Article(id=1239215310163726753, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239215308985136031, articleNumber=null, orderNo=null, doi=10.12465/j.issn.0253-4339.2025.04.097, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1715529600000, receivedDateStr=2024-05-13, revisedDate=1716912000000, revisedDateStr=2024-05-29, acceptedDate=1716998400000, acceptedDateStr=2024-05-30, onlineDate=1773381553450, onlineDateStr=2026-03-13, pubDate=1755273600000, pubDateStr=2025-08-16, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773381553450, onlineIssueDateStr=2026-03-13, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773381553450, creator=13701087609, updateTime=1773381553450, updator=13701087609, issue=Issue{id=1239215308985136031, tenantId=1146029695717560320, journalId=1238823019242635269, year='2025', volume='46', issue='4', pageStart='1', pageEnd='170', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773381553169, creator=13701087609, updateTime=1773381893131, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1239216734947824534, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239215308985136031, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1239216734947824535, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239215308985136031, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=97, endPage=105, ext={EN=ArticleExt(id=1239215310406996387, articleId=1239215310163726753, tenantId=1146029695717560320, journalId=1238823019242635269, language=EN, title=Research on Evaporation and Deposition Characteristics of Suspended Droplets Containing Nanoparticles, columnId=null, journalTitle=Journal of Refrigeration, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Evaporation of functional nanoparticle-containing droplets on solid surfaces plays a key role in applications such as air conditioning, refrigeration, and electronic cooling. In this study, we experimentally investigated the evaporation behavior and particle deposition of nanofluid droplets on solid surfaces. The deposition patterns were photographed, and microscopic characterizations were performed. The results show that the droplets always evaporate in the mode of constant contact radius. Changes in substrate temperature and droplet volume have little influence on the evaporation mode and morphology of the droplets, and the contact angle changes linearly with time. The surfactant can significantly regulate the kinetic behavior of droplet spreading. The addition of only 0.25% of surfactant sodium dodecyl sulfate (SDS) increases the droplet spreading radius from 0.71 mm to 1.12 mm, decreases the initial contact angle from 83° to 54°, and increases the area of spreading by 89%. The substrate temperature and droplet volume significantly affect the deposition patterns after droplet evaporation. The higher the substrate temperature, the larger the droplet volume and the more obvious the coffee-ring pattern formed after evaporation. SDS significantly increases the coffee ring width, which reaches 230 μm when the mass fraction of SDS reaches 1.00%, and the particles have been widely distributed throughout the entire evaporation area, suggesting that the coffee ring effect has been effectively suppressed. By introducing the Ma number, the influence of the Marangoni effect, guided by temperature, volume, and mass fraction changes, on the internal flow of droplets and the mechanism of coffee-ring formation are explained.

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Li Yuanyuan, female, professor, School of Energy Power and Mechanical Engineering, North China Electric Power University, 86-15810949982, E-mail: . Research fields: thermodynamics, thermal properties.
