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catal... Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catalytic contribution of geometric Co site in the electrocatalytic CER plays a pivotal role to precisely modulate electronic configuration of active Co sites to boost CER.Herein,combining density functional theory calculations and experiment results assisted with operando analysis,we found that the Co_(Oh) site acts as the main active site for CER in spinel Co_(3)O_(4),which shows better Cl^(-)adsorption and more moderate intermediate adsorption toward CER than CoTd site,and does not undergo redox transition under CER condition at applied potentials.Guided by above findings,the oxygen vacancies were further introduced into the Co_(3)O_(4) to precisely manipulate the electronic configuration of Co_(Oh) to boost Cl^(-)adsorption and optimize the reaction path of CER and thus to enhance the intrinsic CER activity significantly.Our work figures out the importance of geometric configuration dependent CER activity,shedding light on the rational design of advanced electrocatalysts from geometric configuration optimization at the atomic level. 展开更多
关键词 Chlorine evolution reaction Geometry effects Active chlorine Electronic configuration optimization spinel oxides
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铁素体不锈钢表面电沉积-热处理制备Co-Mn尖晶石涂层的研究进展
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作者 邓佳 宋建丽 +1 位作者 李云逸 童伟 《热加工工艺》 北大核心 2023年第4期18-22,共5页
铁素体不锈钢(ferritic stainless steel,FSS)是中温化环境中固体氧化物燃料电池(solid oxide fuel cell,SOFC)的理想连接体材料。但由于FSS中含有较多的Cr元素,在SOFC工作过程中,连接体表面生成的Cr氧化物薄膜增厚,会造成连接体导电性... 铁素体不锈钢(ferritic stainless steel,FSS)是中温化环境中固体氧化物燃料电池(solid oxide fuel cell,SOFC)的理想连接体材料。但由于FSS中含有较多的Cr元素,在SOFC工作过程中,连接体表面生成的Cr氧化物薄膜增厚,会造成连接体导电性能下降;FSS中的Cr元素与H_(2)O或O_(2)发生反应,还会形成易挥发的化合物,这些化合物在阴极界面沉积,将使阴极活性降低,导致阴极“Cr中毒”和SOFC性能衰减,严重制约了SOFC商业化发展和应用。采用电沉积-热处理技术在FSS表面制备Co-Mn尖晶石保护涂层可有效防止Cr化合物的挥发,改善电池堆的抗氧化性能。在保证SOFC导电性的同时,延长其使用寿命。综述了FSS表面电沉积-热处理制备Co-Mn尖晶石涂层的主要方法、特点及涂层性能等方面的研究进展,对该领域未来的发展趋势进行了展望。 展开更多
关键词 SOFC连接体 铁素体不锈钢 co-mn尖晶石涂层 电沉积-热处理 研究进展
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Co-Mn-Co复合涂层沉积过程及其高温氧化导电性能研究
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作者 张旭 崔文宁 +4 位作者 王玉婷 周晨曦 张力 孙杭 郭平义 《材料研究与应用》 CAS 2023年第3期536-543,共8页
在固体氧化物燃料电池(SOFC)工作温度下,金属连接体氧化生成的铬化物易挥发,导致电池“阴极毒化”问题。为了有效抑制铬化物的挥发,钴锰尖晶石涂层作为最有前途的SOFC连接体涂层,具有良好的高温导电性能、抗氧化性能及与电池其它组件相... 在固体氧化物燃料电池(SOFC)工作温度下,金属连接体氧化生成的铬化物易挥发,导致电池“阴极毒化”问题。为了有效抑制铬化物的挥发,钴锰尖晶石涂层作为最有前途的SOFC连接体涂层,具有良好的高温导电性能、抗氧化性能及与电池其它组件相匹的配热膨胀系数(CTE)。为研究金属Co和Mn离子在水溶液中的电沉积工艺,选择在430 SS金属连接体上制备Co-Mn-Co复合涂层和Co-Mn复合涂层,然后在750℃高温下热生长得到复合尖晶石涂层。同时,对500 h后生成的尖晶石氧化物涂层的表截面形貌、组织结构及高温抗氧化性和导电性能进行研究。结果表明,Co-Mn-Co结构涂层的性能优于Co-Mn双沉积结构涂层,多层复合涂层利于涂层内Co和Mn元素的互扩散,促进Co和Mn氧化物向MnCo2O_(4)尖晶石的转换,从而提高涂层的高温抗氧化与导电性能。 展开更多
