Article(id=1241777700839424063, tenantId=1146029695717560320, journalId=1240670690148397066, issueId=1241777699996368955, articleNumber=null, orderNo=null, doi=10.3963/j.issn.1001-487X.2024.02.020, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1681833600000, receivedDateStr=2023-04-19, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773992474994, onlineDateStr=2026-03-20, pubDate=1717171200000, pubDateStr=2024-06-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773992474994, onlineIssueDateStr=2026-03-20, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773992474994, creator=13701087609, updateTime=1773992474994, updator=13701087609, issue=Issue{id=1241777699996368955, tenantId=1146029695717560320, journalId=1240670690148397066, year='2024', volume='41', issue='2', pageStart='1', pageEnd='252', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773992474792, creator=13701087609, updateTime=1773992784144, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241778997575619516, tenantId=1146029695717560320, journalId=1240670690148397066, issueId=1241777699996368955, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241778997575619517, tenantId=1146029695717560320, journalId=1240670690148397066, issueId=1241777699996368955, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=160, endPage=169, ext={EN=ArticleExt(id=1241777701212717125, articleId=1241777700839424063, tenantId=1146029695717560320, journalId=1240670690148397066, language=EN, title=Research Progress on Synthesis of Carbon Nanomaterials by Gaseous Detonation, columnId=1241046467696193882, journalTitle=Blasting, columnName=SPECIAL BLASTING, runingTitle=null, highlight=null, articleAbstract=

Gaseous detonation synthesis is a novel approach for the production of carbon nanomaterials. This method offers several advantages over other techniques, including rapid reaction kinetics, diverse product types, high yield, exceptional purity, straightforward operation, and cost-effectiveness. These benefits make it highly suitable for promoting the industrial-scale manufacturing of carbon nanomaterials. To elucidate the current research and development status of gaseous detonation-synthesized carbon nanomaterials, this paper provides an overview of the necessary instruments and equipment, experimental procedures, theoretical calculations, and product characterization methods employed in this synthesis technique. Additionally, it summarizes the technologies and methodologies used to synthesize various carbon-based materials such as carbon-coated nanometallic particles, carbon nanospheres, carbon nanotubes (CNTs), carbon dots (CDs), and carbon nanocapsules via gaseous detonation synthesis. The morphology of these synthesized products is analyzed along with their structural features and performance characteristics. Furthermore, this study explores the potential applications and technological advancements associated with these newly developed gaseous detonation-synthesized carbon nanomaterials to lay a solid theoretical foundation for rational design optimization and large-scale production of nanostructured materials in line with industry standards in explosive engineering. Current research indicates that the synthesis of detonation should be integrated with both macroscopic detonation theory and microscopic particle growth. The investigation of detonation wave engine and the analysis of detonation cell structure have become prominent areas of study, particularly in understanding the relationship between macroscopic detonation cells and the microscopic synthesis process of nanomaterials. However, a significant challenge remains in comprehending the growth mechanism of particles synthesized through detonation on a micro-scale, necessitating the utilization of molecular dynamics and lattice Boltzmann calculation methods for resolution.

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LI Xiao-jie (1963-), male, Dalian City, Liaoning Province, Ph. D, professor, engaged in research on explosion mechanics and special blasting, (E-mail) .
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气相爆轰合成是一种新型的碳纳米材料制备方法,相对于其他碳纳米材料制备方法而言具有反应速度快、产物种类多、产量大、纯度高、操作简单和经济性高等优点,有利于促进碳纳米材料的工业化生产。为深入阐明气相爆轰法合成碳纳米材料的研究与发展状况,介绍了气相爆轰法合成所需仪器设备、实验流程、理论计算以及产物的表征方法等,整理归纳了气相爆轰法合成碳包覆纳米金属粒子、碳纳米球、碳纳米管、碳点和碳纳米胶囊等技术与方法,分析了合成产物的形貌、结构及性能特征,展望了气相爆轰下各种新型碳纳米材料的应用潜力与技术发展趋势,以期为合理设计、针对性优化、规模化合成纳米材料奠定理论基础。研究表明:爆轰合成应结合宏观的爆轰理论和微细观的粒子生长。当前借助爆轰波发动机与爆轰胞格结构研究热点,使宏观爆轰胞格与纳米材料微观合成过程构成联系是重点研究方向。然而,在研究爆轰合成粒子的生长机理时,聚集在微细尺度上的纳米粒子生长仍然也是一种跨尺度问题,有必要引入分子动力学和格子波尔兹曼计算方法加以解决。