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含功能性纳米颗粒液滴在固体表面上的蒸发是空调制冷、电子冷却等多个领域的关键过程。实验研究了纳米流体液滴在固体表面上的蒸发和颗粒沉积过程,拍摄沉积图案并进行微观表征。结果表明:液滴始终以恒定接触半径模式蒸发,基板温度和液滴体积的变化对液滴蒸发模式和形态影响较小,接触角随时间基本呈现线性变化。表面活性剂可极大调控液滴铺展动力学行为,仅添加质量分数为0.25%的表面活性剂十二烷基硫酸钠(SDS)可使液滴的铺展半径从0.71 mm增至1.12 mm,初始接触角从83°降至54°,铺展面积增加89%。此外,SDS可以调控增加咖啡环宽度,当SDS质量分数达到1.00%时,咖啡环宽度达到230 μm,颗粒已经较为均匀地分布在整个蒸发区域内,有效抑制了咖啡环效应。基板温度和液滴体积显著影响液滴蒸发后的沉积图案,基板温度越高,液滴体积越大,蒸发后形成更为明显的咖啡环图案。通过引入Ma数,定量表征了温度、体积和质量分数变化引导的Marangoni效应对液滴内部流动及咖啡环形成机理的影响机制。

, correspAuthors=null, authorNote=null, correspAuthorsNote=
李元媛,女,教授,华北电力大学大学能源动力与机械工程学院,15810949982,E-mail:。研究方向:热力学,工质热物性。
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journalId=1238823019242635269, articleId=1239215310163726753, language=CN, orderNo=1, keyword=纳米流体), Keyword(id=1239232340392735418, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310163726753, language=CN, orderNo=2, keyword=液滴蒸发), Keyword(id=1239232340472427197, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310163726753, language=CN, orderNo=3, keyword=颗粒自组装), Keyword(id=1239232340552118982, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310163726753, language=CN, orderNo=4, keyword=咖啡环)], refs=[Reference(id=1239232344700285782, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310163726753, doi=null, pmid=null, pmcid=null, year=2023, volume=22, issue=3, pageStart=209, pageEnd=232, url=null, language=null, rfNumber=[1], rfOrder=0, authorNames=刘联胜, 刘轩臣, 张文瑞, journalName=热科学与技术, refType=null, unstructuredReference=刘联胜, 刘轩臣, 张文瑞, 等. 固着液滴蒸发研究进展及展望[J]. 热科学与技术, 2023, 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A model for contact angle hysteresis[J]. 1984, 81(1): 552-562., articleTitle=A model for contact angle hysteresis, refAbstract=null)], funds=[Fund(id=1239232344184386372, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310163726753, awardId=52076074, language=EN, fundingSource=National Natural Science Foundation of China(52076074), fundOrder=null, country=null), Fund(id=1239232344297632587, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310163726753, awardId=52076074, language=CN, fundingSource=国家自然科学基金(52076074), fundOrder=null, country=null), Fund(id=1239232344385712972, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310163726753, awardId=52376008, language=EN, fundingSource=National