关键词 固体氧化物燃料电池 金属连接体 直流电沉积 co-mn涂层 尖晶石
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Enabling structural and interfacial stability of 5 V spinel LiNi0.5Mn1.5O4 cathode by a coherent interface 被引量:2
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作者 Min Xu Ming Yang +6 位作者 Minfeng Chen Lanhui Gu Linshan Luo Songyan Chen Jizhang Chen Bo Liu Xiang Han 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第1期266-276,I0007,共12页
Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),a 5 V class high voltage cathode,has been regarded as an attractive candidate to further improve the energy density of lithium-ion battery.The issue simultaneously enabling side st... Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),a 5 V class high voltage cathode,has been regarded as an attractive candidate to further improve the energy density of lithium-ion battery.The issue simultaneously enabling side stability and maintaining high interfacial kinetics,however,has not yet been resolved.Herein,we design a coherent Li_(1.3)A_(l0.3)Ti_(1.7)(PO)_(4)(LATP)layer that is crystally connected to the spinel LNMO host lattices,which offers fast lithium ions transportation as well as enhances the mechanical stability that prevents the particle fracture.Furthermore,the inactive Li_(3)BO_(3)(LBO)coating layer inhibits the corrosion of transition metals and continuous side reactions.Consequently,the coherent-engineered LNMO-LATPLBO cathode material exhibits superior electrochemical cycling stability in a window of 3.0–5.0 V,for example a high-capacity retention that is 89.7%after 500 cycles at 200 m A g-1obtained and enhanced rate performance(85.1 m A h g^(-1)at 800 m A g^(-1))when tested with a LiPF6-based carbonate electrolyte.Our work presents a new approach of engineering 5 V class spinel oxide cathode that combines interfacial coherent crystal lattice design and surface coating. 展开更多
关键词 Lithium-ion battery spinel cathode LATP Coherent interface
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Effects of ZnO,FeO and Fe_(2)O_(3)on the spinel formation,microstructure and physicochemical properties of augite-based glass ceramics 被引量:1
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作者 Shuai Zhang Yanling Zhang Shaowen Wu 《International Journal of Minerals,Metallurgy and Materials》 SCIE EI CAS CSCD 2023年第6期1207-1216,共10页
