doi10.1112S0024610706022861 CONSTRUCTIONS RELATED TO THE RéDEI PROPERTY OF GROUPS
On the negative effective mass density in acoustic metamaterials
On the negative effective mass density in acoustic metamaterials
H.H. Huang a, C.T. Sun a,*,G.L. Huang b
a School of Aeronautics and Astronautics, Purdue University, W. Lafayette, IN 47907, USA b Department of Systems Engineering, University of Arkansas at Little Rock, Little Rock, AR, 72204, USA
* Corresponding author. Tel.: +1 765 494 5130; fax: +1 765 494 0307. E-mail address: sun@ (C.T. Sun).
氧化钛纳米片材料的合成及其催化应用进展
CHEMICAL INDUSTRY AND ENGINEERING PROGRESS 2017年第36卷第7期·2488·化 工 进展氧化钛纳米片材料的合成及其催化应用进展李路1,2,徐金铭2,齐世学1,黄延强2(1烟台大学化学与化工学院,山东 烟台 264005;2中国科学院大连化学物理研究所,航天催化与新材料研究室,辽宁 大连 116023)摘要:氧化钛纳米片材料为一种新兴的二维层状材料,在催化、环境、能源和电子领域引起人们广泛的关注。
本文从催化研究的角度出发,综述了氧化钛纳米片材料的结构、制备方法、金属及非金属元素的掺杂、纳米片基复合材料和其在光催化、光电催化和热催化等方面的应用进展。
分析表明氧化钛纳米片材料拥有特殊的形貌和特别的物理化学性质,通过控制材料的组成及结构变化,能够实现氧化钛纳米片材料的多种功能化。
指出氧化钛纳米片材料虽然有着优良的性能,但是在实际应用中远不能满足要求。
因此,优化合成和探索新形式的二氧化钛纳米片材料,对其表面进行改性及开发具有特殊功能纳米复合材料是解决其瓶颈的有效途径。
探索催化反应过程中的反应机理,开发氧化钛纳米片基工业应用催化剂将是今后重要的研究方向。
关键词:氧化钛纳米片;层状钛酸盐;催化;合成;纳米材料中图分类号:O611.4 文献标志码:A 文章编号:1000–6613(2017)07–2488–09 DOI :10.16085/j.issn.1000-6613.2016-2340Recent advances in titanium oxide nanosheets for catalytic applicationsLI Lu 1,2,XU Jinming 2,QI Shixue 1,HUANG Yanqiang 2(1College of Chemistry and Chemical Engineering ,Yantai University ,Yantai 264005,Shandong ,China ;2Laboratory of Catalysts and New Materials for Aerospace ,Dalian Institution of Chemical Physics ,Chinese Academy of Science ,Dalian 116023,Liaoning ,China )Abstract: As a new class 2D layered materials ,Titanium oxide nanosheets have attracted great interest inthe fields of catalysis ,environment ,energy and electronics. In this work ,we provide an overview of the recent advance of titanium oxide nanosheets on their layered structure ,synthetic methods ,doping with metals or nonmetal ,as well as their nanocomposites and applications in catalysis. Recent researches indicate that titanium oxide nanosheets with unique structure and special physical and chemical properties can achieve multiple functions by controlling their compositions and structures. Although titanium oxide nanosheets have a lot of advantages ,they are still far from practical applications. Therefore it is demanded to explore new synthesis ,doping and modification methods ,and develop new composite materials. In addition ,the reaction mechanism in the catalytic reaction process and the industrial application of titanium oxide nanosheets will be important research directions in the future. Key words :titanium oxide nanosheets ;layered titanate compounds ;catalysis ;synthesis ;nanomaterials助理研究员,从事有序介孔材料合成及表面修饰和生物质催化转化制化学品相关科研工作。
深层页岩干酪根纳米孔隙中甲烷微观赋存特征
第 51 卷 第 5 期石 油 钻 探 技 术Vol. 51 No.5 2023 年 9 月PETROLEUM DRILLING TECHNIQUES Sep., 2023doi:10.11911/syztjs.2023086引用格式:黄亮,冯鑫霓,杨琴,等. 深层页岩干酪根纳米孔隙中甲烷微观赋存特征[J]. 石油钻探技术,2023, 51(5):112-120.HUANG Liang, FENG Xinni, YANG Qin, et al. Microscopic occurrence characteristics of methane in kerogen nanopores of deep shale reservoirs [J]. Petroleum Drilling Techniques,2023, 51(5):112-120.深层页岩干酪根纳米孔隙中甲烷微观赋存特征黄 亮1,2, 冯鑫霓1,2, 杨 琴1,2, 吴建发3, 杨学锋3, 黄 山3(1. 油气藏地质及开发工程全国重点实验室(成都理工大学), 四川成都 610059;2. 成都理工大学能源学院,四川成都 610059;3. 中国石油西南油气田分公司页岩气研究院,四川成都 610051)摘 要: 深层页岩储层甲烷高温高压条件下的赋存特征是准确评估页岩气储量的关键。
首先,基于深层页岩龙马溪组干酪根分子结构单元,构建干酪根不同形状和孔径的纳米孔隙分子模型;然后,采用巨正则蒙特卡洛和分子动力学耦合方法,开展甲烷赋存模拟,分析压力、温度、孔径和孔隙形状对甲烷赋存量的影响规律;最后,研究甲烷微观赋存机理,分析甲烷微观分布特征、甲烷–壁面微观作用特征以及甲烷优先吸附位。
研究表明:在深层高压条件下,甲烷过剩吸附量和溶解量受温度影响较小;随温度升高,甲烷绝对吸着量和游离气体量减少;干酪根介孔孔径对甲烷吸附气和溶解气量基本无影响,孔径引起的总气体量变化主要由游离气贡献;与圆管孔相比,狭缝孔中甲烷总气体量更大,但过剩吸附量较少;甲烷分子优先吸附于干酪根结构上的噻吩位点。
生物质成型燃料制备及燃烧过程添加剂应用及研究进展
2017年第36卷第4期 CHEMICAL INDUSTRY AND ENGINEERING PROGRESS·1247·化 工 进展生物质成型燃料制备及燃烧过程添加剂应用及研究进展崔旭阳1,杨俊红1,雷万宁2,黄涛2,王朴方1,贾晨1(1中低温热能高效利用教育部重点实验室,天津大学机械工程学院,天津 300072;2西安瑞行城市热力发展集团有限公司,陕西 西安 710100)摘要:生物质成型燃料(densified biomass briquetting fuel ,DBBF )添加剂的筛选和应用对于DBBF 的规模化制备和高效燃烧均具有重要意义。
目前相关文献综述较多集中在DBBF 和其制备、燃烧设备方面。
本文基于尾气排放管理和高效燃烧,围绕DBBF 的提质改性,针对其在制备和燃烧环节使用的添加剂,从功能分类和作用机理的角度出发,综述了黏结剂、防腐降沉添加剂、助燃剂三大类DBBF 添加剂的研究进展。
相比较,DBBF 黏结剂种类可选择性高、廉价易得,但其对于燃料的机械强度的改善有待提高;DBBF 防腐降沉添加剂来源广泛,但工作效率低,工业运用效果有待提升;DBBF 助燃剂虽然种类较少、机理尚不明确、无统一的研究开发标准,但是助燃剂能够有效改善DBBF 的燃烧性能,提高燃烧效率。
最后,明确给出了常见DBBF 添加剂的筛选原则,并展望了未来DBBF 添加剂的研究方向,即在研究开发新型DBBF 添加剂的同时,提升黏结剂和防腐降沉添加剂的工作效果,大力研发和完善DBBF 助燃剂等具有复合功能效果的新型添加剂。
关键词:生物燃料;添加剂;黏结;腐蚀;燃烧中图分类号:U473.5 文献标志码:A 文章编号:1000–6613(2017)04–1247–11 DOI :10.16085/j.issn.1000-6613.2017.04.013Recent progress in research and application of DBBF additive inpreparation and combustion processCUI Xuyang 1,YANG Junhong 1,LEI Wanning 2,HUANG Tao 2,WANG Pufang 1,JIA Chen 1(1Key Laboratory of Efficient Utilization of Low and Medium Grade Energy ,Ministry of Education ,School of Mechanical Engineering ,Tianjin University ,Tianjin 300072,China ;2Xi 'an Raising Energy Group Co.,Ltd.,Xi 'an710100,Shaanxi ,China )Abstract :The screening and application of densified biomass briquetting fuel (DBBF )additive is of great importance for the large-scale preparation and efficient combustion of DBBF. At present ,the relevant literature reviews are more concentrated on the DBBF ,its preparation ,and combustion equipment. Based on emissions management and efficient combustion ,DBBF modification ,fuel additives preparation ,and functional classification and mechanism ,this paper summarized the research progress of DBBF additives for adhesives ,anti-corrosion additives ,and accelerant. DBBF binders have high selectivity and low price ,but the mechanical strength of the fuel needs to be improved. DBBF additives for anti-corrosion and anti-settling are abundant ,but their work efficiencies are low. There were few DBBF accelerants.Their combustion mechanism is not clear. And there is no unified standards for research and development. The accelerantadditive can effectively improve the combustion performance of DBBF. Finally ,the principles of selecting DBBF common additives and能源开发与管理。
运载火箭自适应增广控制参数设计及稳定性裕度分析
第46卷 第1期2024年1月系统工程与电子技术SystemsEngineeringandElectronicsVol.46 No.1January 2024文章编号:1001 506X(2024)01 0271 09 网址:www.sys ele.com收稿日期:20221212;修回日期:20230425;网络优先出版日期:20230906。
网络优先出版地址:http:∥link.cnki.net/urlid/11.2422.TN.20230906.1020.012基金项目:国家自然科学基金(12002398)资助课题 通讯作者.引用格式:张亮,刘思,赵康伟,等.运载火箭自适应增广控制参数设计及稳定性裕度分析[J].系统工程与电子技术,2024,46(1):271 279.犚犲犳犲狉犲狀犮犲犳狅狉犿犪狋:ZHANGL,LIUS,ZHAOKW,etal.Parametersdesignandstabilitymarginanalysisofadaptiveaugmentingcontrolforlaunchvehicle[J].SystemsEngineeringandElectronics,2024,46(1):271 279.运载火箭自适应增广控制参数设计及稳定性裕度分析张 亮1, ,刘 思2,赵康伟1,胡存明2(1.中山大学航空航天学院,广东深圳518107;2.上海航天控制技术研究所,上海201100) 摘 要:针对运载火箭主动飞行段的强鲁棒姿态控制系统设计要求,提出自适应增广控制器(adaptiveaugmentingcontroller,AAC)的参数设计方法以及稳定性裕度分析方法。
首先,针对传统运载火箭建立了小扰动线性化方程,推导了传递函数,并基于特征点参数设计了比例微分(proportional derivative,PD)控制器及校正网络。
然后,开展了AAC设计,给出调节参数的具体设计方法和准则。
氧吲哚生物碱Humantenine关键骨架的立体选择性构建