, correspAuthors=null, authorNote=null, correspAuthorsNote=
李晓杰(1963-),男,辽宁省大连市,博士、教授,从事爆炸力学和特种爆破方面研究,(E-mail)
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陈端花(1999-),女,山东省新泰市,在读硕士,从事气相爆轰合成碳纳米材料方面研究,(E-mail)

CHEN Duan-hua (1999-), female, Xintai, Shandong Province, studying for a master's degree, engaged in the research on the synthesis of carbon nanomaterials by gaseous detonation, (E-mail) .

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陈端花(1999-),女,山东省新泰市,在读硕士,从事气相爆轰合成碳纳米材料方面研究,(E-mail)

CHEN Duan-hua (1999-), female, Xintai, Shandong Province, studying for a master's degree, engaged in the research on the synthesis of carbon nanomaterials by gaseous detonation, (E-mail) .

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陈端花(1999-),女,山东省新泰市,在读硕士,从事气相爆轰合成碳纳米材料方面研究,(E-mail)

CHEN Duan-hua (1999-), female, Xintai, Shandong Province, studying for a master's degree, engaged in the research on the synthesis of carbon nanomaterials by gaseous detonation, (E-mail) .

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Study on the synthesis and application of carbon dots by gaseous detonation[D]. Dalian: Dalian University of Technology, 2020. (in Chinese), articleTitle=Study on the synthesis and application of carbon dots by gaseous detonation, refAbstract=null), Reference(id=1241777728358252821, tenantId=1146029695717560320, journalId=1240670690148397066, articleId=1241777700839424063, doi=null, pmid=null, pmcid=null, year=2018, volume=87, issue=null, pageStart=233, pageEnd=241, url=null, language=null, rfNumber=[52], rfOrder=73, authorNames=YAN Hong-hao, HE Chuang, LI Xiao-jie, journalName=Diamond & Related Materials, refType=null, unstructuredReference=YAN Hong-hao, HE Chuang, LI Xiao-jie, et al. A solvent-free gaseous detonation approach for converting benzoic acid into graphene quantum dots within milliseconds[J]. 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气相爆轰合成碳纳米材料的研究进展
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陈端花 a , 李晓杰 a, b , 闫鸿浩 a, b , 王小红 a, b , 王宇新 a, b
爆破 | 特种爆破 2024,41(2): 160-169
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爆破 | 特种爆破 2024, 41(2): 160-169
气相爆轰合成碳纳米材料的研究进展
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陈端花a , 李晓杰a, b , 闫鸿浩a, b, 王小红a, b, 王宇新a, b
作者信息
  • a.大连理工大学 工程力学系,大连 116024
  • b.大连理工大学 工业装备结构分析优化与CAE软件全国重点实验室,大连 116024
  • 陈端花(1999-),女,山东省新泰市,在读硕士,从事气相爆轰合成碳纳米材料方面研究,(E-mail)

    CHEN Duan-hua (1999-), female, Xintai, Shandong Province, studying for a master's degree, engaged in the research on the synthesis of carbon nanomaterials by gaseous detonation, (E-mail) .

通讯作者:

李晓杰(1963-),男,辽宁省大连市,博士、教授,从事爆炸力学和特种爆破方面研究,(E-mail)
Research Progress on Synthesis of Carbon Nanomaterials by Gaseous Detonation
Duan-hua CHENa , Xiao-jie LIa, b , Hong-hao YANa, b, Xiao-hong WANGa, b, Yu-xin WANGa, b
Affiliations
  • a.Department of Engineering Mechanics, Optimization and CAE Software for INDUSTRIAL Equipment, Dalian University of Technology, Dalian 116024, China
  • b.State Key Laboratory of Structural Analysis, Optimization and CAE Software for INDUSTRIAL Equipment, Dalian University of Technology, Dalian 116024, China
出版时间: 2024-06-01 doi: 10.3963/j.issn.1001-487X.2024.02.020
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气相爆轰合成是一种新型的碳纳米材料制备方法,相对于其他碳纳米材料制备方法而言具有反应速度快、产物种类多、产量大、纯度高、操作简单和经济性高等优点,有利于促进碳纳米材料的工业化生产。为深入阐明气相爆轰法合成碳纳米材料的研究与发展状况,介绍了气相爆轰法合成所需仪器设备、实验流程、理论计算以及产物的表征方法等,整理归纳了气相爆轰法合成碳包覆纳米金属粒子、碳纳米球、碳纳米管、碳点和碳纳米胶囊等技术与方法,分析了合成产物的形貌、结构及性能特征,展望了气相爆轰下各种新型碳纳米材料的应用潜力与技术发展趋势,以期为合理设计、针对性优化、规模化合成纳米材料奠定理论基础。研究表明:爆轰合成应结合宏观的爆轰理论和微细观的粒子生长。当前借助爆轰波发动机与爆轰胞格结构研究热点,使宏观爆轰胞格与纳米材料微观合成过程构成联系是重点研究方向。然而,在研究爆轰合成粒子的生长机理时,聚集在微细尺度上的纳米粒子生长仍然也是一种跨尺度问题,有必要引入分子动力学和格子波尔兹曼计算方法加以解决。