Augite-based glass ceramics were synthesised using ZnO,FeO,and Fe_(2)O_(3)as additives,and the spinel formation,matrix structure,crystallisation thermodynamics,and physicochemical properties were investigated.The resu... Augite-based glass ceramics were synthesised using ZnO,FeO,and Fe_(2)O_(3)as additives,and the spinel formation,matrix structure,crystallisation thermodynamics,and physicochemical properties were investigated.The results showed that oxides resulted in numerous preliminary spinels in the glass matrix.FeO,ZnO,and Fe_(2)O_(3)influenced the formation of spinel,while FeO simplified the glass network.FeO and ZnO promoted bulk crystallisation of the parent glass.After adding oxides,the grains of augite phase were refined,and the relative quantities of augite crystal planes were also influenced.All samples displayed good mechanical properties and chemical stability.The 2wt%ZnO-doping sample displayed the maximum flexural strength(170.3 MPa).Chromium leaching amount values of all the samples were less than the national standard(1.5 mg/L),confirming the safety of the materials.In conclusion,an appropriate amount of zinc-containing raw material is beneficial for the preparation of augite-based glass ceramics. 展开更多
关键词 spinel network structure thermodynamics MICROSTRUCTURE glass ceramics
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Development of bimetallic spinel catalysts for low-temperature decomposition of ammonium dinitramide monopropellants
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作者 C.Shamjitha Anuj A.Vargeese 《Defence Technology(防务技术)》 SCIE EI CAS CSCD 2023年第12期47-54,共8页
Ammonium dinitramide(ADN)based liquid monopropellants have been identified as environmentally benign substitutes for hydrazine monopropellant.However,new catalysts are to be developed for making ADN monopropellants co... Ammonium dinitramide(ADN)based liquid monopropellants have been identified as environmentally benign substitutes for hydrazine monopropellant.However,new catalysts are to be developed for making ADN monopropellants cold-start capable.In the present study,performance of Co and Ba doped CuCr_2O_4 nanocatalysts prepared by hydrothermal method was evaluated on the decomposition of aqueous ADN solution and ADN liquid monopropellant(LMP103X).The catalysts were characterized by PXRD(Powder X-ray Diffraction),FTIR(Fourier Transform Infrared spectroscopy),SEM(Scanning Electron Microscopy),TEM(Transmission Electron Microscopy),EDS(Energy Dispersive X-ray Spectroscopy),and XPS(X-ray Photoelectron Spectroscopy).The nanosize was confirmed by SEM and TEM,while the nanoflake morphology was confirmed by the SEM analysis.Further,we obtained the elemental composition from the EDS analysis.We investigated the catalytic activity of the catalysts by thermogravimetric(TG)analysis and the developed catalysts lowered the decomposition temperature of ADN monopropellant by about 55℃.The XPS analysis confirmed the presence of metal ions with different chemical states.Apparently,increase in the surface area of the catalysts and the mixed active sites as well as the development of oxygen vacancy on the catalyst surface introduced by metal doping are influencing the decomposition temperature of ADN samples. 展开更多