Vol.33高等学校化学学报No.122012年12月 CHEMICAL JOURNAL OF CHINESE UNIVERSITIES 2676~2680氧吲哚生物碱Humantenine 关键骨架的立体选择性构建肖 涛,周 旋,宋 颢(四川大学华西药学院,成都610041)摘要 通过炔锂试剂11与环氮化合物10的区域和立体选择性加成构建了humantenine 等钩吻生物碱不对称全合成路线中的重要中间体13;通过酸催化的烯醇⁃氧环合策略一步构建了humantenine 等钩吻生物碱结构中的四氢吡喃环㊁环氧己烷㊁C7季碳中心和C3手性中心;最终从已知化合物7出发,以16步1.5%的总收率完成了humantenine(2),humantenine N 4⁃oxide(3),gelseganines A(4)和gelseganines B(5)等钩吻生物碱关键中间体化合物6的不对称合成.关键词 Humantenine;不对称合成;烯醇⁃氧环合;氧吲哚生物碱中图分类号 O621.3 文献标识码 A doi :10.7503/cjcu20120494收稿日期:2012⁃05⁃23.基金项目:国家自然科学基金(批准号:21021001)资助.联系人简介:周 旋,男,博士,主要从事天然产物全合成研究.E⁃mail:zhouxuan526@宋 颢,女,博士,讲师,主要从事天然产物全合成研究.E⁃mail:songhao@钩吻即马钱科植物胡蔓藤(Gelsemium elegans Benth.),由于其有剧毒,民间主要以外用为主,近年来人们逐渐发现钩吻还具有抗肿瘤[1~4]㊁消炎镇痛[5~6]及影响免疫功能[7~9]等药理作用.钩吻生物碱是一个庞大的家族,按结构可分为gelsemine 类㊁gelsenicine 类㊁humantenine 类㊁sarpagine 类㊁semper⁃virine 类和koumine 类等6类[10].钩吻碱(Gelsemine)在钩吻生物碱中最具代表性,合成化学家们已对其合成方法进行了深入研究[11~15],而对于humantenine(2),humantenine N 4⁃oxide(3)[16],gelseganines A(4)和gelseganines B(5)等钩吻生物碱单体的合成研究鲜见报道[17].为了开发更多高效低毒的创新药物,对于钩吻碱以外的钩吻生物碱单体进行合成研究也非常必要.如Scheme 1所示,humantenine (2),humantenine N 4⁃oxide(3),gelseganines A(4)和gelseganines B(5)等生物碱的结构中均包含有相同的氧吲哚螺环骨架6,因此对笼状化合物6的制备是合成以上4个钩吻生物碱单体的关键所在.本文主要对氧吲哚螺环化合物6的不对称合成进行研究.Scheme 1 Structures of gelsemium alkaloids在前文[15]报道的(+)⁃钩吻碱的全合成路线中,以环氮化合物7为原料经过6步反应高立体选择性地构建了C5和C16手性中心并得到了关键化合物13.化合物13同时也是制备氧吲哚螺环化合物6的关键中间体.然而,以上制备中间体13的合成路线较长,官能团转化繁琐,不利于大规模制备.因此,有必要对原有的合成路线进行优化,以期高效地制备关键中间体13,为humantenine(2),humante⁃nine N 4⁃oxide(3),gelseganines A(4)和gelseganines B(5)等生物碱的合成提供物质基础.基于以上分析,本文对重要中间体13的合成路线进行了改进(见Scheme 2).由化合物7出发,以三氟甲烷磺酸甲酯季铵盐10与炔锂试剂11的区域和立体选择性加成为关键反应,最终以3步30%的总收率高效㊁简洁地制备了关键中间体13.Scheme 2 Improved synthesis routes of compound 13在制得关键化合物13的基础上,参照文献[15]方法经过11步反应,以13%的总收率制备了化合物14.从化合物14出发,通过氢化加成得到化合物15,然后经过酸催化的烯醇⁃氧环合策略一步构建了humantenine 等钩吻生物碱结构中的四氢吡喃环㊁环氧己烷㊁C7季碳中心和C3手性中心(见Scheme 3).最终从已知化合物7出发,以16步1.5%的总收率完成了关键化合物6的不对称合成,为humantenine(2),humantenine N 4⁃oxide(3),gelseganines A(4)和gelseganines B(5)等生物碱的不对称全合成提供了物质基础.Scheme 3 Asymmetric synthesis of compound 61 实验部分1.1 试剂与仪器所用无水溶剂均按照标准方法进行处理.所用试剂均为分析纯试剂,除特别说明外均直接使用;薄层层析硅胶板(烟台江友硅胶开发有限公司);柱层析硅胶(安徽良臣硅源材料有限公司).Bruker AC⁃E200型核磁共振仪和Varian Unit INOVA 400型高分辨超导核磁共振仪(CDCl 3为溶剂,TMS 为内标);Nicolet MX⁃1型红外光谱仪;Bruker FT⁃MS 型高分辨质谱仪.7762 No.12 肖 涛等:氧吲哚生物碱Humantenine 关键骨架的立体选择性构建8762高等学校化学学报 Vol.33 1.2 实验过程1.2.1 化合物9的合成 参照文献[15]方法合成化合物9.以化合物7(1g,4.6mmol)为原料,所得粗产品经硅胶柱层析纯化[V(石油醚)∶V(乙酸乙酯)=1∶1],得到产物9(1.21g,4.5mmol),收率98%.[α]20D=-8.5°(c=0.75,CHCl3).1H NMR(400MHz,CDCl3),δ:4.04(dd,J=2.8,12.4Hz, 1H),3.84(d,J=11.2Hz,1H),3.74(dd,J=8.4,12.4Hz,1H),3.53~3.47(m,1H),3.06~3.00 (m,1H),2.83~2.76(m,1H),2.73~2.62(m,2H),2.30~2.26(m,1H),1.90~1.87(m,1H), 0.90(s,9H),0.08(s,6H).13C NMR(100MHz,CDCl3),δ:118.9,61.6,59.1,46.6,42.9,40.6, 25.8,25.7,18.8,-5.4.IR(KBr),~ν/cm-1:3395,2930,2884,2250,1256,1104,838,778.HRMS (M+H+)(C13H26N2O2Si计算值),m/z:271.1848(271.1842).1.2.2 化合物12的合成 将化合物9(1.21g,4.5mmol)溶于10mL二氯甲烷中,于0℃下加入三氟甲烷磺酸甲酯(1.48g,9mmol),并在此温度下反应2h,然后减压蒸除溶剂,得到粗产品季铵盐,不经纯化直接进行下一步反应.将季铵盐置于干燥反应器中,充氮除氧,加入干燥的四氢呋喃溶液(10 mL),降温至-78℃,慢慢滴加炔锂试剂11(13.5mmol)的四氢呋喃溶液,于-78℃反应1h后升至0℃反应2h.然后加入饱和氯化铵溶液,分出有机层,水层用乙酸乙酯萃取3次,合并有机层,用无水硫酸镁干燥,过滤,抽干溶剂,经柱层析[V(石油醚)∶V(乙酸乙酯)=1∶1]得到淡黄色油状化合物12(1.11g),收率60%.[α]20D=-6.7°(c=0.65,CHCl3).1H NMR(400MHz,CDCl3),δ:5.23(s, 1H),4.03(dd,J=2.8,10.8Hz,1H),3.87~3.82(m,3H),3.71~3.67(m,2H),3.57~3.54(m, 2H),3.06(t,J=6.8Hz,2H),3.96(t,J=2.4Hz,1H),2.72(brs,1H),2.49(t,J=6.8Hz,2H), 2.38(s,1H),1.23(t,J=7.2Hz,6H),0.90(s,9H),0.70(s,6H).13C NMR(100MHz,CDCl3),δ: 118.6,91.2,83.7,79.6,67.5,65.5,61.5,60.7,60.6,52.5,36.1,32.7,25.8,18.0,17.5, 15.0,-5.6.IR(KBr),~ν/cm-1:3450,2931,2859,2248,1360,1260,1140,1056,839,780,670. HRMS(M+H+)(C21H40N2O4Si计算值),m/z:413.2838(413.2836).1.2.3 化合物13的合成 参照文献[18]方法合成化合物13.以化合物12(1.11g,2.7mmol)为原料,所得粗产品经硅柱层析纯化[V(石油醚)∶V(乙酸乙酯)=5∶1],得到淡黄色油状化合物13(0.62 g,1.35mmol),收率50%.HRMS(M+H+)(C23H45N2O5Si计算值),m/z:457.3102(457.3098).谱图数据与文献[15]结果一致.1.2.4 化合物15的合成 将化合物14(0.3g,0.65mmol)溶于甲醇(15mL)中,加入0.03g Lindlar 催化剂,充换氢气,室温下反应45min后将催化剂滤掉,抽干溶剂,经柱层析[V(石油醚)∶V(乙酸乙酯)=1∶1]得到主㊁次异构体摩尔比为3∶2的淡黄色油状混合物15(0.285g,0.61mmol),收率95%.主要异构体:1H NMR(400MHz,CDCl3),δ:7.30(t,J=7.6Hz,1H),7.22(d,J=7.6Hz,1H),7.08 (t,J=7.6Hz,1H),6.98(t,J=7.6Hz,1H),4.69(d,J=6.4Hz,1H),4.64(d,J=6.0Hz,1H), 4.55~4.52(m,1H),4.14~4.10(m,1H),3.92(d,J=10Hz,1H),3.85(dd,J=4,11.2Hz,1H), 3.39(s,3H),3.36(s,3H),3.35(s,3H),3.34(d,J=4Hz,1H),3.08(d,J=12Hz,1H),2.95(s, 1H),2.41(dd,J=6.8,11.6Hz,1H),2.26(s,3H),2.18~2.11(m,4H),2.08~1.92(m,5H). 13C NMR(100MHz,CDCl3),δ:172.3,140.0,127.9,126.2,123.7,123.0,121.2,107.0,103.2, 96.5,64.1,63.4,63.0,55.5,53.9,52.9,42.2,40.7,40.0,36.5,34.5,32.0,30.6,29.6.IR (KBr),~ν/cm-1:2927,2851,1723,1464,1322,1198,1104,1047,957,752.HRMS(M+H+) (C24H35N3O6计算值),m/z:462.2604(462.2604).次要异构体:1H NMR(400MHz,CDCl3),δ:7.31(t,J=7.6Hz,1H),7.14(d,J=7.6Hz,1H), 7.06(t,J=7.6Hz,1H),6.98(t,J=7.6Hz,1H),4.64(d,J=6Hz,2H),4.55~4.52(m,1H), 4.04~4.02(m,1H),3.92(d,J=10Hz,1H),3.85(dd,J=4,11.2Hz,1H),3.38(s,3H),3.36(s, 3H),3.35(s,3H),3.17~3.14(m,1H),2.89(d,J=4Hz,1H),2.83(d,J=10Hz,1H),2.50 (brs,1H),2.34(s,3H),2.18~2.11(m,4H),2.08~1.92(m,5H).13C NMR(100MHz,CDCl3),δ: 172.3,140.0,128.1,126.2,124.6,122.6,120.9,107.2,103.2,96.8,64.1,63.3,63.0,55.6,54.1,52.9,42.0,41.2,40.0,36.5,34.5,32.0,30.6,29.6.IR(KBr),~ν/cm -1:2927,2851,1723,1464,1322,1198,1104,1047,957,752.HRMS (M +H +)(C 24H 35N 3O 6计算值),m /z :462.2604(462.2604).1.2.5 化合物6的合成 将化合物15(29mg,0.062mmol)溶于干燥甲苯(3mL)中,加入D (+)⁃10⁃樟脑磺酸(14g,0.6mmol),加热回流12h 后加入饱和碳酸氢钠溶液,分出有机层,水层用乙酸乙酯萃取3次,用无水硫酸镁干燥,过滤,抽干溶剂,经柱层析[V (石油醚)∶V (乙酸乙酯)=1∶4]得到淡黄色油状化合物6(6.5mg,0.019mmol),收率30%.[α]20D =-85.6°(c =0.25,CHCl 3).1H NMR(400MHz,CDCl 3),δ:7.37(d,J =7.6Hz,1H),7.33(t,J =7.6Hz,1H),7.12(t,J =7.6Hz,1H),7.02(d,J =7.6Hz,1H),4.20(d,J =11.2Hz,1H),4.07(dd,J =6,11.2Hz,1H),4.02(s,3H),3.71(d,J =8Hz,1H),3.41~3.38(m,1H),3.29(t,J =12.4Hz,1H),3.12~3.09(m,1H),2.79(dd,J =5.2,12.8Hz,1H),2.50(t,J =7.6Hz,1H),2.44~2.38(m,2H),2.33(s,3H),2.31~2.29(m,1H),2.26~2.22(m,1H),1.74(dd,J =9.2,15.6Hz,1H).13C NMR(100MHz,CDCl 3),δ:174.4,139.4,130.8,128.3,125.5,123.1,119.2,107.5,72.0,66.7,63.3,60.2,54.9,44.1,42.0,37.2,31.9,27.2,24.4,23.1.IR(KBr),~ν/cm -1:2962,2921,2239,1719,1463,1261,1100,955,802,750.HRMS(M+H +)(C 20H 23N 3O 3计算值),m /z :354.1815(354.1818).2 结果与讨论2.1 中间体13合成路线的优化对中间体13的合成路线进行了改进(见Scheme 2),仅通过3步反应即可高效简洁地制备目标化合物.但化合物13的总产率不高,其原因可能是化合物9转化成季铵盐的转化率不高,且季铵盐10未经纯化直接用于下一步反应,导致化合物12的收率低;化合物12可能因为丙烯腈位阻的原因,导致在羟基上进行MOM 保护时产率不高.2.2 通过酸催化的烯醇⁃氧环合策略构建Humantenine 等氧吲哚生物碱螺环骨架通过D (+)⁃10⁃樟脑磺酸催化的烯醇⁃氧环合策略一步构建了humantenine 等钩吻生物碱结构中的四氢吡喃环㊁环氧己烷㊁C7季碳中心和C3手性中心,得到了关键化合物6.通过二维谱确定了化合物6的结构,并通过化合物6与humantenine 的1H NMR 和13C NMR 图谱[10]对比确定了化合物6中C7季碳中心的构型与humantenine 中C7位构型相同.最终从已知化合物7出发,以16步1.5%的总收率完成了humantenine(2),humantenine N 4⁃oxide(3),gelseganines A(4)和gelseganines B(5)等生物碱的关键中间体化合物6的不对称合成.Table 1 Asymmetric synthesis of compound 6through enol⁃oxonium cyclization Entry Acid Solvent Yield(%)1p⁃TsOH Chloroform 02p ⁃NsOH 03D (+)⁃10⁃camphorsulfonic acid 04TFA /TFAA(volume ratio,1∶1)Acetonitrile 05p ⁃TsOH 06p ⁃NsOH 07D (+)⁃10⁃camphorsulfonic acid 08TFA /TFAA(volume ratio,1∶1)Toluene 09p ⁃TsOH 010p ⁃NsOH 011D (+)⁃10⁃camphorsulfonic acid 3012TFA /TFAA(volume ratio,1∶1)013D (+)⁃10⁃camphorsulfonic acid Benzene 1014D (+)⁃10⁃camphorsulfonic acid Xylene 5由于通过酸催化的烯醇⁃氧环合策略制备化合物6时产率不高.以对甲苯磺酸㊁对硝基苯磺酸㊁D (+)⁃10⁃樟脑磺酸和三氟醋酸/三氟醋酐(体积比1∶1)分别在不同溶剂中的催化反应为对象对反应条件进行了优化.