气相爆轰合成  /  碳纳米材料  /  冲击波  /  碳包覆纳米金属  /  碳纳米胶囊

Gaseous detonation synthesis is a novel approach for the production of carbon nanomaterials. This method offers several advantages over other techniques, including rapid reaction kinetics, diverse product types, high yield, exceptional purity, straightforward operation, and cost-effectiveness. These benefits make it highly suitable for promoting the industrial-scale manufacturing of carbon nanomaterials. To elucidate the current research and development status of gaseous detonation-synthesized carbon nanomaterials, this paper provides an overview of the necessary instruments and equipment, experimental procedures, theoretical calculations, and product characterization methods employed in this synthesis technique. Additionally, it summarizes the technologies and methodologies used to synthesize various carbon-based materials such as carbon-coated nanometallic particles, carbon nanospheres, carbon nanotubes (CNTs), carbon dots (CDs), and carbon nanocapsules via gaseous detonation synthesis. The morphology of these synthesized products is analyzed along with their structural features and performance characteristics. Furthermore, this study explores the potential applications and technological advancements associated with these newly developed gaseous detonation-synthesized carbon nanomaterials to lay a solid theoretical foundation for rational design optimization and large-scale production of nanostructured materials in line with industry standards in explosive engineering. Current research indicates that the synthesis of detonation should be integrated with both macroscopic detonation theory and microscopic particle growth. The investigation of detonation wave engine and the analysis of detonation cell structure have become prominent areas of study, particularly in understanding the relationship between macroscopic detonation cells and the microscopic synthesis process of nanomaterials. However, a significant challenge remains in comprehending the growth mechanism of particles synthesized through detonation on a micro-scale, necessitating the utilization of molecular dynamics and lattice Boltzmann calculation methods for resolution.