Natural Science Foundation of China(52376008), fundOrder=null, country=null), Fund(id=1239232344457016142, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310163726753, 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温度/℃纳米流体
动力黏度/(10-3 Pa·s)导热系数/[W/(m·K)]动力黏度/(10-3 Pa·s)导热系数/[W/(m·K)]
201.0020.5981.100.65
300.7970.6160.940.67
400.6530.6310.870.70
500.5470.6440.790.72
600.4660.6540.720.75
700.4040.6630.660.79
), ArticleFig(id=1239232344020808513, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310163726753, language=CN, label=表1, caption=水和纳米流体的动力黏度与导热系数取值, figureFileSmall=null, figureFileBig=null, tableContent=
温度/℃纳米流体
动力黏度/(10-3 Pa·s)导热系数/[W/(m·K)]动力黏度/(10-3 Pa·s)导热系数/[W/(m·K)]
201.0020.5981.100.65
300.7970.6160.940.67
400.6530.6310.870.70
500.5470.6440.790.72
600.4660.6540.720.75
700.4040.6630.660.79
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含纳米颗粒悬浮液滴蒸发及颗粒沉积特性研究
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高峰 , 李元媛 , 陆规
制冷学报 | 2025,46(4): 97-105
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制冷学报 | 2025, 46(4): 97-105
含纳米颗粒悬浮液滴蒸发及颗粒沉积特性研究
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高峰, 李元媛 , 陆规
作者信息
  • 华北电力大学能源动力与机械工程学院 北京 102206

通讯作者:

李元媛,女,教授,华北电力大学大学能源动力与机械工程学院,15810949982,E-mail:。研究方向:热力学,工质热物性。
Research on Evaporation and Deposition Characteristics of Suspended Droplets Containing Nanoparticles
Feng Gao, Yuanyuan Li , Gui Lu
Affiliations
  • School of Energy Power and Mechanical Engineering, North China Electric Power University, Beijing, 102206, China
出版时间: 2025-08-16 doi: 10.12465/j.issn.0253-4339.2025.04.097
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含功能性纳米颗粒液滴在固体表面上的蒸发是空调制冷、电子冷却等多个领域的关键过程。实验研究了纳米流体液滴在固体表面上的蒸发和颗粒沉积过程,拍摄沉积图案并进行微观表征。结果表明:液滴始终以恒定接触半径模式蒸发,基板温度和液滴体积的变化对液滴蒸发模式和形态影响较小,接触角随时间基本呈现线性变化。表面活性剂可极大调控液滴铺展动力学行为,仅添加质量分数为0.25%的表面活性剂十二烷基硫酸钠(SDS)可使液滴的铺展半径从0.71 mm增至1.12 mm,初始接触角从83°降至54°,铺展面积增加89%。此外,SDS可以调控增加咖啡环宽度,当SDS质量分数达到1.00%时,咖啡环宽度达到230 μm,颗粒已经较为均匀地分布在整个蒸发区域内,有效抑制了咖啡环效应。基板温度和液滴体积显著影响液滴蒸发后的沉积图案,基板温度越高,液滴体积越大,蒸发后形成更为明显的咖啡环图案。通过引入Ma数,定量表征了温度、体积和质量分数变化引导的Marangoni效应对液滴内部流动及咖啡环形成机理的影响机制。

纳米流体  /  液滴蒸发  /  颗粒自组装  /  咖啡环