关键词 ADN monopropellant Mixed metal oxides Doped spinels Catalytic decomposition
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Effects of Al and Co doping on the structural stability and high temperature cycling performance of LiNi_(0.5)Mn_(1.5)O_(4) spinel cathode materials
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作者 Jianfeng Cheng Meixuan Li +4 位作者 Yutong Wang Jiexiang Li Jiawei Wen Chunxia Wang Guoyong Huang 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2023年第9期201-209,共9页
The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)limits their further application.Herein,Al and Co were doped in LNMO materials for a more stable struct... The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)limits their further application.Herein,Al and Co were doped in LNMO materials for a more stable structure and capacity.The LNMO,LiNi_(0.45)Al_(0.05)Mn_(1.5)O_(4)(LNAMO)and LiNi_(0.45)Co_(0.05)Mn_(1.5)O_(4)(LNCMO)were synthesized by calcination at 900℃ for 8 h,which was called as solid-phase method and applied universally in industry.XRD,FT-IR and CV test results showed the synthesized samples have cation disordering Fd-3m space group structures.Moreover,the incorporation of Al and Co increased the cation disordering of LNMO,thereby increasing the transfer rate of Li+.The SEM results showed that the doped samples performed more regular and ortho-octahedral.The EDS elemental analysis confirmed the uniform distribution of each metal element in the samples.Moreover,the doped samples showed better electrochemical properties than undoped LNMO.The LNAMO and LNCMO samples were discharged with specific capacities of 116.3 mA·h·g^(-1)and 122.8 mA·h·g^(-1)at 1 C charge/discharge rate with good capacity retention of 95.8% and 94.8% after 200 cycles at room temperature,respectively.The capacity fading phenomenon of the doped samples at 50℃ and 1 C rate was significantly improved.Further,cations doping also enhanced the rate performance,especially for the LNCMO,the discharge specific capacity of 117.9 mA·h·g^(-1)can be obtained at a rate of 5 C. 展开更多
关键词 High voltage spinel Al/Co doping High temperature cycling stability
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Effect of Al Powder and Si Powder Additions on Structure and Properties of Unburned Magnesium Aluminate Spinel Refractories
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作者 ZHOU Lianzhuo WANG Zhoufu +3 位作者 WANG Xitang LIU Hao MA Yan QUAN Zhenghuang 《China's Refractories》 CAS 2023年第3期14-19,共6页