gaseous detonation synthesis  /  carbon nanomaterials  /  shock wave  /  carbon coated nanometals  /  carbon nanocapsules
陈端花, 李晓杰, 闫鸿浩, 王小红, 王宇新. 气相爆轰合成碳纳米材料的研究进展. 爆破, 2024 , 41 (2) : 160 -169 . DOI: 10.3963/j.issn.1001-487X.2024.02.020
Duan-hua CHEN, Xiao-jie LI, Hong-hao YAN, Xiao-hong WANG, Yu-xin WANG. Research Progress on Synthesis of Carbon Nanomaterials by Gaseous Detonation[J]. Blasting, 2024 , 41 (2) : 160 -169 . DOI: 10.3963/j.issn.1001-487X.2024.02.020
碳作为自然界中最重要的元素之一,具有sp、sp2、sp3等多种杂化轨道,因此以碳为基础的纳米材料丰富多样[1]。如:碳量子点、碳纳米管、碳球、碳壳、石墨烯、富勒烯以及众多的碳包覆金属等纳米材料。这些新型碳纳米材料,不仅具有独特的结构,还具有良好的物理、化学性能,被广泛应用于各个领域。碳纳米材料比表面积大,具有很强的吸附能力,可以用作固体杂质的吸附剂,降低环境中的铅、汞、铜、铬、锌等重金属物质[2]。加之化学性能稳定、密度较小、价格低廉,所以非常适合作为储氢材料;碳纳米材料特殊的电子效应和表面效应,在催化剂领域也具有很大应用潜力;因其具有高导电性、良好化学稳定性及丰富孔结构,所以可用来充当电极[3],将碳纳米材料与ZIBs正极活性材料或锌负极复合,可有效提升ZIBs性能;从电磁波吸收方面来看,碳纳米材料显示出很强的宽带微波吸收性能,已成为新型吸波材料研究热点之一。除此之外,碳纳米材料在医学领域也能发挥很大作用,例如碳纳米管因具有质量轻、物理化学性质良好且稳定、生物相容性好、细胞穿透能力强等特点,被应用于载送生物活性分子及药物进入细胞或组织。碳量子点等碳纳米材料具有荧光性,可将其应用在治疗过程中的药物追踪方面,促进医疗技术与新型药物的发展[4]。目前制备碳纳米材料的方法主要有,石墨电弧放电法(Arc)[5,6]、固相热解法[7]、化学气相沉积法(CVD)[8]、激光蒸发法[9]、热解聚合物法[10]、原位合成法、模板法等[11]。虽然利用这些方法均可获取目标碳纳米材料,但这些方法普遍存在着仪器设备昂贵、能耗高、有效产物分离率低、经济效益差、连续性差等问题,导致对所需碳纳米材料无法实现大规模生产。为解决这一问题,大连理工大学爆炸研究组提出了合成碳纳米材料的新方法——气相爆轰法[12]。爆轰法合成碳纳米材料主要包含两种方式,固相爆轰法和气相爆轰法。对于固相爆轰法[13,14],早在20世纪80年代初期,苏联科研人员就利用负氧平衡炸药合成了纳米金刚石,之后我国也开始该领域的研究。固相爆轰合成法具有反应速率快、效率高、产量大、能耗低等优点,大连理工大学研究组也成功利用该方法制备了纳米金刚石、碳包覆纳米金属材料,以及各种纳米氧化物和硫化物,但是由于炸药、雷管以及合成环境的影响会使固相爆轰法合成材料中存在杂质,影响产品纯度。因此,使后处理复杂、制备流程繁琐,同时安全性也较低。对于气相爆轰法而言[15,16],合成纳米材料过程中不需要固体炸药、雷管,在兼具了一些固相爆轰法优点的同时,能够克服其缺点,制备过程简单,安全性高,所得产物纯度较高等。技术发展初期利用气相爆轰法成功制备纳米TiO2、SnO2、SiO2等产物[17-21],随着气相爆轰合成法的发展,逐渐将合成碳纳米材料作为研究的重点。采用类型恰当且适量的催化剂,将可燃性气体与前驱体置于气相爆轰容器中,进行电火花引爆,借助爆轰波所具有的强冲击、可控反应热、极快化学反应速率、爆轰波传播稳定的特点,能够快速、高效、安全、可控的合成高纯碳纳米材料。本文将较详细地介绍气相爆轰法合成碳纳米材料的合成体系、合成原理、表征方法等,并对目前采用气相爆轰法已合成的碳纳米材料进行归纳分析,以便进一步利用气相爆轰合成技术制备更多种类的纳米新材料,完善制备方法、理论与分析手段,为碳纳米材料科研发展与规模化生产提供参考。