Evaporation of functional nanoparticle-containing droplets on solid surfaces plays a key role in applications such as air conditioning, refrigeration, and electronic cooling. In this study, we experimentally investigated the evaporation behavior and particle deposition of nanofluid droplets on solid surfaces. The deposition patterns were photographed, and microscopic characterizations were performed. The results show that the droplets always evaporate in the mode of constant contact radius. Changes in substrate temperature and droplet volume have little influence on the evaporation mode and morphology of the droplets, and the contact angle changes linearly with time. The surfactant can significantly regulate the kinetic behavior of droplet spreading. The addition of only 0.25% of surfactant sodium dodecyl sulfate (SDS) increases the droplet spreading radius from 0.71 mm to 1.12 mm, decreases the initial contact angle from 83° to 54°, and increases the area of spreading by 89%. The substrate temperature and droplet volume significantly affect the deposition patterns after droplet evaporation. The higher the substrate temperature, the larger the droplet volume and the more obvious the coffee-ring pattern formed after evaporation. SDS significantly increases the coffee ring width, which reaches 230 μm when the mass fraction of SDS reaches 1.00%, and the particles have been widely distributed throughout the entire evaporation area, suggesting that the coffee ring effect has been effectively suppressed. By introducing the Ma number, the influence of the Marangoni effect, guided by temperature, volume, and mass fraction changes, on the internal flow of droplets and the mechanism of coffee-ring formation are explained.

nanofluids  /  droplet evaporation  /  particle self-assembly  /  coffee ring
高峰, 李元媛, 陆规. 含纳米颗粒悬浮液滴蒸发及颗粒沉积特性研究. 制冷学报, 2025 , 46 (4) : 97 -105 . DOI: 10.12465/j.issn.0253-4339.2025.04.097
Feng Gao, Yuanyuan Li, Gui Lu. Research on Evaporation and Deposition Characteristics of Suspended Droplets Containing Nanoparticles[J]. Journal of Refrigeration, 2025 , 46 (4) : 97 -105 . DOI: 10.12465/j.issn.0253-4339.2025.04.097