Unburned magnesium aluminate spinel refractories were prepared using sintered magnesium aluminate spinel as the main raw material,phenolic resin as the binder,aluminum powder(2%,4%,and 6%by mass)and silicon powder(whe... Unburned magnesium aluminate spinel refractories were prepared using sintered magnesium aluminate spinel as the main raw material,phenolic resin as the binder,aluminum powder(2%,4%,and 6%by mass)and silicon powder(when Al powder addition is 4%,Si powder addition varies:1%and 2%,by mass)as additives.The effects of the Al powder and Si powder additions on the properties and microstructure of the refractories heat treated at different temperatures(1000,1400,and 1600℃for 3 h)were studied.The results show that the Al powder addition can greatly enhance the cold modulus of rupture of the samples fired at 1000 or 1400℃,and meanwhile AlN reinforcement phase forms in the matrix,which greatly improves the hot modulus of rupture of the samples at 1400℃;however,the heat treatment at 1600℃has little influence on the strength;the addition of Al powder and Si powder results in the formation of low melting point phases,greatly reducing the hot modulus of rupture.However,the low melting point phases promote sintering,which enhances the density and the cold modulus of rupture,and decreases the volume change during heating.The samples added with Al and Si all have higher cold modulus of rupture than those added with Al powder only. 展开更多
关键词 aluminum powder silicon powder magnesium aluminate spinel unburned refractories STRENGTH
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Gemological-Mineralogical Characteristic of Spinels from Sri Lanka
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作者 Pantaree Lomthong Dietmar Schwarz +2 位作者 Gamini Zoyza Yanyu Chen Yicen Liu 《宝石和宝石学杂志(中英文)》 CAS 2023年第6期42-57,共16页
Detailed mineralogical and gemological records were conducted on 340 unheated spinels from the Horana, Eheliyagoda, Ratnapura, and Okkampatiya mining areas in Sri Lanka. The color of Sri Lankan spinel varies greatly: ... Detailed mineralogical and gemological records were conducted on 340 unheated spinels from the Horana, Eheliyagoda, Ratnapura, and Okkampatiya mining areas in Sri Lanka. The color of Sri Lankan spinel varies greatly: in addition to the mainstream pink to purple pink, green and blue can also be seen. Compared with spinel from other regions such as Myanmar, Vietnam, and Tanzania, Sri Lanka's spinel has more abundant inclusions: several mining areas generally have inclusions such as dolomite, apatite, zircon, and chondrodite. Minerals such as graphite and forsterite are also found in spinel produced in the Horana region;graphite and rutile have been found in spinel produced in the Okkamptiya region. Partially healed fissures are most common in spinel in the Okkampatiya mining area;Unlike Vietnamese