气相爆轰合成碳纳米材料是将前驱体与CH4、C2H2等纯净的可燃性气体,与氧气、空气等氧化性气体混合后,置于气相爆轰容器中点火引爆,通过燃烧爆轰的能量合成纳米材料的新技术。气相爆轰容器通常根据反应物及加热条件等选取、加工制作,可采用反应釜、球形容器和爆轰管等。常用的气相爆轰管如图1所示,采用爆轰管的优点是利于对合成工艺参数的测量与研究。为了抵抗高温化学腐蚀,采用钛质衬里,两端由法兰盘密封。管内主要有四个系统:抽气、压力监测和高能点火、温度控制系统。抽气系统包含真空泵及连接排气管道,负责将管内抽成真空;压力监测系统通过精密压力表实时监测管内压力和真空度;高能点火系统包含一个高能点火器,可产生超过20 J的能量来引爆气体混合物。高能点火器安置于爆轰管起爆端的延伸管内,该管用于扩展气体点火区域,有利于促进初始爆轰波的快速稳定生长。为保证前驱体与爆源气体充分混合,获取更均匀、反应更充分的产物,通常需要利用温度控制系统对固态、液态前驱体进行加热,使其蒸发、升华或者反应生成气体,进而保证其与爆轰气体达到分子级别的均匀混合。温度控制系统则是通过控制爆轰管周围的加热油浴来实现调节的,最高温度可至453.15 K,油浴加热相对于电加热更安全、可控性更好,但相对较慢,能够实现更稳定的控制反应初始温度。
爆轰合成碳纳米材料的过程中,氧平衡是衡量气体爆炸性能、合成产物特征的重要指标。由于在合成碳纳米材料时需要生成一定量的游离碳来为碳纳米材料的生长提供碳源,因此在设计反应气体时,必须考虑反应气体中的氧含量,以及可燃元素能否被完全氧化等爆轰反应问题,通常保证实验过程处于负氧状态。
爆轰波是强冲击波,由于伴有化学反应不断提供的放热支持,可以形成稳定的爆轰传播速度,并由此对应有稳定的爆轰压力。对爆轰合成而言,就有了快速而稳定的压力、温度等反应控制条件。
气相爆轰参数爆速D的计算建立在理想模型C-J理论基础上[22],根据爆轰波的传播的质量、动量、能量方程,加之熟知的C-J条件,可求得,其中γ是多方指数,Q为反应所释放的能量。也可以计算出爆轰压力,其中ρ0是气体初始密度,P0为气体初始压力。如将混合气体爆轰反应冲击能量关系,结合化学反应的盖斯定律和热力学第一定律,还可以利用线性内插法计算理论爆温Tcj值。由此可见,可以通过改变爆轰气体的组成(γ值)、初始压力、温度等条件,控制稳定爆轰的压力、爆速、温度等,即可控制合成纳米材料的反应条件,由这些反应参数的调整变化控制影响纳米合成物的分散状态以及其形貌、结构、组分,利用爆轰的快速反应过程合成优质的纳米材料。因此,在合成实验前通常需要对爆轰过程进行模拟计算,以取得合成的爆速、爆压、爆温等参数,实现对实验可行性的预估。另外可在气相爆轰管上安装玻璃视窗,利用高速摄影仪测量爆速,安装压力传感器来测量爆压。
透射电子显微镜(TEM)通过干涉波成像得到物质的投影形貌[23],通常可以研究数纳米至微米量级的材料特征。对爆轰纳米产物进行TEM表征可以直接观察其分布情况,以及颗粒大小、形状等外观形貌,如图2即是爆轰合成的碳包覆铁纳米材料TEM镜像。
从由图中可以观察到深色纳米铁颗粒外面包覆有明显的碳层,内核的纳米铁颗粒呈现出圆形、椭圆形特征,并且壳内铁颗粒的粒径由5 nm至18 nm不等。根据TEM得到直观的信息后,结合其他表征方法对产物的组成成分、结构以及其他物理化学性能进行探究。另外,利用高分辨率HRTEM还可以观测石墨层的构成与分布情况,利用电子衍射还可以研究分析局部材料的晶体结构信息。
X射线衍射分析(XRD)是利用定波长的X射线在晶体中的衍射现象来获得衍射后的X射线特征,经过处理得到衍射图谱。利用XRD谱图确定材料晶体结构,鉴定物相,也可以观察晶体内部的位错或晶格缺陷等。通过对爆轰产物进行XRD表征[23],能够对产物的晶体组分进行分析,确定材料的结晶状态。XRD衍射图谱中的每一个衍射峰都是由某一晶体的某个晶面产生的,通过查阅PDF卡片与实验产物所得图谱进行对比,完成物相鉴定,从而确定晶体结构类型。图3为XRD对气相爆轰碳包覆铁纳米颗粒的衍射图谱,经过特征衍射线位置与标准卡对比判断产物的类型。图中五组实验均在26.5°附近有一个强度比较大的明显特征谱,对应的是石墨结构(002)晶面,图谱衍射背底浮动较大,说明产物以无定形碳为主,并且其中一些无定形碳已经具有了石墨化特征。第四组在26.5°附近峰值最高,最尖锐,说明此组产物石墨化程度最高。若想进一步确定爆轰产物的结构,还可以结合拉曼光谱进行分析。