由表1可见,底物在甲苯(表1Entry 11)㊁苯(表1Entry 13)或二甲苯(表1Entry 14)中用D (+)⁃10⁃樟脑磺酸催化才能得到目标产物,其它条件均未得到目标产物.甲苯中的反应效果最好,但产率仅为30%.其原因可能是底物15在酸性条件下脱去保护基形成烯醇氧16.化合物16的骨架趋向于平面结构,氧吲哚的C7位与C3氧距离较远,不易成9762 No.12 肖 涛等:氧吲哚生物碱Humantenine 关键骨架的立体选择性构建0862高等学校化学学报 Vol.33 环;当用苯作溶剂回流时,因为温度不高,达不到环合时需要的能量,所以原料大量剩余;当用甲苯作溶剂时,虽然能达到环合时需要的能量,可能又因为温度太高造成了底物大量分解;当用二甲苯作溶剂时,温度更高,效果更不理想.参 考 文 献[1] Chi D.B.,Lei L.S.,Jin H..J.First Mil.Med.Univ.[J],2003,23:911 913[2] Lu J.M.,Qi Z.R.,Liu G.L..Chin.J.Cancer[J],1990,9:472 474[3] Chen Z.L..J.Navy.Med.[J],1984,3:52 53[4] Wu D.R.,Qin R.,Cai J..Pharmacol.Clin.Chin.Mater.Med.[J],2006,22:6 8[5] Tan J.Q.,Qiu C.Z.,Zhen L.Z..Pharmacol.Clin.Chin.Mater.Med.[J],1988,4:24 28[6] Rujjanawate C.,Kanjanapothi D.,Panthong A..J.Ethnopharmacol.[J],2003,89:91 95[7] Wang Z.R.,Huang C.Q.,Zhang Z.Y..Acad.J.First Med.Coll.PLA[J],2005,25:562 564[8] Lei L.S.,Sun L.S.,Yang S.Q..Pharmacol.Clin.Chin.Mater.Med.[J],1999,15:10 13[9] Zhou L.Y.,Wan K.,Huang L.Q..Chin.J.Exp.Clin.Immunol.[J],1992,4:14 15[10] Lin L.Z.,Ni C.Z.,Clardy J.,Cordell G.A..J.Nat.Prod.[J],1989,52:588 594[11] Fukuyama T.,Liu G..J.Am.Chem.Soc.[J],1996,118:7426 7427[12] Ng F.W.,Lin H.,Danishefsky S.J..J.Am.Chem.Soc.[J],2002,124:9812 9824[13] Madin A.,O’Donnell C.J.,Oh T.,Old D.W.,Overman L.E.,Sharpe M.J..Angew.Chem.Int.Ed.[J],1999,38:29342936[14] Danishefsky S.J..Angew.Chem.Int.Ed.[J],2003,42:36 51[15] Zhou X.,Xiao T.,Iwama Y.,Qin Y..Angew.Chem.Int.Ed.[J],2012,51:4909 4912[16] Yin S.,He X.F.,Wu Y.,Yue n J.[J],2008,3:1824 1829[17] Takayama H.,Masubuchi K.,Kitajima M.,Aimi N.,Sakai S.I..Tetrahedron[J],1989,45:1327 1336[18] ZHANG Ying⁃Peng(张应鹏),LI Ying(李瀛),XUE Ji⁃Jun(薛吉军),NIU Ying⁃Hui(牛颖辉),WU Jiang(吴疆).Chem.J.ChineseUniversities(高等学校化学学报)[J],2004,25(2):292 293Stereoselective Construction of the Key Skeleton ofOxindole Alkaloid HumantenineXIAO Tao,ZHOU Xuan*,SONG Hao*(West China School of Pharmacy,Sichuan University,Chengdu610041,China)Abstract Humantenine⁃type compounds are a group of Gelsemium alkaloids isolated from Gelsemium elegans Benth that possess complex structures and remarkable activities.In this work,the synthetic approaches of them were investigated.The key structure of Gelsemium alkaloids humantenine(13)was efficiently constructed through a region⁃and stereoselectivity addition of compound11to compound10.A multi⁃step,one pot eno⁃loxonium cyclization cascade was used in a highly efficient way to construct,simultaneously,the tetrahydropy⁃ran ring,oxepane ring,C3chiral carbon and C7chiral quaternary carbon of humantenine(2).Based the above created methodology,the key skeleton(6)of oxindole alkaloid humantenine(2),humantenine N4⁃oxide (3),gelseganines A(4)and gelseganines B(5)was asymmetric synthesized in16steps with a total yield of 1.5%.The structures of the compounds were confirmed by IR,1H NMR,13C NMR and high resolution mass spectrometer(HRMS).Especially,we successfully synthesized hmantenine⁃type skeleton which indicates this method has a widely range of applications.Keywords Humantenine;Asymmetric synthesis;Enol⁃oxonium cyclization;Oxindole alkaloid(Ed.:J,Z,K)。
甲烷微尺度燃烧中气相反应与催化反应间的相互作用
CHEMICAL INDUSTRY AND ENGINEERING PROGRESS 2017年第36卷第6期·2094·化 工 进展甲烷微尺度燃烧中气相反应与催化反应间的相互作用刘子琨,周俊虎,杨卫娟,王业峰,岑可法(浙江大学能源清洁利用国家重点实验室,浙江 杭州 310027)摘要:以往对甲烷微尺度催化燃烧的研究中,甲烷的气相反应往往没有受到足够的重视,有时候甚至被忽略。
为了了解气相反应在甲烷的微尺度燃烧中所起的作用,本文使用了计算流体力学软件Fluent 对CH 4和空气的预混气体在微尺度平板燃烧器中的催化燃烧过程进行了数值模拟,对比在0.2mm 和1mm 两种间距的微尺度平板燃烧器内CH 4的催化燃烧过程,研究了微尺度平板燃烧器内CH 4气相反应与CH 4催化反应的相互影响,其中重点研究了CH 4气相反应对CH 4催化反应的影响。
模拟结果显示:①在间距为0.2mm 和1mm 的微尺度平板燃烧器中,CH 4气相反应均是由CH 4催化反应所引起;②在0.2mm 间距的微尺度平板燃烧器中,CH 4气相反应产生的OH 促进了CH 4催化反应的进行;③在1mm 间距的微尺度平板燃烧器中,CH 4气相反应对CH 4催化反应仍然具有促进作用,但对CH 4催化反应的抑制作用更为显著。
研究结果可以为设计和开发高效稳定的微尺度平板燃烧器提供参考。
关键词:催化;甲烷;微尺度;模拟中图分类号:TK16 文献标志码:A 文章编号:1000–6613(2017)06–2094–07 DOI :10.16085/j.issn.1000-6613.2017.06.018Interactions between gas-phase reaction and catalytic reaction in methanemicroscale combustionLIU Zikun ,ZHOU Junhu ,YANG Weijuan ,WANG Yefeng ,CEN Kefa(State Key Laboratory of Clean Energy Utilization ,Zhejiang University ,Hangzhou 310027,Zhejiang ,China )Abstract :In previous studies of CH 4 microscale catalytic combustion ,CH 4 gas-phase reaction usually was not paid enough attention and even was ignored sometimes. To know the role of CH 4 gas-phase reaction playing in CH 4 microscale catalytic combustion ,a simulation of CH 4/air premixed gas catalytic combustion in microscale parallel plate combustor was done in computational fluid dynamics software. CH 4 catalytic combustion inmicro scale parallel plate combustors of 0.2mm and 1mm distance were compared. The interactions between CH 4 gas-phase reaction and CH 4 catalytic reaction were investigated ,and the effect of CH 4 gas-phase reaction on CH 4 catalytic reaction was investigated particularly. Several regularities were revealed by simulation results. First ,CH 4 gas-phase reaction was caused by CH 4 catalytic reaction in microscale parallel plate combustors of 0.2mm and 1mm distance. Second ,in microscale parallel plate combustor of 0.2mm distance ,OH produced from CH 4 gas-phase reaction promoted CH 4 catalytic reaction. Third ,in microscale parallel plate combustor of 1mm distance ,CH 4 gas-phase reaction still had positive effect on CH 4 catalytic reaction ,but its negative effect was more remarkable. The results can be used to provide reference to the development of efficient and stable microscale parallel plate combustor. Key words :catalysis ;methane ;microscale ;simulation究。
First-principles study of the structural, vibrational, phonon and thermodynamic
1. Introduction Ultra-high temperature ceramics (UHTCs) with melting temperatures in excess of 3000 K are usually composed by the refractory borides, carbides and nitrides of early transition metals [1–7]. Among the UHTCs, transition metal carbides (TMC) such as TiC, ZrC and HfC are metallic compounds with unique physical and chemical properties including an extremely high melting point and hardness, chemical stability, corrosion resistance combined with metallic electrical and thermal conductivities [5–10]. These features give transition metal carbides the capability to withstand high temperatures in oxidizing environments, making them candidates for applications in the atmosphere of extreme thermal and chemical environments [6,7]. The structural, vibrational, phonon and thermodynamic properties of IVb group transition metal carbides have been investigated experimentally [10–17] and theoretically [13,18–28] in the earlier reports. In the 1970s, the phonon dispersion relations of TiC, ZrC and HfC were measured using inelastic neutron scattering by Pintschovius et al. [10] and Smith et al. [15–17]. Lattice dynamics calculation and the phonon dispersion relations of transition metal carbides such as ZrC and HfC were reported using a phenomenological ‘‘double-shell’’ model theory [18] where long-range interatomic interactions were taken into account in order to get a
Low-K Gate Spacer and Formation Thereof