spinel, dislocations and growth structures are almost absent in Sri Lankan spinel. The LA-ICP-MS analysis results showed that there were no significant differences among the mining areas. LA-ICP-MS analysis of 5 Sri Lankan cobalt blue spinels showed a variation of 11 to 120 ppm in this chromogenic element. The UV visible absorption spectrum results show that Sri Lankan spinel has a combination spectra with variable ratios of the spectral components Cr 3+ , V 3+ and Fe 2+ from pink to red, orange, purple to purple, and blue-green. The results of infrared spectroscopy and laser Raman spectroscopy analysis showed that all samples showed no indications for heat treatment. 展开更多
关键词 gemological-mineralogical characteristic spinel Sri Lanka SPECTROSCOPY INCLUSION
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卤化钾改性Mn-Co-Fe尖晶石脱除气相Hg0的性能研究
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作者 徐元强 仲兆平 +1 位作者 许月阳 黄佳伟 《中国电机工程学报》 EI CSCD 北大核心 2024年第4期1481-1492,I0019,共13页
为提高Mn-Co-Fe尖晶石吸附剂的脱汞性能,该研究首先采用溶胶凝胶自燃烧法和浸渍法结合制备了KX(X表示Cl、Br和I)改性的Mn-Co-Fe尖晶石吸附剂。然后,分别利用SEM、SEM结合EDS能谱Mapping、BET、XRD和VSM来表征其表面形貌、表面元素占比... 为提高Mn-Co-Fe尖晶石吸附剂的脱汞性能,该研究首先采用溶胶凝胶自燃烧法和浸渍法结合制备了KX(X表示Cl、Br和I)改性的Mn-Co-Fe尖晶石吸附剂。然后,分别利用SEM、SEM结合EDS能谱Mapping、BET、XRD和VSM来表征其表面形貌、表面元素占比及分布、比表面积及总孔容积、晶相结构和比饱和磁化特性。并通过固定床探究了卤化钾种类、KI负载量、吸附温度和入口汞浓度对模拟燃煤烟气中汞脱除性能的影响。最后,通过动力学模拟、XPS表征和程序升温脱附实验研究了吸附剂对汞脱除的控制步骤、机制以及汞在吸附剂表面的存在形态。研究结果表明:在相同实验条件下,0.10KX@MCFS对汞的平均脱除效率KI(92.84%)>KBr(88.39%)>KCl(86.61%)。此外,增加KI的负载量、吸附温度和入口汞浓度在一定程度上能够促进改性MCFS的脱汞性能。虽然KI的负载导致了MCFS的磁性能下降,但综合分析得出:0.10KI@MCFS具有一个相对优异的汞脱除性能和饱和磁化强度值(34.0 emu/g)。因此,该研究的这一发现对汞污染排放控制和吸附剂磁回收的实践研究具有重要的参考价值。 展开更多
关键词 Mn-Co-Fe尖晶石 卤化钾 浸渍改性 饱和磁化强度
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不同碱度渣对刚玉-尖晶石浇注料的侵蚀行为研究
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作者 杨宗源 王景然 +4 位作者 王桐 张锦化 韩兵强 倪月娥 柯昌明 《耐火材料》 CAS 北大核心 2024年第1期13-18,共6页
浇注料的抗渣侵蚀性能与钢渣的碱度密切相关。以烧结刚玉、缺陷尖晶石微粉、活性α-Al_(2)O_(3)微粉、电熔镁砂细粉和铝酸钙水泥(Secar71)为主要原料,制备了刚玉-尖晶石浇注料,采用静态坩埚法于1600℃保温3 h进行抗渣试验,并用热力学模... 浇注料的抗渣侵蚀性能与钢渣的碱度密切相关。以烧结刚玉、缺陷尖晶石微粉、活性α-Al_(2)O_(3)微粉、电熔镁砂细粉和铝酸钙水泥(Secar71)为主要原料,制备了刚玉-尖晶石浇注料,采用静态坩埚法于1600℃保温3 h进行抗渣试验,并用热力学模拟计算了液相量和液相组成,研究了刚玉-尖晶石浇注料对3种不同碱度渣(1.6、2.3和7.6)的抗渣侵蚀性能。结果表明:刚玉-尖晶石浇注料在高碱度渣中溶解能力有限,在熔渣-耐火材料界面极易形成尖晶石固溶体和六铝酸钙等高熔点物相,形成致密层阻挡熔渣渗透和侵蚀。而其在低碱度渣中溶解度较高,在浇注料-熔渣达到较高反应程度时,才开始形成尖晶石固溶体和六铝酸钙等高温相,无法形成有效的致密层阻止熔渣对浇注料的侵蚀和渗透。因此,刚玉-尖晶石浇注料对高碱度渣抗渣侵蚀能力较强,对低碱度渣抗渣侵蚀能力较弱。 展开更多
关键词 刚玉-尖晶石浇注料 碱度 抗渣侵蚀性能 热力学模拟
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高效MFe_(2)O_(4)(M=Zn、Mg、Cu和Mn)尖晶石催化剂应用于费托合成
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作者 王超 陈建刚 +3 位作者 朱华青 张文绍 白洪彬 张娟 《燃料化学学报(中英文)》 EI CAS CSCD 北大核心 2024年第5期667-676,共10页