使用XRD表征时要注意阳极靶的选择,常用的阳极靶材有Fe、Co、Cu、Mo等。选择合适的靶材尽量减少样品对X射线的吸收,降低样品所产生的荧光X射线对衍射图背底的影响。阳极靶材一般选用规则:Z靶材<<Z试样-1或者Z靶材>>Z试样Z为物质原子序数)。同时需要注意扫描速度,同一份样品物质,不同的扫描速度,所得结果有很大差异。若XRD表征结果只用来做定性分析时,扫描速度不能超过4°/min,若用来做定量分析,则扫描速度不大于1°/min。
在明确产物的形貌,分子组成结构、成分之后,为了能更好地研究碳纳米材料,则还要对其更多的性能特征进行研究与表征,以下为几种常见的探究物质性能的表征方法。
首先,可以通过热分析测定物质加热或者冷却过程中热重与差热变化来研究物质的物理性质[24],包括物质的质量变化、相变热焓、熔点变化、结构变化、抗氧化性等性能。
其次,通过BET表征探究产物的吸附能力、比表面积、孔洞与孔容分布等等[25-27]。若产物比表面积大,吸附能力强,则可用作优秀的催化剂载体。特殊的孔洞与孔容分布有利于对特定物质产生吸附,更利于作为分离载体使用。
另外,若纳米材料有很优异的吸波效应,可以利用矢量网格分析仪进行电磁波吸收性能测定。赵铁军、李雪琪的研究中提到[28],碳包铁、碳包钴、碳纳米管以及碳包覆坡莫合金等碳基磁性复合材料具有良好的电磁波吸波性能[29],可用于复杂环境下的电磁战中对空中电磁干扰域的掩护。并且通过氩气等惰性气体保护热处理后,其吸波能力明显得到提升。
最后,作为化学分析中常用的Raman光谱分析也被广泛用于碳材料研究[30],通过谱图中无定形碳D峰与石墨的特征峰G峰的比值大小可以判断碳纳米材料的石墨化程度,由2D峰的大小可以判断石墨层的厚度,从而结合XRD、TEM等其他表征结果可以对纳米碳产物进行更准确的判断。另外,还可以利用红外光谱分析表征纳米粒子表面的化学官能团,鉴定紫外吸收光谱和可见吸收光谱,利用VSM表征磁性能等等。
随着气相爆轰法合成纳米材料技术逐渐趋向成熟,将气相爆轰合成技术应用于碳纳米材料合成,并取得可观的成果。
2013年起李晓杰、殷永等人开始利用气相爆轰法合成碳纳米材料,殷永以易升华的二茂铁为前驱体[31],分别以氢、氧混合气体和氢气、空气混合气体作为爆源,在气相爆轰管中进行实验。当以氢气和空气的混合气体作为爆源进行试验时,虽然可以成功制成碳包覆铁纳米结构,但是产物中含有二茂铁杂质,后期提纯过程较为复杂。当以氢氧混合气作为爆源进行试验时,不但能够成功获得碳包覆铁纳米颗粒,并且产物中不含二茂铁,纯度比较高。因此后续气相爆轰合成碳包覆铁纳米颗粒探究实验均选用氢气、氧气混合气体作为爆源进行。改变前驱体含量和初始温度分别进行实验发现[32,33],随着前驱体二茂铁含量的增加,生成的颗粒大小逐渐均匀,但团聚现象愈加明显;随着初始温度的升高,碳包覆纳米铁颗粒的晶粒尺寸均为30~50 nm,并且开始趋于均匀化,但是铁碳化合物含量增加。对产物进行退热处理以及VSM表征,结果表明,碳包覆铁纳米颗粒呈现出良好的硬磁性和顺磁性双重性质。在此基础上,闫鸿浩、赵铁军等人仍然以二茂铁为前驱体[34-37],改变氢气和氧气的混合比例进行实验,实验表明,氢气和氧气的比例会影响所生成的碳包铁纳米颗粒的形貌大小及分散性。当氢气与氧气比例为2∶1,二茂铁质量为2.5~3.5 g时,所得产物最为理想,呈现球形或椭圆形,并且有明显的核壳结构。产物的形貌如图4所示。从安全性与前驱体利用率着手考虑,潘训岑等人利用五羰基铁取代二茂铁作为铁源与氧气、乙炔混合气体爆轰合成[38],成功制备了粒径5~8 nm碳包覆纳米铁颗粒。五羰基铁常温常压下以液体状态存在,沸点103℃,相较二茂铁沸点较低,更容易气化与可爆气体均匀混合,从而生成更细更小更纯净的纳米材料。因为五羰基铁常温下是有毒气体,所以通过无毒的九羰基二铁加热分解发生如下反应:3Fe2(CO)9=3Fe(CO)5↑+Fe3(CO)12,从而得到五羰基铁。实验发现当九羰基二铁与乙炔物质的量比值约为1%时,即处于少铁状态时,产物呈现出一种新型结构——碳纳米胶囊[39-42],如图5所示。经BET表征比表面积达253.857 m2·g-1,孔体积为0.940 cm·g-1,平均孔径为2.731 nm,这种结构比表面积较大,具有很强的吸附性。但值得注意的是,目前为止,尚未得出获得此结构单一产物时前驱体与爆源的具体配比。