液滴在固体表面上的蒸发广泛存在于制冷行业,如建筑空调、3D打印、喷雾冷却等[1-4]。在实际应用中,液滴内部常混杂着不同尺寸的非挥发性溶质或颗粒,当固着液滴完全蒸发后,会形成一个边缘比中央颜色深的环状沉积,这被称为咖啡环效应[5-7]。咖啡环效应在蒸发系统中普遍存在,不仅会导致沉积图案不均匀,影响打印部件的性能,还对电子器件冷却产生一定影响,如某些特定的制冷和冷却系统中通过自组装形成的纳米结构可以增强制冷剂的传热效率[8]。因此调控液滴蒸发及颗粒的沉积自组装特性至关重要,以避免环形沉积的形成,确保产品质量和性能稳定。
R. D. Deegan等[9]研究了咖啡环效应的形成机理,指出其主要原因在于液滴边缘的蒸发速度高于中心,该差异促使液滴内部形成向外的毛细流动,进而将溶质或颗粒携带至液滴边缘,最终形成环状沉积。除了毛细流动之外,当液滴与基板、外界环境的温度或溶质浓度存在差异时,液滴内部会产生表面张力梯度,促使流体从低表面张力处流向高表面张力处,这种由于表面张力差引起的流动称为马拉格尼(Marangoni)流动,固着液滴内的Marangoni流一般沿着自由界面从液滴边缘向顶部流动,与液滴内毛细流动方向相反[10]。通常用无量纲的Marangoni数(Ma)来表征液体中Marangoni效应的强弱。定义式为:
式中:β为表面张力-温度系数;ΔT为液体表面温差,℃;R为特征长度,mm;η为液体动力黏度,Pa·s;α为热扩散率,m2/s。
Ma大于一定值时,液体内部通常会产生Marangoni对流[11]。1939年,A. V. Hershey[12]早期发现液滴中存在Marangoni对流,观察到了铺在显微镜载玻片上的薄液层中膨润土颗粒的循环。随后,Hu Hua等[13]进一步研究发现,液滴内的Marangoni流会将颗粒携带至液滴中心而非边缘,这对抑制咖啡环效应提供了重要启示。根据咖啡环效应的形成机理,调控咖啡环效应可以从抑制外向毛细流动、控制三相线滑移、增大内部Marangoni流动3个方向进行[14]。当蒸发驱动的向外毛细流动受到抑制时,可以最大限度地减少甚至完全避免颗粒向接触线的运动,进而抑制咖啡环效应。K. Keserŏɡlu等[15]在蒸发液滴中心插入毛细管,毛细管表面浸润性抑制了液滴内毛细流动,实现均匀沉积;K. N. Al-Milaji等[16]通过调节溶液pH改变了颗粒沉积形貌;S. Bhattacharjee等[17]通过调控颗粒与基板相互作用,在改变了蒸发模式的同时得到了均匀沉积。此外,在液滴蒸发体积减小时,控制三相线随蒸发回缩,使颗粒难以全部聚集到液滴边缘,也可以形成均匀沉积。D. Mampallil等[18]使用电润湿方法蒸发乳滴,在不同浓度下均能实现对咖啡环效应的抑制;Yang Quansan等[19]通过在蒸发过程中触发气泡,导致凹弯月面和后退接触角增加,三相线快速且平滑后移从而得到均匀沉积。此外,改变液滴蒸发条件,增强Marangoni流动,可以抑制外向毛细流动,进而改变颗粒的自组装特性,形成均匀沉积图案。A. K. Thokchom等[20]借助激光诱导温度梯度引起强烈的Marangoni流动,使液滴内的颗粒重新根据流场分布;Li Dongdong等[21]通过颗粒表面改性,控制纳米颗粒表面的官能团,显著提高了蒸发速率,同时得到了均匀沉积的图案;Yang Xiaoye等[22]分别在液滴中添加了3种不同的表面活性剂进行实验,在一定浓度内均会抑制咖啡环效应。
虽然目前关于液滴蒸发沉积图案形成的研究大多聚焦于不同参数对蒸发沉积过程的影响,但对于Marangoni流动如何具体介入并影响蒸发过程,进而决定最终的沉积图案仍有待揭示。本文以含纳米颗粒液滴为研究对象,搭建液滴蒸发实验系统进行实验,研究不同条件下含纳米颗粒液滴的蒸发及沉积特性,深入了解并调控颗粒的沉积形态,并借助无量纲Marangoni数的变化解释沉积图案的形成。
搭建了用于进行液滴蒸发及颗粒自组装观测的实验系统,如图1所示。该实验台主要用于液滴蒸发及完全蒸发后沉积图案的观测实验,主要由液滴蒸发平台、温度控制仪、移液装置、控制系统及高速摄像机等5个部分组成。利用温度控制仪设定不同的初始基板温度,通过移液器将配置好的纳米流体精准吸取并滴落到蒸发平台上,同时调节平台角度与位置,对液滴蒸发过程进行完整拍摄,当液滴完全蒸发后,再调整相机位置拍摄沉积图案。为确保实验结果精确可靠,进行单一变量实验,每种实验条件重复进行3次以降低误差。
在研究含纳米颗粒液滴蒸发的实验中,常用的实验材料主要包括SiO2、Al2O3、聚苯乙烯、氧化铁以及其他多种氧化物。通常颗粒密度越小,在纳米流体中的沉降效应就越不明显,在液滴蒸发时能较好地保持悬浮状态。本实验拟选取SiO2颗粒作为实验材料,SiO2纯度为99.9%,平均粒径为20 nm,白色,密度为2.2~2.6 g/cm3,具有良好的悬浮性。SiO2颗粒需要使用去离子水溶解稀释至实验所需浓度。其他材料包括用于清洗的无水乙醇,表面活性剂十二烷基硫酸钠(SDS)、去离子水等。搭建的实验系统实物如图2所示,包含实验设备如下:
1)接触角测量仪。
本实验选用JY-Phb型接触角测量仪,主要包括镜头、高速相机、载物台、进样器等部件,同时配备了半导体冷光源,主要用于液滴蒸发过程中对气-液-固三相界面进行录像、拍照,得到清晰的界面图像,并精确测定固-液-气三相界面间形成的接触角。
2)相机镜头。