一系列尖晶石催化剂,包括ZnFe_(2)O_(4)、MgFe_(2)O_(4)、CuFe_(2)O_(4)和MnFe_(2)O_(4)被用于费托合成反应(Fischer-Tropsch synthesis,FTS)。Zn、Mg、Cu和Mn很容易与Fe形成尖晶石。其中,在前处理和反应过程中,Zn和Mg能够显著维持尖晶... 一系列尖晶石催化剂,包括ZnFe_(2)O_(4)、MgFe_(2)O_(4)、CuFe_(2)O_(4)和MnFe_(2)O_(4)被用于费托合成反应(Fischer-Tropsch synthesis,FTS)。Zn、Mg、Cu和Mn很容易与Fe形成尖晶石。其中,在前处理和反应过程中,Zn和Mg能够显著维持尖晶石结构,使得CO转化率较低。在反应过程中,Cu和Mn有利于碳化铁的生成,导致CuFe_(2)O_(4)和MnFe_(2)O_(4)对FTS性能影响显著。C_(2)^(=)-C_(4)^(=)ZnFe_(2)O_(4)对烃分布和C_(2)−C_(4)烯/烷比影响很小。MgFe_(2)O_(4)的C_(5+)选择性较低,同时由于Mg的碱性作用,从而提高了选择性和C_(2)−C_(4)烯/烷比。Cu可以促进催化剂的碳化,从而使CuFe_(2)O_(4)具有较高的活性。同时,CuFe_(2)O_(4)可以显著提高C_(5+)选C_(2)^(=)-C_(4)^(=)择性。此外,Cu可以促进H_(2)的解离和活化,从而有利于烯烃的二次加氢,降低选择性和C_(2)−C_(4)烯/烷比。虽然Mn在反应过程中会促进催化剂的碳化,但MnFe_(2)O_(4)对碳链的长短影响很小。然而,Mn能促进少量ε-Fe_(2)C的生成,这是导C_(2)^(=)-C_(4)^(=)致MnFe_(2)O_(4)具有较高选择性和C_(2)−C_(4)烯/烷比的原因。同时,所有尖晶石催化剂都具有较低的二氧化碳选择性,符合当前的绿色环保发展要求。 展开更多
关键词 费托合成 尖晶石 物相结构 C_(2)-C_(4)烯/烷比
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强钴—氧键合作用提升缺陷型Co_(2)MnO_(4)酸性析氧反应稳定性
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作者 谢静宜 吕千喜 +6 位作者 乔韦珍 卜辰宇 张昱声 翟雪君 吕仁庆 柴永明 董斌 《物理化学学报》 SCIE CAS CSCD 北大核心 2024年第3期48-49,共2页
通过实验和理论已经验证钴基氧化物是一种很有前景的析氧反应(OER)催化剂。然而,普通的钴基催化剂在酸性环境中非常不稳定,在酸性电解质中容易被腐蚀。因此,在目前的研究中,设计出能在强酸性条件下同时保持活性和稳定性的析氧催化剂是... 通过实验和理论已经验证钴基氧化物是一种很有前景的析氧反应(OER)催化剂。然而,普通的钴基催化剂在酸性环境中非常不稳定,在酸性电解质中容易被腐蚀。因此,在目前的研究中,设计出能在强酸性条件下同时保持活性和稳定性的析氧催化剂是实现大规模工业制氢应用的一项重要挑战。因此,我们报道了通过在四氧化三钴的尖晶石晶格中引入锰(Mn)从而产生富含缺陷的催化剂(CoMn_(1)O),它在酸性电解质中具有较长的使用寿命。我们利用X射线衍射(XRD)、X射线光电子能谱(XPS)、高分辨率透射电子显微镜(HRTEM)和能量色散光谱(EDS)元素图研究了晶相结构和化学价态。在引入锰后,由于局部晶体结构的改变,产生了大量的缺陷。此外,随着锰含量的增加,可以观察到Co 2p光谱的红移,这表明Co的总价逐渐增加,形成了更稳定的Co-O键。此外,当Mn与Co的比例达到1(CoMn_(1)O)时,目标催化剂表现出良好的OER活性,在10和50mA·cm^(-2)时,过电位分别为415和552 mV。详细的物理表征和电化学测试表明,CoMn_(1)O比不含锰的Co_(3)O_(4)(CoMn_(0)O)能稳定4倍以上的时间。这可以归因于锰的引入调节了Co的电子密度偏向O,从而形成更稳定的Co-O键。Mn可以通过延缓Co活性位点的氧化速率来促进酸性氧的进化,并进一步提升稳定性。密度泛函理论(DFT)计算进一步分析了CoMn_(1)O和CoMn_(0)O的电子结构。与CoMn_(0)O相比,CoMn_(1)O中Co 3d的d带中心(εd)向费米能级(EF)移动。这表明CoMn_(1)O通过加强与OER中间物的键合作用从而降低了反应能垒。本研究为设计非贵金属电催化剂实现高效稳定的酸性析氧提供有前景的策略。 展开更多
关键词 中空结构 钴锰尖晶石氧化物 钴锰普鲁士蓝类似物 酸性析氧反应
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固体废弃物铝灰和粉煤灰原位合成Spinel-Sialon复相材料的研究 被引量:5
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作者 董锦芳 黄朝晖 +3 位作者 陈博 黄军同 房明浩 刘艳改 《人工晶体学报》 EI CAS CSCD 北大核心 2009年第S1期371-374,共4页
本文利用铝灰和粉煤灰为原料,经原位铝热还原氮化法合成了Spinel-Sialon复相材料。通过XRD、SEM、EDS等分析手段,研究了合成温度和还原剂铝的添加量对合成产物物相及微观形貌的影响。结果表明:合成Spinel-Sialon的优化工艺参数为铝的添... 本文利用铝灰和粉煤灰为原料,经原位铝热还原氮化法合成了Spinel-Sialon复相材料。通过XRD、SEM、EDS等分析手段,研究了合成温度和还原剂铝的添加量对合成产物物相及微观形貌的影响。结果表明:合成Spinel-Sialon的优化工艺参数为铝的添加量为过量100%、合成温度为1550℃,保温时间3 h,合成得到发育良好的柱状β-Sialon及八面体形的镁铝尖晶石。合成温度、还原剂铝的添加量均是影响氮化产物的重要因素。随着温度的升高或还原剂铝的添加量增多,Al2O3越来越少,β-Sialon和镁铝尖晶石均增多,且β-Sialon的Z值增大,MgAl2O4转变成富铝尖晶石。 展开更多
关键词 铝灰 粉煤灰 铝热还原氮化 spinel-Sialon复相材料
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东南极米洛半岛尖晶石-堇青石麻粒岩变质作用与年代学研究
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作者 刘昕淑 王伟 +4 位作者 保红 龚庭楠 湛礼卿 刘晓春 赵越 《地质力学学报》 CSCD 北大核心 2024年第3期487-505,共19页