2017年闫鸿浩等人将乙酰丙酮铜作为前驱体[43,44],分别以氢气、氧气混合气体以及氢气、空气混合气体作为爆源置于气相爆轰管中,在保证负氧条件下发生反应。实验得到分散性良好的碳包覆铜纳米晶粒,晶粒呈现大多为10 nm以下的圆形或椭圆形结构,如图6所示,石墨层厚度仅在2~5 nm。纳米铜是诸多非磁性导体纳米金属中低成本、高储量、具有优良导电性和高催化性的材料,碳包覆解决了单质纳米铜颗粒易氧化、团聚等问题,可广泛地应用于电子印刷、催化剂、生物医学等领域。
杨瑞利用苯作为碳源与氧气发生气相爆轰反应[45,46],成功合成碳纳米球。实验改变参与反应的气体浓度发现,随着苯氧混合气体浓度的增加,反应体温度、压力有所提高并且产物的结晶度也会有所提高,产物的分散性变好,团聚现象减弱,如图7中(a)~(b)所示。同时结合颗粒长大模型对产物碳纳米球的合成机理做出假设并进行分析[47],得出通过气相爆轰合成的碳纳米球的形成经历了碰撞、凝聚、长大、形成四个阶段。另外,杨瑞利用二茂铁作催化剂的条件下,引爆浓度比为1∶1的甲烷和氧气,制备碳纳米管。当二茂铁质量达到2.0 g时,此时有大量的碳纳米管的生成,少量的碳包覆纳米颗粒。所生成的碳纳米管形貌及尺寸比较单一,如图8所示,碳纳米管纹路清晰,基本上是由铁纳米颗粒一端生长延长而成,呈现出杂序生长,此种碳纳米管包覆金属颗粒材料[48,49],其电磁波吸收性能良好常常可用于电磁屏蔽材料[50]
何闯利用气相爆轰法在毫秒级别内一步合成石墨烯量子点和聚合物点两类碳点[51-54],形貌如图9图10所示。由气相爆轰产物石墨烯量子点TEM图像可观察到,产物分散均匀,无团聚现象,并且碳核内部有蜂窝状结构出现。通过改变爆源气体的混合比例,得到单个结晶度高,内核同样出现类蜂窝状石墨烯结构的聚合物碳点。两种产物均呈现高亮的蓝色荧光,将二者分别与硅胶和水混合制作白光转换层,能够将紫外光LED转换为白光LED。此外,利用四球摩擦测试两类碳点,平均摩擦系数、磨斑直径和磨斑深度较150SN基础油分别降低65%、43.5%和90.9%,将其分别用作油基和水基润滑液的添加剂,能够用于提高润滑液的减磨抗磨性能,产物具有很大实用性。
从现有的研究可见,目前利用气相爆轰合成碳纳米材料一般选择易燃气体(H2、C2H2等)与氧气、空气混合作为爆炸气体,选择相应金属源和碳源,在容器内进行气相爆轰合成。合成中,可以通过改变爆源气体组分含量、前驱体种类、初始温度、初始压强等因素,控制稳定爆轰的压力、爆速、温度等反应条件,调整合成出各种组分、形貌、结构、分散状态的纳米碳材料,已合成出的纳米材料有,碳量子点、纳米碳管、纳米碳包金属、纳米碳胶囊等等。也利用TEM、XRD、BET以及拉曼光谱实验等技术研究表征了这些爆轰合成产物的形貌特征、晶体结构、表面性能、热稳定性表面理化特性等,从而得出最利于目标产物生成的条件。
但在利用气相爆轰法合成碳纳米材料过程中,无论是在理论上还是合成技术上仍存在着很多难点。在理论上的难点是既有宏观的爆轰理论问题,也有粒子生成与成长的微观问题。在宏观上气相爆轰合成在高温高压下反应十分迅速,达到毫微秒级别,很难观测其高速的反应过程。加之,近年由于对爆轰波发动机的研究热点,人们发现了爆轰胞格结构可能是由于不均匀的热点所形成,这就使宏观的爆轰胞格会对纳米材料的微观合成过程构成影响,因此,研究气相爆轰合成时紧跟爆轰学研究前沿问题就显得十分必要。另外,在宏观上的爆轰观测技术也十分必要,对于如何对中间的复杂反应过程进行实验追踪和表征,不仅是爆轰合成的难题,也是爆轰学本身尚待解决的难题。需要研究的微观难题是爆轰合成的粒子生长机理。通常爆轰过程中高温可达3000~4000 K,这样的高温使分子的热运动十分剧烈,甚至会发生电离。在3000~4000 K高温下,碳原子的平均热运动速率会高达2000~2500 m·s-1,甚至与爆速D相接近,远超过了爆轰的质点运动速度。