专利名称:Low-K Gate Spacer and Formation Thereof发明人:Bo-Cyuan Lu,Chunyao Wang,Jr-HungLi,Chung-Ting Ko,Chi On Chui申请号:US16203814申请日:20181129公开号:US20190148239A1公开日:20190516专利内容由知识产权出版社提供专利附图:摘要:Gate structures and gate spacers, along with methods of forming such, are described. In an embodiment, a structure includes an active area on a substrate, a gate structure on the active area and over the substrate, and a low-k gate spacer on the activearea and along a sidewall of the gate structure. The gate structure includes a conformal gate dielectric on the active area and includes a gate electrode over the conformal gate dielectric. The conformal gate dielectric extends vertically along a first sidewall of the low-k gate spacer. In some embodiments, the low-k gate spacer can be formed using a selective deposition process after a dummy gate structure has been removed in a replacement gate process.申请人:Taiwan Semiconductor Manufacturing Co., Ltd.地址:Hsinchu TW国籍:TW更多信息请下载全文后查看。
METHOD AND DEVICE FOR PROCESSING GEOLOGICAL INFORM
摘要:Disclosed in the invention are a method and a device for processing geological information. The method for processing the geological information comprises: acquiring multiple geological image graphs; determining the relation between the image coordinate and the ground coordinate of each of the multiple geological image graphs by an imaging mode of geological images; and joining the multiple geological image graphs together according to the relation between the image coordinate and the ground coordinate of each of the multiple geological image graphs. The large-scale ground images can be acquired by processing the geological images according to the present inve nt ion.
专利内容由知识产权出版社提供
专利名称:METHOD AND DEVICE FOR PROCESSING GEOLOGICAL INFORMATION
砂岩在不同应变率条件下的劈裂破坏特性
第52卷第2期2021年2月中南大学学报(自然科学版)Journal of Central South University (Science and Technology)V ol.52No.2Feb.2021砂岩在不同应变率条件下的劈裂破坏特性周磊1,2,朱哲明1,2,董玉清1,2,邓帅1,2,王蒙1,2(1.四川大学深地科学与工程教育部重点实验室,四川成都,610065;2.四川大学建筑与环境学院,四川成都,610065)摘要:为了研究围岩内3种典型砂岩材料在静载荷与冲击载荷作用下破坏行为的差异,采用巴西圆盘试样进行静态与动态劈裂试验,获得不同应变率条件下的抗拉强度,并从细观结构角度进行深层分析,获得抗拉强度差异的主要原因,并利用有限元程序进行数值模拟分析圆盘劈裂试验中的破坏机理。
研究结果表明:抗拉强度从大到小的砂岩材料依次为黑砂岩、红砂岩、青砂岩,青砂岩抗拉强度随应变率变化最大;砂岩的动态破坏强度差异的主要由砂岩内晶体强度与晶体黏结强度共同决定,且砂岩的抗拉强度与盒维数呈正比;砂岩材料的动态破坏行为与静态破坏行为有较大差异,圆盘劈裂破坏行为的拉伸破坏占主导地位。
关键词:砂岩;静载荷;冲击载荷;拉伸强度;盒维数中图分类号:U45文献标志码:A文章编号:1672-7207(2021)02-0555-13Fracture properties of sandstone materials at different strain ratesZHOU Lei 1,2,ZHU Zheming 1,2,DONG Yuqing 1,2,DENG Shuai 1,2,WANG Meng 1,2(1.MOE Key Laboratory of Deep Underground Science and Engineering,Sichuan University,Chengdu 610065,China;2.College of Architecture and Environment,Sichuan University,Chengdu 610065,China)Abstract:To study the properties of failure behavior of sandstone in a real tunnel under static or impact loads,a series of static and dynamic splitting tests of Brazilian disc specimens were conducted to acquire the tensile strength at different loading rates,and the causes of the differences in the tensile toughness were obtained throughDOI:10.11817/j.issn.1672-7207.2021.02.024收稿日期:2020−04−03;修回日期:2020−06−23基金项目(Foundation item):国家自然科学基金资助项目(U19A2098);四川省科技计划项目(2021YJ0511);四川大学深地科学与工程教育部重点实验室开放基金资助项目(DESE202005);浙江省岩石力学与地质灾害重点实验室开放基金资助项目(ZJRMG-2020-01)(Project(U19A2098)supported by the National Natural Science Foundation of China;Project(2021YJ0511)supported by Sichuan Provincal Science and Technology Program;Project(DESE202005)supported by the Open Fund of Key Laboratory of Deep Underground Science and Engineering of Sichuan University;Project(ZJRMG-2020-01)supported by the Key Laboratory of Rock Mechanics and Geohazards of Zhejiang Province)通信作者:朱哲明,教授,博士生导师,从事岩石力学与采矿工程研究;E-mail:**********************引用格式:周磊,朱哲明,董玉清,等.砂岩在不同应变率条件下的劈裂破坏特性[J].中南大学学报(自然科学版),2021,52(2):555−567.Citation:ZHOU Lei,ZHU Zheming,DONG Yuqing,et al.Fracture properties of sandstone materials at different strain rates[J].Journal of Central South University(Science and Technology),2021,52(2):555−567.第52卷中南大学学报(自然科学版)the analysis of the micro-fracture surfaces.Then,the failure behavior of sandstone brittle materials was also simulated by employing finite element software.The results show that the tendency from the largest to the smallestof the tensile strength of sandstone is black sandstone,red sandstone,green sandstone,and the sensitivity of green sandstone to tensile strength is the greatest.The difference of dynamic failure strength of sandstone material is decided by the strength of crystal particles and their bonding strength in rock material,and the tensile strength of sandstone are proportional to the fractal dimension.The dynamic fracture behavior of sandstone is greatly different from that of static fracture behavior,and the tensile failure of disc splitting failure is dominant in static or dynamic loading experiments.Key words:sandstone;static loads;impact loads;tensile strength;box dimension岩石材料的抗压强度远大于其抗拉强度,在大多数情况下工程岩体破坏行为表现出拉伸破坏特性。
深层硬脆性泥页岩井壁稳定力学化学耦合研究进展与思考
doi:10.11911/syztjs.2023024引用格式:金衍,薄克浩,张亚洲,等. 深层硬脆性泥页岩井壁稳定力学化学耦合研究进展与思考[J]. 石油钻探技术,2023, 51(4):159-169.JIN Yan, BO Kehao, ZHANG Yazhou, et al. Advancements and considerations of chemo-mechanical coupling for wellbore stability in deep hard brittle shale [J]. Petroleum Drilling Techniques ,2023, 51(4):159-169.深层硬脆性泥页岩井壁稳定力学化学耦合研究进展与思考金 衍1,2, 薄克浩1,2, 张亚洲1,2, 卢运虎1,2(1. 中国石油大学(北京)石油工程学院, 北京 102249;2. 油气资源与探测国家重点实验室(中国石油大学(北京)), 北京 102249)摘 要: 深层及超深层油气资源正逐步成为我国重点勘探开发的关键领域,但钻井过程中深层硬脆性泥页岩地层井壁失稳问题频发,严重制约着深层及超深层油气资源高效开发。
力学化学耦合作用下的深层硬脆性泥页岩井壁稳定问题,是一个涉及微观、细观及宏观跨尺度演化的复杂问题。
阐述了力学化学耦合作用下硬脆性泥页岩井壁失稳的基本原理,并分别从微观、细观和宏观尺度,总结了硬脆性泥页岩与入井流体间的作用机理、细观结构损伤演化的定量表征、泥页岩水化宏观力学劣化效应及井壁稳定性定量分析方面的研究进展,从考虑化学效应的断裂力学角度,提出了探索硬脆性泥页岩井壁稳定性问题的新思路。
关键词: 深层;硬脆性泥页岩;井壁失稳;多尺度演化;化学断裂;力学化学耦合中图分类号: TE28 文献标志码: A 文章编号: 1001–0890(2023)04–0159–11Advancements and Considerations of Chemo-Mechanical Coupling forWellbore Stability in Deep Hard Brittle ShaleJIN Yan 1,2, BO Kehao 1,2, ZHANG Yazhou 1,2, LU Yunhu1,2(1. College of Petroleum Engineering, China University of Petroleum (Beijing ), Beijing, 102249, China ; 2. State Key Laboratory of Petroleum Resources and Prospecting (China University of Petroleum (Beijing )), Beijing, 102249, China )Abstract: The oil and gas resources from deep and ultra-deep reservoirs in China are the most important target of exploration and development. However, pervasive and ubiquitous wellbore instability in hard brittle deep shale seriously compromises the efficient development of deep and ultra-deep oil and gas resources. Wellbore instability in deep hard brittle shale under the chemo-mechanical coupling is a complicated problem involving multi-scale evolution among micro-scale, meso-scale and macro-scale. The basic principle of wellbore instability in hard brittle shale under chemo-mechanical coupling was briefly introduced. In addition, the previous studies on the mechanism between hard brittle shale and drilling fluid, quantitative description of the evolution of damage in mesocosm structures, macroscopic mechanical deterioration of shale after hydration, and quantitative analysis of wellbore stability, were reviewed in terms of micro-scale, meso-scale and macro-scale. Moreover, a new idea was proposed for wellbore stability in hard brittle shale from the perspective of fracture mechanics considering chemical effects.Key words: deep formation; hard brittle shale; wellbore instability; multi-scale evolution; chemical induced fracture;chemo-mechanical coupling effect深层钻井钻遇硬脆性泥页岩地质体时,井壁易发生坍塌、掉块,引起阻卡等井下复杂,严重时甚至导致井眼报废,而90%的井壁失稳问题都与硬脆性泥页岩地层有关,研究硬脆性泥页岩地层井壁稳定收稿日期: 2022-12-19;改回日期: 2023-02-13。