东南极普里兹构造带被认为受到格林维尔期及泛非期两期构造热事件的影响,分别与罗迪尼亚和冈瓦纳超大陆的演化密切相关,但对两期构造热事件的性质还存在争议。为了进一步完善该构造带的演化历史,从矿物学、岩石学、相平衡模拟、锆石年... 东南极普里兹构造带被认为受到格林维尔期及泛非期两期构造热事件的影响,分别与罗迪尼亚和冈瓦纳超大陆的演化密切相关,但对两期构造热事件的性质还存在争议。为了进一步完善该构造带的演化历史,从矿物学、岩石学、相平衡模拟、锆石年代学等角度对普里兹构造带米洛半岛尖晶石-堇青石麻粒岩进行了研究。结果表明其主期矿物组合为尖晶石+堇青石+黑云母+矽线石+少量石榴子石+钾长石+钛铁矿,温压条件为870~910℃、0.64~0.69 GPa,晚期退变至810~820℃、0.49~0.53 GPa,并暗示了更高的峰期变质条件(T>910℃,P>0.69 GPa)。CL图像显示锆石具有明显的核-幔-边结构,LA-ICP-MS锆石U–Pb年代学分析显示核部年龄主要集中在613±7 Ma到877±9 Ma,最大值916±11 Ma,比典型的格林维尔期年龄年轻。锆石边部加权平均年龄为526±8 Ma,其Th/U比值范围较大(0.06~1.23),多数Th/U比值较高(>0.1),应代表峰后冷却结晶阶段。尖晶石-堇青石麻粒岩记录了中低压/高温—超高温的变质条件,结合区域已有资料,可能具有顺时针轨迹,其变质演化历史可能反映了碰撞造山之后的伸展阶段,推测与冈瓦纳超大陆的聚合过程有关。 展开更多
关键词 东南极 尖晶石-堇青石麻粒岩 P-T轨迹 高温—超高温变质 相平衡模拟
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不同种类铝镁尖晶石细粉对刚玉尖晶石浇注料性能的影响
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作者 阎宁波 刘岩 +2 位作者 陈卢 郭鹏 钱凡 《耐火与石灰》 2024年第2期18-21,共4页
以板状刚玉颗粒和电熔尖晶石颗粒为骨料,以板状刚玉细粉、烧结或电熔尖晶石细粉、活性α-Al_(2)O_(3)微粉为基质,高纯铝酸钙水泥为结合剂,振动浇注成型,经1550℃高温烧成后制备刚玉尖晶石试样。研究了不同厂家烧结尖晶石细粉和电熔尖晶... 以板状刚玉颗粒和电熔尖晶石颗粒为骨料,以板状刚玉细粉、烧结或电熔尖晶石细粉、活性α-Al_(2)O_(3)微粉为基质,高纯铝酸钙水泥为结合剂,振动浇注成型,经1550℃高温烧成后制备刚玉尖晶石试样。研究了不同厂家烧结尖晶石细粉和电熔尖晶石细粉的化学成分、物相组成和粒度分布对刚玉尖晶石浇注料显微结构、烧后永久线变化率、显气孔率、体积密度、常温抗折强度、高温抗折强度和常温耐压强度的影响。 展开更多
关键词 铝镁尖晶石 刚玉尖晶石浇注料 热震稳定性 抗折强度 耐压强度
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Al_2O_3-ZrO_2-Spinel三元纳米复相陶瓷超塑性变形及组织演变 被引量:1
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作者 陈国清 杜巍 +2 位作者 王旭东 董红刚 侯晓多 《稀有金属材料与工程》 SCIE EI CAS CSCD 北大核心 2009年第A02期110-113,共4页
采用真空热压烧结工艺制备了三元纳米复相陶瓷并进行了超塑性压缩试验。结果表明:纳米复相陶瓷中的第二相在烧结和变形过程中有效地阻止了基体Al2O3的晶粒长大。在1650℃材料表现出良好的高应变速率超塑变形能力,变形抗力小于30MPa。微... 采用真空热压烧结工艺制备了三元纳米复相陶瓷并进行了超塑性压缩试验。结果表明:纳米复相陶瓷中的第二相在烧结和变形过程中有效地阻止了基体Al2O3的晶粒长大。在1650℃材料表现出良好的高应变速率超塑变形能力,变形抗力小于30MPa。微观组织观察表明由于变形过程中存在有益压应力,材料变形后晶界处未出现空洞,经变形量为60%的压缩变形后材料中存在较高密度的位错,位错主要存在于尖晶石和氧化锆第二相中,基体Al2O3的晶粒仍为等轴状,表明位错运动对晶界滑移起到了积极地协调作用。 展开更多
关键词 三元纳米复相陶瓷 超塑性 组织演变 位错
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连接体用Co-Mn基合金与尖晶石涂层的设计及其初期热生长与导电性能研究
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作者 邵勇 周天池 +5 位作者 赖永彪 孙杭 丁江涛 毛胜勇 黄铭瑞 郭平义 《江苏科技大学学报(自然科学版)》 CAS 2020年第1期26-33,共8页
MnxCo3-xO4尖晶石具有很好的铬离子外扩散抑制性能,且通过调整组成可设计最佳的热膨胀系数与电导率,以满足铁素体连接体的应用.Co-Mn合金涂层在热生长/氧化过程中要转化为性能优异的尖晶石层,除受到涂层成分、厚度与制备方法等因素的影... MnxCo3-xO4尖晶石具有很好的铬离子外扩散抑制性能,且通过调整组成可设计最佳的热膨胀系数与电导率,以满足铁素体连接体的应用.Co-Mn合金涂层在热生长/氧化过程中要转化为性能优异的尖晶石层,除受到涂层成分、厚度与制备方法等因素的影响,还受到热生长过程中的氧分压、温度等的影响.文中通过研究高Mn的Co-40Mn和低Mn的Co-10Mn合金,在不同温度和氧分压下初期热生长特点选择涂层成分,在相对低温(750℃)时氧化物组分受氧分压影响明显;并研究了高Mn合金Co-38Mn-2La和Co-40Mn涂层在固体氧化物燃料电池服役温度中的初期热生长特点,结果表明所生成的产物为Co 3O 4夹杂少量(Co,Mn)3O 4尖晶石,这与相同反应条件下铸态合金存在着差异.Co-40Mn和Co-38Mn-2La氧化后涂层面比电阻遵循半导体氧化物随温度的变化规律,lg(ASR/T)vs.10^3/T之间均满足线性关系,Co-38Mn-2La涂层面比电阻值在500~800℃时低于Co-40Mn涂层. 展开更多
关键词 尖晶石 co-mn 涂层 热生长
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