因此,爆轰合成的一次粒子直径除受元素空间密度、化学性质影响外,单从分子运动碰撞的角度上,受爆轰温度的影响高于波后质点运动;而当爆轰反应结束稀疏波使温度下降时,二次粒子的聚集会受爆轰湍流运动的影响。因此,爆轰的纳米粒子生成与生长在微细尺度上也是一种跨尺度问题,有必要引入分子动力学和格子波尔兹曼计算才可能解决;再者是在爆轰合成技术上,尽管爆轰合成的效率较高,理论上每立方米容器可单次合成0.5~0.7 kg纳米碳材料。但要进一步提高爆轰合成效率,就必须研究大型爆炸合成容器和自动化爆轰合成技术。针对自动化爆轰合成技术,近期大量研究爆轰波发动机技术无疑对爆轰合成将是极大的促进。对于大型爆炸合成容器,对其设备强度等安全性问题研究是极为必要的。除此之外,对充入容器的气体均匀混合、温控预热、快速抽充气体等都是设计的关键问题。另外,爆轰合成中影响产物生成的因素很多,需要设计更多的实验,以排除环境的不可控因素等等。最后,利用不同的前驱体、爆源可能得到同一种产物,也可以合成出不同的产物,以上需要研究者从产物的优良性以及获得产物的经济性、安全性着手选择合适的前驱体、爆源。
综上所述,经过研究人员的不断摸索研究,对利用气相爆轰法合成碳纳米材料技术的已经逐渐获得了较丰富的研究成果。作为高效、经济、简便、可控的纳米碳材料合成新技术,经过进一步深入的理论研究与技术探索,会发展出更为广阔的应用领域空间。
  • 国家自然科学基金(12072067)
  • 金属粉末的爆炸压焊及其机理研究(11672067)
  • 爆炸焊接界面细观缺陷产生的力学机理研究(12172084)
  • 碳点的气相爆轰扫掠法制取及其水基润滑剂抗磨减摩机制研究
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2024年第41卷第2期
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doi: 10.3963/j.issn.1001-487X.2024.02.020
  • 接收时间:2023-04-19
  • 首发时间:2026-03-20
  • 出版时间:2024-06-01
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  • 收稿日期:2023-04-19
基金
National Natural Science Foundation of China(12072067)
国家自然科学基金(12072067)
explosive pressure welding of metal powder and its mechanism research(11672067)
金属粉末的爆炸压焊及其机理研究(11672067)
mechanical mechanism research on the generation of micro defects at explosive welding interface(12172084)
爆炸焊接界面细观缺陷产生的力学机理研究(12172084)
preparation of carbon dots by gas detonation sweeping method and research on anti-wear and friction reduction mechanism of water-based lubricant
碳点的气相爆轰扫掠法制取及其水基润滑剂抗磨减摩机制研究
作者信息
    a.大连理工大学 工程力学系,大连 116024
    b.大连理工大学 工业装备结构分析优化与CAE软件全国重点实验室,大连 116024

通讯作者:

李晓杰(1963-),男,辽宁省大连市,博士、教授,从事爆炸力学和特种爆破方面研究,(E-mail)
参考文献
分享链接
https://castjournals.cast.org.cn/joweb/bp/CN/10.3963/j.issn.1001-487X.2024.02.020
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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