固体酸催化纤维素水解转化葡萄糖的研究进展
2017年第36卷第2期 CHEMICAL INDUSTRY AND ENGINEERING PROGRESS ·555·化工进展固体酸催化纤维素水解转化葡萄糖的研究进展赵博,胡尚连,龚道勇,李会萍(西南科技大学生命科学与工程学院,四川绵阳 621010)摘要:固体酸催化剂具有很好的重复使用性以及产物易于分离的特点,近年来在纤维素降解转化葡萄糖的研究中得到越来越多的关注。
这篇综述总结了不同类型的固体酸在水解纤维素上的研究进展,如金属氧化物、高分子聚合物固体酸、磺化的碳基固体酸、杂多酸、氢型分子筛、磁性固体酸、负载型金属氧化物以及固体超强酸和石墨烯衍生物等。
分析了固体酸催化剂存在的问题如与纤维素接触困难、活性组分容易损失等。
另外指出酸强度、酸密度、底物的吸附性以及固体材料上的微孔都是纤维素水解的一些关键因素。
同时对一些提高纤维素水解效率的方法如纤维素的预处理、离子液体的使用以及微波照射等也进行了讨论。
此外,对于纤维素降解转化葡萄糖的一些更加绿色、简单、有效以及低成本的有价值的策略如仿酶催化进行了讨论。
关键词:生物质;聚合物;纤维素;葡萄糖;固体酸;催化中图分类号:O643.32 文献标志码:A 文章编号:1000–6613(2017)02–0555–13DOI:10.16085/j.issn.1000-6613.2017.02.022New advances on hydrolysis of cellulose to glucose by solid acidZHAO Bo,HU Shanglian,GONG Daoyong,LI Huiping(School of Life Science and Engineering,Southwest University of Science and Technology,Mianyang 621010,Sichuan,China)Abstract:Solid acid catalysts have been commonly employed for the hydrolysis of cellulose into glucose in recent years due to the ease of product separation and good catalyst recyclability. This paper summarizes the recent advances in the hydrolysis of cellulose using different types of solid acids,such as metal oxides,polymer based acids,sulfonated carbonaceous based acids,heteropoly acids,H-form zeolites,magnetic solid acids,supported metals,solid superacid,and graphene derivative. The catalysts still need to be improved in cellulose contact and active components retainment. The acid strength,acid site density,adsorption of the substance,and micropores of the solid material are all key factors for effective hydrolysis processes. Meanwhile,methods used to promote reaction efficiency,such as the pretreatment of cellulose to reduce its crystallinity and the use of ionic liquids or microwave irradiation to improve the reaction rate,are also discussed. Finally,the potential research trends are also suggested to provide valuable ideas for the hydrolysis of cellulose into glucose in a green,simple,efficient,and inexpensive way.Key words:biomass;polymers;cellucose;glucose;solid acids;catalysis石化资源的发现和利用极大地改善了人类的生活水平,目前人类使用的能源仍然是以石油、煤和天然气等石化能源为主。
多孔介质与SDS复配体系中天然气水合物生成过程分析
2018年第37卷第6期 CHEMICAL INDUSTRY AND ENGINEERING PROGRESS·2203·化 工 进展多孔介质与SDS 复配体系中天然气水合物生成过程分析刘志明1,商丽艳2,潘振1,孙秀丽2,王喆1,侯朋朋1(1辽宁石油化工大学石油天然气工程学院,辽宁 抚顺 113001;2辽宁石油化工大学化学化工与环境学部,辽宁 抚顺 113001)摘要:天然气水合物巨大的储量和本身高储气量的特点,决定了其在能源和工业领域的重要作用。
自然界中水合物赋存于沉积层多孔介质的孔隙中,因而研究其在多孔介质条件下的基础物性和快速生成,对水合物的工业应用具有重要意义。
为此,本文采用了不同粒径的多孔氧化铝颗粒和实心二氧化硅颗粒,并将其与十二烷基硫酸钠(SDS )溶液进行复配,研究该体系中275.15K 和7MPa 条件下水合物的生成情况。
结果表明:多孔介质与SDS 复配体系中生成水合物的储气量大于纯SDS 溶液中,二氧化硅颗粒和氧化铝颗粒分别在促进水合物成核和提升储气量方面效果显著;实验条件下颗粒粒径对于水合物生成的压降过程和相平衡条件影响不大;实验所处pH 条件下,氧化铝表面会因为水解带正电,二氧化硅表面则会在极化和水合作用的共同影响下带负电,带电表面和SDS 的相互作用能够促进水合物的生成;多孔介质孔隙产生的毛细作用力及其对体系传热条件的改善有助于水合物的贴壁生成。
因此可以认为多孔介质与表面活性剂复配体系对水合物生成的促进效果明显,并且将多孔材料作为水合物生成的基质是一种提高储气量的有效方法。
关键词:天然气水合物;多孔介质;表面活性剂;粒径;诱导时间;双电层模型中图分类号:TE89 文献标志码:A 文章编号:1000–6613(2018)06–2203–11 DOI :10.16085/j.issn.1000-6613.2017-1459Analysis of natural gas hydrate formation process in porous media andSDS complex systemLIU Zhiming 1,SAHNG Liyan 2,P AN Zhen 1,SUN Xiuli 2,WANG Zhe 1,HOU Pengpeng 1(1Petroleum and Natural Gas Engineering, Liaoning Shihua University ,Fushun 113001,Liaoning ,China ;2College of Chemistry ,Chemical Engineering and Environmental Engineering ,Liaoning Shihua University, Fushun113001,Liaoning, China )Abstract :Natural gas hydrate has an important role in energy and industry fields because of its huge reserves and high gas storage capacity ,it is present in the pores of the porous media in the sedimentary layer under natural conditions ,so it is of great significance to study the rapid formation and basic properties of the hydrate in the porous medium. And thus ,porous alumina and solid silica particles with different particle size compounded with SDS solution were used to study the hydrate formation in the system at 275.15K and 7MPa. The following results are revealed. Firstly ,the storage capacity of the hydrate in the porous medium and the SDS complex system is larger than that in the pure SDS solution. The silica particles and the alumina particles have significant effect in the hydration of the hydrate and the gas storage capacity respectively. Secondly ,the particle size has no obvious effect on the pressure drop process of hydrate formation. Under the experimental conditions ,the particle size has little influence气水合物快速生成技术。
基于太阳能蓄热过程的甲烷二氧化碳重整研究进展
2016年第35卷第6期CHEMICAL INDUSTRY AND ENGINEERING PROGRESS ·1723·化工进展基于太阳能蓄热过程的甲烷二氧化碳重整研究进展谢涛,杨伯伦(西安交通大学化学工程与技术学院,陕西西安 710049)摘要:热化学储能技术因为其储能密度高、热损小、能长距离运输等优点而成为保证太阳能长久稳定供应的关键技术。
本文对基于甲烷二氧化碳重整反应的太阳能热化学储热系统研究现状进行了回顾,重点讨论了甲烷重整催化剂、重整反应器以及储能系统整体的传热特性等3个方向的研究进展。
指出新型高效催化剂以及反应器开发和性能测试是目前该领域的主要研究方向。
发现辐射热损失、非均匀温度分布特性、辐射热流的时变波动特性,以及由此造成的能量与化学反应的不匹配限制了热化学系统能量储存效率的进一步提高,并提出催化剂的催化特性与物性/结构参数依变关系,反应器辐射吸收特性、传热传质特性和反应特性之间的相互作用机制,以及系统时变动态特性与反应物流/辐射能流的匹配关系是建立甲烷重整热化学储能系统优化设计理论亟待解决的关键问题。
关键词:太阳能;热化学储能;甲烷重整反应;催化剂;反应器;传热特性中图分类号:TK519 文献标志码:A 文章编号:1000–6613(2016)06–1723–010DOI:10.16085/j.issn.1000-6613.2016.06.012Advances of CO2 reforming of methane based on the solar energy storageXIE Tao,YANG Bolun(School of Chemical Engineering and Technology,Xi’an Jiaotong University,Xi’an 710049,Shaanxi,China)Abstract:Thermochemical energy storage is the key technique to guarantee long term and steady supply of solar energy due to its advantages of high energy density,low heat loss as well as transportability over long distance. In this work,the development of CO2 reforming of methane that has been applied in the solar thermochemical energy storage system was summarized. Particular emphasis was put on the studies of methane reforming catalyst,methane reforming reactor,and thermal analysis of thermochemical energy storage system. New high-efficiency catalysts and reforming reactors were the main interests of the current researches. Radiation heat loss,non-uniform temperature distribution,time-varying radiation heat flux,as well as the mismatching between energy and chemical reaction restricted the improvement of thermochemical energy storage efficiency. In order to further improve the performance of thermochemical energy storage system and establish its optimization design theory,some key questions were proposed to be answered,including the relationship between the catalytic performance and properties/structure parameters of the catalyst,the interaction mechanism of thermal radiation absorption,heat/mass transfer and thermochemical reaction characteristics of the chemical reactor,as well as the time-varying dynamic features and matching relationship with radiation heat flux of the thermochemical system.Key words:solar energy;thermochemical energy storage;reforming of methane;catalyst;reforming reactor;heat transfer characteristics收稿日期:2016-01-25;修改稿日期:2016-02-01。
深层页岩欠平衡钻井气液固三相瞬态流动传热模型研究
第 51 卷 第 5 期石 油 钻 探 技 术Vol. 51 No.5 2023 年 9 月PETROLEUM DRILLING TECHNIQUES Sep., 2023doi:10.11911/syztjs.2023089引用格式:张文平,许争鸣,吕泽昊,等. 深层页岩欠平衡钻井气液固三相瞬态流动传热模型研究[J]. 石油钻探技术,2023, 51(5):96-105.ZHANG Wenping, XU Zhengming, LYU Zehao, et al. Research on a transient flow heat transfer model of gas-liquid-solid three-phase flow for unbalanced drilling in deep shale wells [J]. Petroleum Drilling Techniques,2023, 51(5):96-105.深层页岩欠平衡钻井气液固三相瞬态流动传热模型研究张文平1, 许争鸣2, 吕泽昊3, 赵 雯4(1. 中石化石油工程技术研究院有限公司,北京 102206;2. 中国地质大学(北京)能源学院,北京 100083;3. 中国石油油气和新能源分公司,北京 100007;4. 中国石油青海油田分公司采气二厂,青海茫崖 816499)摘 要: 井底压力的准确预测和有效控制是深层页岩欠平衡钻井作业的关键,但岩屑及环空流体与周围环境之间的对流换热对传统井底压力计算模型精度的影响较大。
为此,建立了瞬态非等温井筒气液固三相流动模型,根据连续性方程和动量守恒方程,计算了流体速度、相体积分数和压力,并求解了不同径向层的能量守恒方程,得到了整个井筒–地层系统的温度分布,并采用迭代法,耦合求解了深度和径向方向上的温度、压力和流体性质;模型计算结果与欠平衡钻井作业的现场数据之间误差小于5.0%,验证了该模型的准确性与可靠性。
Zener-Hollomon 参数对AZ61 镁合金热变形行为的影响
第45卷第4期燕山大学学报Vol.45No.42021年7月Journal of Yanshan UniversityJuly 2021㊀㊀文章编号:1007-791X (2021)04-0328-07Zener-Hollomon 参数对AZ61镁合金热变形行为的影响李㊀玮,戴浩浩,阎泽文,刘孝轲,徐㊀岩∗(先进锻压成形技术与科学教育部重点实验室(燕山大学),河北秦皇岛066004)收稿日期:2020-05-06㊀㊀责任编辑:王建青基金项目:国家自然科学基金资助项目(51605421);河北省高等学校科学技术研究项目(QN2019129)作者简介:李玮(1995-),男,江西抚州人,硕士研究生,主要研究方向为镁合金先进成形技术;∗通信作者:徐岩(1983-),女,吉林松原人,博士,副教授,博士生导师,主要研究方向为镁合金先进塑性成形工艺与理论,Email:xuyan_916@㊂摘㊀要:利用Gleeble-3500热模拟试验机,对均匀化退火处理后的铸态AZ61镁合金进行了等温热压缩变形实验,研究了合金在变形温度为220ħ~380ħ㊁应变速率为0.001s -1~10s -1条件下的热变形行为和组织演变特征,并基于双曲正弦模型建立了合金的本构模型㊂研究了Zener-Hollomon 参数对热压缩变形组织演变的影响规律,揭示了高Z 值㊁中等Z 值和低Z 值对应参数条件下的变形合金呈现不同的组织形貌特征,并阐明了随Z 参数的逐渐减小,变形组织逐渐由失稳组织㊁不完全动态再结晶组织转变为粗化的完全动态再结晶组织,确定了合理的热成形工艺参数区间对应的ln Z 数值范围为22.17~29.25㊂关键词:AZ61镁合金;热变形;本构模型;Zener-Hollomon 参数;动态再结晶中图分类号:TG316.1㊀㊀文献标识码:A㊀㊀DOI :10.3969/j.issn.1007-791X.2021.04.0050㊀引言镁合金是目前可工业化应用的最轻质金属结构材料,具有资源丰富㊁比强度高㊁比刚度大㊁延展性好㊁环保性能优异及机械加工性能优良等诸多优点[1]㊂但是由于镁具有密排六方晶体结构,其核外电子排列方式决定镁合金特殊的物理化学性质和力学性能,镁合金在室温下存在三个滑移系,不满足多晶塑性变形协调机制,这是常温下镁合金成形难㊁塑韧性差的主要原因[2-3]㊂因此,提高镁合金的塑性和综合力学性能成为镁合金研究的热点㊂镁合金材料的成形大多是在热状态下进行,即在高于再结晶温度的条件下,使镁合金材料同时产生塑性变形和再结晶细化的加工方法㊂AZ61镁合金作为典型的Mg-Al-Zn 系变形镁合金,具有较高的强度和塑性等综合性能,得到广泛的市场应用㊂其热加工成形过程比较复杂,温度㊁应变速率㊁变形方式等过程参数对成形能力和热变形微观组织都会产生影响㊂通过合理的变形参数协调与匹配,能够避免失稳变形组织产生,获得AZ61镁合金细小均匀的热变形组织,获得更优的综合力学性能,从而满足对结构件优异综合性能日益增长的需要,同时对变形镁合金的二次加工提供指导和借鉴㊂本文以均匀化退火热处理后的铸态AZ61镁合金为研究对象,通过等温热压缩变形试验获得真实应力-应变曲线,构建了均匀化处理态AZ61合金的本构模型,获得综合反映应变速率和温度对流变应力影响的Z 参数值㊂通过光学显微镜(Optical microscope,OM )和扫描电子显微镜(Scanning electron microscope,SEM)等表征测试技术,建立Z 参数与热变形组织的匹配关系,揭示热变形组织的形貌特征和演变规律,最终确定均匀化处理态AZ61镁合金的最优热成形工艺参数区间㊂1㊀实验方法本研究将连铸态AZ61镁合金作为初始材料,. All Rights Reserved.第4期李㊀玮等㊀Zener-Hollomon 参数对AZ61镁合金热变形行为的影响329㊀其化学成分含量(质量分数)为6.50Al㊁0.86Zn㊁0.32Mn㊁0.014Si㊁0.0035Fe㊁0.0018Cu㊁0.00059Ni㊁Mg (其余)㊂在LK-JS 型号电阻式加热炉中完成铸态合金的均匀化退火处理,首先以5ħ/s 的升温速率,将试样随炉升温至420ħ,保温5h 后随炉冷却㊂通过线切割将均匀化退火处理后的铸态棒料切割成为ϕ10mm ˑ15mm 的圆柱试样,在Gleeble-3500热模拟试验机完成等温热压缩试验㊂热压缩变形参数与操作流程如图1所示㊂变形温度为220ħ~380ħ㊁应变速率为0.001s -1~10s -1㊁真实压缩应变为0.916㊂首先以5ħ/s 的速率升温至目标温度后保温180s,然后进行试样的压缩变形,变形结束后立即进行水淬以保留变形组织㊂将热压缩后的试样沿中心轴线切割成两部分,镶嵌后进行机械抛磨和腐蚀,腐蚀液成分为:苦味酸2.5g +冰醋酸2.5mL +蒸馏水5mL +无水乙醇50mL,腐蚀时间约8~12s㊂腐蚀后的试样通过Scope.A1型光学显微镜和Sigma 500型扫描电子显微镜进行微观组织表征和观察分析,采用截线法进行晶粒尺寸统计㊂同一条件下选择3张组织照片进行计算,将计算平均值作为最终统计结果㊂图1㊀热压缩变形试验过程Fig.1㊀Process of hot compression tests2㊀实验结果与分析讨论2.1㊀均匀化处理AZ61镁合金的微观组织均匀化退火态AZ61镁合金的微观组织如图2所示,晶界和晶内分布着连续或不连续的层片状β-Mg 17Al 12相,仍有少量尺寸不足3μm 的条块状β-Mg 17Al 12相分布在晶界上,经统计得到基体Mg 的平均晶粒直径尺寸约为16.84μm㊂图2㊀均匀化退火AZ61镁合金的微观组织Fig.2㊀Microstructure of the as homogenizedAZ61magnesium alloy2.2㊀真实应力-应变曲线通过热压缩实验获得在不同温度和应变速率条件下的真实应力-应变曲线,如图3所示㊂由图可知,真实应力-应变曲线的变化可分为4个阶段:1)在压缩初始阶段,真实应力随应变的增加线性增大,加工硬化占主导地位㊂2)随着变形量增大至达峰值应力之前,变形体内部动态再结晶晶粒开始形核,加工硬化逐渐被动态再结晶软化作用抵消,直至真实应力达到最大值㊂3)当应力达到峰值后,真实应力在峰值附近短暂保持后快速下降,且应变速率越高,温度越低,下降趋势越明显,此时动态再结晶的软化作用为主导变形机制,从而降低的材料的强度㊂4)动态再结晶软化作用和加工硬化达到动态平衡,流动应力趋于稳定㊂由此可知,真实应力-应变曲线整体变化特征,归因于加工硬化和动态软化之间的动态平衡问题,这种曲线特征在6A02铝合金和Al-Si-Mg 合金中也观察到[4-5]㊂此外,峰值应力随着温度的升高和应变速率降低而降低,这是由于高温能促进晶界的迁移速率,加快动态再结晶晶粒形核和生长,而低应变速率能够为组织转变提供较长的时间,促进动态再结晶行为[5]㊂从图3(a)可知,在220ħ/10s -1㊁220ħ/1s -1的低温高应变速率条件下,试样在较小应变下发生剪切断裂㊂此外,260ħ/10s -1条件下的变形试样也观察到了宏观的剪切断裂㊂因为位错密度随着变形量的增大而急剧增大,导致位错塞积,而在低温和高应变速率条件下,软化作用来不及抵消加工硬化现象,造成应力. All Rights Reserved.330㊀燕山大学学报2021剧烈集中㊂当应变累积到一定程度,微裂纹萌生并进一步扩展,造成试样沿与轴线成45ʎ方向的断裂㊂由于镁合金塑性较差,在低温高应变速率下(220ħ/10s-1㊁220ħ/1s-1和260ħ/10s-1)发生失稳断裂,呈现如图3(a)中所示的不完整应力-应变曲线㊂图3㊀不同应变速率条件下的真实应力-应变曲线Fig.3㊀True stress-strain curves obtainedat various temperatures and strain rates 2.3㊀应力-应变本构模型双曲正弦函数模型(式(1))㊁幂函数本构模型(式(2))和指数函数本构模型(式(3))能够全面地描述高温变形的峰值应力㊁变形温度和应变速率之间的关系,能够准确预测热变形的流动应力[6]:ε㊃=A[sinh(ασ)]n exp-Q RT(),(1)ε㊃=A1σn1exp-Q RT(),(2)ε㊃=A2[exp(βσ)]exp-Q RT(),(3)其中,ε㊃是应变速率(s-1);A是材料常数;σ是峰值应力(MPa);n是应力指数(1/m);Q是表观激活能(kJ㊃mol-1),R是气体常数(8.314J㊃mol-1㊃K-1),T是绝对温度(K)㊂A1㊁A2㊁β㊁n1㊁α是材料常数(MPa-1)㊂常数α㊁β和n1之间的关系满足α=β/n1且n1=∂lnε㊃∂lnσ和β=∂lnε㊃∂σ,根据热压缩实验获得的真实应力-应变数据,分别用lnε㊃-lnσ和lnε㊃-σ两种形式来表达热压缩应变速率和峰值应力之间关系,如图4(a)和(b)㊂图中的斜率分别代表n1㊁β,最终求得αi的平均值为7.39ˑ10-3㊂Zener和Hollomon研究了激活控制的热变形过程,用变形影响因子Z参数,即Zener-Hollomon 参数,来表达应变速率ε㊃和温度T之间的关系[11]㊂表达式为Z=ε㊃exp Q RT(),(4)结合式(1)可得Z=A[sinh(ασ)]n,(5)由式(1)两边取对数可得QRT=ln A-lnε㊃+n ln(sinh(ασ))㊂(6)㊀㊀从式(6)可知,在应变速率恒定下,1/T与ln(sinh(ασ))之间存在线性关系,通过恒定温度下的ln(sinh(ασ))-lnε㊃和恒定应变速率下ln(sinh(ασ))-1/T之间拟合线性关系的斜率,可以求得合金在一定温度下的变形激活能:Q=R∂ln(sinh(ασ))∂(1/T)éëêêùûúúε㊃∂lnε㊃∂ln(sinh(ασ))éëêêùûúúT,(7). All Rights Reserved.第4期李㊀玮等㊀Zener-Hollomon 参数对AZ61镁合金热变形行为的影响331㊀式中∂ln(sinh(ασ))∂(1/T)éëêêùûúúε㊃和∂ln ε㊃∂ln(sinh(ασ))éëêêùûúúT分别为恒定应变速率条件下ln(sinh(ασ))-1/T 关系直线的斜率和恒定温度条件下ln ε㊃-ln (sinh(ασ))关系直线的斜率n ,n 即为应变速率敏感指数的倒数1/m ㊂根据热压缩实验数据绘制上述关系直线,如图5(a)和(b),可得不同参数温度和应变速率条件下∂ln(sinh(ασ))∂(1/T)éëêêùûúúε㊃和∂ln ε㊃∂ln(sinh(ασ))éëêêùûúúT的值㊂由式(7)可得合金的表观激活能Q 和应变速率敏感指数m 分别为148.134kJ㊃mol -1和0.17㊂图4㊀应变速率与峰值应力之间的拟合关系Fig.4㊀Relationships between peak stress and strain rate㊀㊀对式(4)两边取对数得ln Z =ln ε㊃+QRT,(8)将求得的变形激活能Q 和变形条件代入式(8)可以求得不同变形条件下的ln Z 值,绘制ln Z -ln(sinh(ασ))关系图,如图6所示㊂通过线性拟合可知两者之间存在明显的线性关系,其线性相关系数为0.99,由此可知用双曲正选函数能够准确描述均匀化处理态AZ61镁合金的热压缩变形行为㊂图5㊀不同参数间的线性关系拟合Fig.5㊀Linear relationships between different parameters图6㊀ln Z -ln(sinh(ασ))的线性关系Fig.6㊀Linear relationship of ln Z -ln(sinh(ασ))㊀㊀根据图6中的截距值(即ln A )可求得A =2.12ˑ1012,并可以求得更为精确的n 值为5.58㊂将上述求得的相关数值代入式(1)中,求得应力-. All Rights Reserved.332㊀燕山大学学报2021应变本构关系模型为ε㊃=2.12ˑ1012[sinh(0.00739σ)]5.58㊃exp(-148134/RT)㊂(9) 2.4㊀热压缩变形组织随Z参数的演变规律Zener-Hollomon参数(简称Z参数)是体现在特定变形条件下,材料热变形微观组织演变的一个重要指标,是衡量温度和应变速率对热变形行为影响的重要参数[7-9]㊂因此,采用Z参数数值水平来研究对AZ61镁合金热变形行为的影响具有理论和实践意义㊂根据式(8)可计算获得不同温度和应变速率条件下的ln Z值,如表1所示㊂图7显示了具有不同Z值水平对应变形参数条件下的热压缩变形组织㊂表1㊀不同温度和应变速率条件下的ln Z值Tab.1㊀ln Z values at various temperatures and strain ratesε㊃/s-1T/ħ220260300340380 0.00129.2526.5424.2022.1720.39 0.0131.5528.8426.5024.4722.69 0.133.8631.1428.8126.7824.99 136.1633.4431.1129.0827.30 1038.4635.7533.4131.3829.60㊀㊀图7(a)和(b)为220ħ/1s-1和260ħ/1s-1条件下的压缩变形组织,分别对应较高的ln Z值36.16和33.44㊂由图可知,在较高的Z参数下变形组织中出现了微观开裂,这是因为低温㊁高应变速率条件下,合金变形剧烈㊁不均匀造成的局部应力集中,从而发生开裂㊂此外,由于低温下滑移系有限,镁合金会通过孪晶开启协调变形,因此在图7(a)中还可以观察到在220ħ/1s-1条件下的变形组织中的贯穿性裂纹两侧粗晶内存在大量的变形孪晶㊂图7(b)显示260ħ/1s-1条件下的变形组织是由非贯穿的微观裂纹㊁明显的局部变形带㊁第二相颗粒的聚集以及局部的动态再结晶组织构成的非均匀混合组织形态,呈现流变失稳组织的典型特征㊂类似的失稳变形组织在AZ91D[10]和ZK60[11]镁合金的热变形研究中也报道过,但因材料初始状态和变形参数的不同,混合组织的构成和比例会有所不同㊂流变失稳组织转变不充分,呈现动态再结晶组织㊁变形孪晶㊁局部变形带㊁微观裂纹㊁空洞等构成的极不均匀混合组织形态,宏观力学性能差,因此在AZ61铸态合金的热加工过程中应当避免高Z值(ln Z=33.41~38.46)所在的变形参数区域㊂与相同工艺参数条件下铸态AZ61镁合金的热变形行为研究结果相比较[12],本文经均匀化处理的AZ61合金流变失稳组织对应的变形参数范围显著缩小,且相同条件下的ln Z 值更小,这也说明均匀化热处理有益于铸态合金塑性成形能力的提高㊂图7(c)和(d)为300ħ/0.01s-1和260ħ/ 0.01s-1条件下的变形组织形貌,分别对应中等的ln Z值26.50和28.84㊂由图可知,在较高温度和较低应变速率下,热变形组织中的绝大部分被细小等轴状的动态再结晶组织覆盖㊂在300ħ/ 0.01s-1条件下,动态再结晶比例约89.65%,且晶粒细小均匀,平均晶粒尺寸约为1.42μm,如图7 (c)㊂如图7(d),在260ħ/0.01s-1条件下的变形组织由动态再结晶和原始粗大晶粒组成,动态再结晶组织约占87.93%,再结晶晶粒细小均匀㊁平均直径约2.43μm㊂由上述分析可知,在中等Z 值(ln Z=26.50~31.55)所在的变形工艺条件下,均匀化AZ61合金的热变形组织以细小的动态再结晶组织为主,且Z值越小,动态再结晶越充分㊂这是因为随着温度升高和应变速率降低,晶界位错的迁移能力随着原子扩散的增强而提高,促进了动态再结晶的形核和长大,因此形成了不断宽化扩展的室温项链状动态再结晶组织形貌㊂通过比较还发现,动态再结晶体积分数随着Z值的减小而增大㊂Li等人[8]在Mg-Zn-Zr-Yb镁合金的热压缩变形行为的研究中,在中等Z值(ln Z=28.3㊁25.9)对应的参数条件下也观察到显著宽化的项链状动态再结晶组织㊂图7(e)和(f)为340ħ/0.001s-1和380ħ/ 0.001s-1条件下的变形组织形貌,分别对应较低的ln Z值22.17和20.39㊂随着变形温度的升高和应变速率的降低,Z值逐渐减小,在较低的Z值对应的参数条件下,热变形组织呈现出等轴且粗化长大的完全动态再结晶形貌㊂此时动态再结晶晶粒的形核速率将低于其生长速率,动态再结晶晶粒将获得足够的时间和能量自由长大,因此在340ħ/0.001s-1和380ħ/0.001s-1条件下的变形组织可以观察到显著粗化的等轴状动态再结晶晶粒,平均晶粒尺寸分别约为5.49μm和7.05. All Rights Reserved.第4期李㊀玮等㊀Zener-Hollomon参数对AZ61镁合金热变形行为的影响333㊀μm,如图7(e)和(f)㊂值得注意的是,与高Z值(图7(a)和(b))相比较,在低Z值(图7(e)和(f))参数条件下的变形组织中,细小的第二相数量明显减少㊂因为高温变形促进了Al元素的固溶,第二相数量和尺寸均减小,削弱了第二相钉扎抑制动态再结晶长大作用,因此动态再结晶组织显著粗化[13-14]㊂Yang等人[15]研究了Z参数对粉末冶金Ti-22Al-25Nb-1.0B合金热变形行的影响规律,研究结果揭示了在低Z值(ln Z=24~29.7)参数区间内,动态再结晶组织发生显著粗化,并将其归因为溶质元素的拖曳效应随温度的升高而减小,从而提高了晶界的迁移率㊂高温低应变速率会形成组织粗化,影响力学性能,因此在热加工中应避免极小的Z值参数区间㊂图7㊀不同变形参数和Z值条件下的压缩变形微观组织(ε=0.9)Fig.7㊀Microstructures deformed at different deformation conditions and Z values(ε=0.9) . All Rights Reserved.4 结论1)均匀化处理态AZ61镁合金的热压缩应力-应变曲线经历4个主要阶段:a)加工硬化占主导地位,应力随应变线性增大;b)加工硬化作用逐渐被增强的动态再结晶软化作用抵消,应力缓慢增加至应力峰值;c)动态再结晶软化主导,应力缓慢减小;d)动态再结晶软化和加工硬化达到动态平衡,应力趋于稳定㊂2)双曲线正弦函数模型适用于描述AZ61镁合金的热变形行为,并获得应力-应变本构关系模型:ε㊃=2.12ˑ1012[sinh(0.00739σ)]5.58㊃exp(-148134/RT)㊂㊀㊀3)均匀化处理态AZ61镁合金的热变形组织受Z参数影响,其热成形适宜在ln Z=(22.17~ 29.25)对应的变形参数区间进行㊂参考文献1杨冲彭艳杨硕等.AZ31镁合金轧制板材各向异性行为的晶体塑性研究 J .燕山大学学报2016 40 2 123-129. YANG C PENG Y YANG S et al.Study on anisotropic mechanical behavior of AZ31Mg alloy sheet based on crystal plasticity modeling J .Journal of Yanshan University 2016 40 2 123-129.2李建孙惠学郭朋等.镁合金车轮成形工艺及模具研究 J .燕山大学学报2013 37 6 494-498.LI J SUN H X GUO P et al.Development of forming technology and die of magnesium alloy wheels J .Journal of Yanshan University 2013 37 6 494-498.3戚文军冯晓伟刘汪涵博等.Mg-3Zn-2Gd合金轧制态和退火态的组织与力学性能 J .材料研究学报2016 307 531-537.QI W J FENG X W LIU W H B et al.Microstructure and mechanical properties of rolled-and annealed-Mg-3Zn-2Gd alloy J .Chinese Journal of Materials Research 2016 307 531-537.4LIAO H C WU Y ZHOU K X et al.Hot deformation behavior and processing map of Al-Si-Mg alloys containing different amount of silicon based on Gleebe-3500hot compression simulation J . Materials&Design 2015 65 1091-1099. 5XU Y HU L X SUN Y et al.Deformation behaviour and dynamic recrystallization of AZ61magnesium alloy J .Journal of Alloys and Compounds 2013 580 262-269.6SELLARS C M MCTEGART W J.On the mechanism of hot deformation J .Acta Metallurgica 1966 14 1136-1138. 7SUN Y W PAN Q L HUANG Z Q et al.Evolutions of diffusion activation energy and Zener-Hollomon parameter of ultra-high strength Al-Zn-Mg-Cu-Zr alloy during hot compression J . Progress in Natural Science Materials International 2019 18 635-646.8LI L WANG Y LI H et al.Effect of the Zener-Hollomon parameter on the dynamic recrystallization kinetics of Mg-Zn-Zr-Yb magnesium alloy J .Computational Materials Science 2019 166 221-229.9LIU W Y ZHAO H LI D et al.Hot deformation behavior of AA7085aluminum alloy during isothermal compression at elevated temperature J .Materials Science and Engineering A 2014 596 176-182.10XU Y HU L X SUN Y et al.Processing map and kinetic analysis for hot deformation of an as-cast AZ91D magnesium alloy J .Materials Science and Engineering A 2013 578 402-407.11LI J Q LIU J CUI Z S et al.Characterization of hot deformation behavior of extruded ZK60magnesium alloy using3D processing maps J .Materials&Design 2014 56 889-897. 12XU Y HU L X DENG T Q et al.Hot deformation behavior and processing map of as-cast AZ61magnesium alloy J . Materials Science and Engineering A 2013 559 528-533. 13MAGHSOUDI M H ZAREI-HANZAKI A ABEDI H R. Modification of the grain structure γphase morphology and texture in AZ81Mg alloy through accumulative back extrusion J .Materials Science and Engineering A 2014 595 99-108. 14JIA J B XU Y YANG Y et al.Microstructure evolution of an AZ91D magnesium alloy subjected to intense plastic straining J .Journal of Alloys and Compounds 2017 721 347-362. 15YANG J L WANG G F JIAO X Y et al.Hot deformation behavior and microstructural evolution of Ti-22Al-25Nb-1.0B alloy prepared by elemental powder metallurgy J .Journal of Alloys and Compounds 2017 695 1038-1044.下转第342页. All Rights Reserved.Pattern Analysis and Machine Intelligence 2017 394 640-651.14SIMONYAN K ZISSERMAN A.Very deep convolutional networks for large-scale image recognition C//3rd International Conference on Learning Representations San Diego CA USA 2015 1-14.BAU-Net for buildings segmentation in high resolution remote sensing imagesLI Linxiang1 2YUAN Yi1 2WEN Shuhuan1 21.Engineering Research Center of the Ministry of Education for Intelligent Control System and Intelligent EquipmentYanshan University Qinhuangdao Hebei066004 China2.Key Laboratory of Industrial Computer Control Engineering of Hebei ProvinceYanshan University Qinhuangdao Hebei066004 ChinaAbstract The segmentation of buildings in high resolution remote sensing images is an important technical issue in the constructionof modern digital city economic prediction resources exploration and the national defense security.Based on U-Net a doubleU-Net encoder-decoder framework of boundary awareness is proposed.In the model the coarse feature extraction network is usedfor the first time to recognize and extract the buildings and then the edge contour is modified by the refined feature extractionnetwork of the residual structure.Through valid experiments and comparison with some classic feature extraction networks theresults show that the algorithm adopted in this paper could overcome the disturbance produced by roads vehicles trees andbuilding shadow effectively recognize the main part of the buildings precisely and completely segment the edge of the buildings.And the precision recall F-measure and MAE of the test set are90.48% 91.30% 90.58%and0.0325respectively all ofwhich are superior to the classical segmentation algorithms.Keywords remote sensing images BAU-Net deep neural network building segmentation(上接第334页)Impact of Zener-Hollomon parameter on hot deformationbehavior of AZ61magnesium alloyLI Wei,DAI Haohao,YAN Zewen,LIU Xiaoke,XU Yan(Key Laboratory of Advanced Forging&Stamping Technology and Science(Yanshan University),Ministry of Education of China,Qinhuangdao,Hebei066004,China)Abstract:In the present work,hot compression tests of an as-cast AZ61magnesium alloy after homogenizing annealing treatmentwas conducted at temperatures of220ħ~380ħand strain rates of0.001s-1~10s-1by using a Gleeble-3500thermal simulator.The hot deformation behavior and deformed microstructure characteristics were investigated.Based on the hyperbolic sine model,the constitutive modelling was established.The impact of the Zener-Hollomon parameters on the microstructural evolution wasstudied.The results reveal that the deformed alloys are featured by various microstructure characteristics under deformationconditions falling within high,medium and low Z values.It is also shown that the deformed microstructure gradually changes frominstability microstructure,incomplete dynamic recrystallized structure to complete and coarsened dynamic recrystallized structurewith the decrease of the Z value.Furthermore,the optimal hot processing parameters are determined with the ln Z value rangingfrom22.17to29.25.Keywords:AZ61magnesium alloy;hot processing;constitutive modelling;Zener-Hollomon parameter;dynamic recrystallization . All Rights Reserved.。
基于Oxley’s 理论的Al7050 合金JC 本构模型参数优化
The project supported by the Shaanxi Provincial Science and Technology Department Key Research Project( No. 2020GY ̄
121) .
Manuscript received 20200803ꎬ in revised form 20200827.
with the software are 15 08% and 25 97% respectivelyꎬ and the conclusion that the simulation value of the cutting force with the
custom material model is more consistent with the test result is drawn.
simulation and test values of the main cutting force and feed force using the custom material model are 4 79% and 16 08%ꎬ
respectively. The average errors of the simulation and test values of the main cutting force and feed force of the material model
OF AL7050 ALLOY BASED ON OXLEY’ S THEORY
王 运 ∗∗1 张昌明 ∗∗∗1ꎬ2 张 昱1
(1. 陕西理工大学 机械工程学院ꎬ 汉中 723000)
Copyright©博看网
. All Rights Reserved.
Li_(2)O-Al_(2)O_(3)-SiO_(2)系微晶玻璃的研究进展
Li_(2)O-Al_(2)O_(3)-SiO_(2)系微晶玻璃的研究进展任贝贝;刘亚鑫;黄欣;王霆;王娜;姜宏;熊春荣;郝红勋【期刊名称】《硅酸盐通报》【年(卷),期】2024(43)4【摘要】Li_(2)O-Al_(2)O_(3)-SiO_(2)(LAS)系微晶玻璃由于具有热膨胀系数低、透明度高、力学性能优良等特点,被广泛应用于国防、建筑、化工、生物医药等多个领域,近年来受到研究者的广泛关注。
本文综述了LAS系微晶玻璃的研究现状,介绍了LAS晶相体系及相关玻璃产品,对比分析了LAS系微晶玻璃各制备工艺的特点,并讨论了LAS系微晶玻璃晶核剂的种类及成核机理,最后总结了LAS系微晶玻璃性能、应用以及相应表征技术和测试手段,并指出了LAS系微晶玻璃存在的问题及未来的发展方向。
【总页数】16页(P1181-1196)【作者】任贝贝;刘亚鑫;黄欣;王霆;王娜;姜宏;熊春荣;郝红勋【作者单位】天津大学国家工业结晶工程技术研究中心;海南大学海南省特种玻璃重点实验室【正文语种】中文【中图分类】TQ171.73【相关文献】1.混合碱效应对Li_(2)O-Al_(2)O_(3)-SiO_(2)系玻璃结构和热膨胀性能的影响2.Na_(2)O-Al_(2)O_(3)-SiO_(2)-P_(2)O_(5)玻璃的结构和析晶性能研究3.晶化温度对MgO-Al_(2)O_(3)-SiO_(2)系尖晶石微晶玻璃结构与性能的影响4.晶核剂对Li_(2)O-Al_(2)O_(3)-SiO_(2)体系微晶玻璃性能的影响5.不同Al_(2)O_(3)/SiO_(2)比的MgO-Al_(2)O_(3)-SiO_(2)微晶玻璃制备及性能研究因版权原因,仅展示原文概要,查看原文内容请购买。
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Received 19 January 2005; 29 September 2005. 2000 Mathematics Subject Classification 20K01 (primary), 20D60 (secondary).
a small fraction of the finite abelian groups can have the R´edei property. Also it will be shown that if p, q are distinct primes then groups of type (p, p, q) have the
If G is a direct product of cyclic groups of orders t1, . . . , ts, then we will say that G is of type (t1, . . . , ts). The group G is called an elementary p-group if it is of type (p, . . . , p) for some prime p. We say that a p-group is of rank k if it is a direct product of k cyclic groups. We have to point out that a finite abelian group can be decomposed into a direct product of cyclic groups in essentially different ways. This will not cause any problem since the uniqueness of t1, . . . , ts plays no role in our arguments. There is of course a canonical type, where one insists that ti | ti+1 for each i, 1 i s − 1. However, it is more sensible to be flexible here, as one wishes to highlight the structure of each Sylow subgroup.
R´edei property.
2. A group with the R´edei property
A subset A of a finite abelian group G is called periodic if there is an element g ∈ G \ {e} such that Ag = A. Each element g with this property is called a period of A. All the periods of A together with the identity element form a subgroup H of G. In addition there is a subset C of G such that A = HC, where the product is direct. We say that a subset A of G can be replaced by A if G = A B is a factorization whenever G = AB is a factorizationact
We say that a finite abelian group does not have the R´edei property if it can be expressed as a direct product of two of its subsets such that both subsets contain the identity element and both subsets span the whole group. It will be shown that only a small fraction of the finite abelian groups can have the R´edei property. For groups of odd order an explicit list of the possible exceptions is compiled.
Initially it was not obvious if there is any group without the R´edei property. Fraser and Gordon [2] gave the first examples for p-groups without the R´edei property. Their smallest example is an elementary 5-group of rank 6. Szabo´ [6] exhibited the first cyclic group without the R´edei property. In this paper we will show that only
Assume first that |A| = p and |B| = pq. If A contains only p-elements, then A ⊂ x, y and so A = G. We may assume that A contains not only p-elements. By Proposition 3 of [5], A can be replaced by A in the factorization G = AB, where A consists of the p-components of the elements of A. From the factorization G = A B it follows that the p-components of the elements of A are distinct. This gives that the p-components of the elements of A \ {e} have order p. (The point is that none of them can be e.) There is an element a ∈ A such that |a| = pq. It follows from Satz 6 and Hilfsatz 17 of [3] that in the factorization G = AB the factor A can be replaced by
Theorem 1. Let p, q be distinct primes. Groups of type (p, p, q) have the R´edei property.
Proof. Let G be a group of type (p, p, q) and let x, y, z be basis elements of G with |x| = |y| = p and |z| = q. Let G = AB be a normalized factorization of G. We will show that A = G or B = G.
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SA´ NDOR SZABO´
(iv) (32, 32), (3, 3, 3, 3) (see [9]); (v) (23, 23), (22, 22, 2) (see [9] and [7]); (vi) (2, . . . , 2), with rank 7 (see [1]). Here p, q are distinct primes and α, β 2 are integers.
It is a famous result of R´edei [3] that if a finite abelian group is a direct product of its normalized subsets such that each subset has a prime number of elements then at least one of the factors must be a subgroup. We will refer to this result simply as R´edei’s theorem.
J. London Math. Soc. (2) 73 (2006) 701–715 Ce 2006 London Mathematical Society
doi:10.1112/S0024610706022861
CONSTRUCTIONS RELATED TO THE RE´DEI PROPERTY OF GROUPS
If e ∈ A and e ∈ B, then we say that A and B are normalized subsets of G. If in the factorization G = AB the factors A and B are normalized subsets then we call the factorization a normalized factorization. We will use A to denote the smallest subgroup of G which contains the subset A of G. The subgroup A is also called the span of the subset A in G or the subgroup generated by A in G.