接触角测量仪配备了国产工业相机与显微镜头,其相机图像最大分辨率为2 048×1 536,自带软件控制亮度及曝光时间,最大放大倍数130倍,最佳拍摄距离为95 mm,镜头曝光时间为1.7 μs~2.3 s,能够满足不同实验条件下的需求。
3)温度控制仪。
加热装置选用XKMKQ-A型温度控制仪,由温控器和加热铜板组成,温控器控制功率为3 500 W,采用NTC-10K热敏电阻测温,控制温度为0~ 800 ℃,测试精度为0.1 ℃。
4)超声波清洗机。
SiO2纳米颗粒密度略大于水,长时间静置会导致颗粒沉降在流体底部,因此需要超声波清洗器使颗粒分布均匀。实验选用SN-QX-20超声波清洗机,使用超声波清洗机可将纳米颗粒分散并悬浮在基础液体中,使其均匀分布。此外,需要添加表面活性剂时,使用超声波清洗机也可以促进纳米颗粒的表面修饰。
5)微量可调移液器。
微量移液器用于纳米流体液体的精确取样和转移,选取SN-HPT微量可调移液器,共有0.1~2.5 μL和0.5~10 μL这2种量程。
1)配置纳米流体,用天平称取一定量的SiO2颗粒置于烧杯中,按比例倒入去离子水并不断搅拌,待颗粒分布相对均匀后,放入超声波清洗机25 ℃恒温清洗2 h,得到分布均匀的纳米流体。
2)将实验用载玻片1A5107(20 mm×75 mm)放入超声波清洗机,用无水乙醇清洗30 min,去除表面污染物,再用去离子水二次清洗10 min,去除残留乙醇和其他杂质,用试纸将载玻片擦干备用。
3)用温度控制仪将载玻片提前加热至指定温度,将摄像机的焦距、帧数等参数调整好,使拍摄画面达到最佳状态,随后调整载玻片位置使其实时画面处于显示器中间位置。
4)将配置好的纳米流体用去离子水稀释至实验所需浓度,放入超声波清洗机中振荡清洗30 min,随后取出,用移液器吸取一定量的液滴,小心滴至载玻片上,迅速微调接触角测量仪并进行拍摄,记录液滴蒸发过程。
5)液滴完全蒸发后保存好载玻片,实验结束后进行沉积图案的观测与拍摄,并进行SEM(扫描电子显微镜,scanning electron microscope)扫描。
为了获取固着液滴蒸发时的几何参数(接触的变化数据,使用Picpick软件对液滴的接触直径和高度进行测量,使用JY-PHb接触角测定仪自带的后处理软件测量液滴接触角。
图3所示为不同基板温度、液滴体积以及SDS质量分数下液滴蒸发过程中铺展半径和接触角随无量纲时间的变化,横坐标t/t0代表当前时间与液滴总蒸发时间的比值,SiO2颗粒质量分数为0.20%,当研究基板温度变化时,液滴体积恒为2 μL,而当研究体积变化时,基板温度恒为50 ℃。可知液滴的蒸发过程基本符合恒定接触半径蒸发模式,这主要是由于三相接触线被固定,引发了液滴内部的强烈毛细补偿流动,不仅将液滴牵引至三相接触线附近,还携带着大量的纳米颗粒,增强了基板与液滴间的相互作用,进而阻碍了三相接触线的收缩。此外,不同基板温度及液滴体积下液滴的形态变化基本一致,蒸发特性也未表现出明显差异,液滴的蒸发时间会随着基板温度的升高而减少,体积随时间的增大而减小,且对蒸发模式基本无影响。液滴体积减小会导致蒸发时间变短,但蒸发速率并未显著变化,因此对液滴内部流动的直接影响较小,而高温会增加液滴内部分子的热运动速度,使更多的分子具有足够的能量逃离液滴表面,从而加速蒸发过程,同时也会进一步影响液滴内部的流场,进而对液滴内部颗粒的运动和完全蒸发后的沉积图案形成产生影响。
图3(c)可知,添加SDS虽然也并未改变液滴的蒸发模式,却使液滴的铺展程度得到很大提升,质量分数仅0.25%就使液滴的铺展半径从0.71 mm增至1.12 mm,初始接触角从83°降至54°,铺展面积增加了89%。这主要因为添加的表面活性剂显著降低了液滴气-液界面的表面张力,当其他外界因素不变的情况下,液滴的铺展程度得到明显改善,铺展半径增大,接触角降低。但随着SDS质量分数逐渐增加,该变化趋势逐渐平缓,即使SDS质量分数增至1.00%时,相对于质量分数为0.75%的提升并未很大,高浓度(本文浓度均指质量分数)SDS对接触角的降低速率逐渐变慢,对液滴铺展程度的影响也逐渐减小,说明SDS对液滴铺展及蒸发的影响是有一定限度的。
对上述条件下液滴完全蒸发后的图案进行拍摄,并进行SEM表征,不同基板温度下的沉积形貌如图4所示,可以看出颗粒在较高基板温度下呈现出边缘厚中心薄的特点,为明显的咖啡环现象,且随着基板温度升高,咖啡环边缘聚集的颗粒逐渐增多,边缘沉积越厚,咖啡环效应越明显,SEM表征发现当基板温度较高时沉积图案会呈现裂纹,而当基板温度逐渐降低,直至低于室温时,沉积样貌逐渐发生改变,在20 ℃时可以看到中心部分沉积变厚,与边缘的差距变小,且大部分颗粒呈较均匀的分布。这是因为较低的基板温度减缓了液滴的蒸发速率,使得液滴形态相对平坦,并减小了液滴边缘的曲率。这样的形态减小了液滴边缘处的表面张力梯度,抑制了颗粒向液滴边缘的迁移,从而减少了咖啡环效应的形成,使得颗粒沉积更加均匀。基板温度对咖啡环效应的影响主要体现在2方面:1)基板温度影响液滴蒸发速率。高温加速蒸发,导致溶质迁移加快,进而加剧咖啡环效应。2)基板温度与液滴内部温度差异相关,形成温度梯度,引发对流现象,使溶质迁移更为剧烈。
不同液滴体积的沉积形貌如图5所示,可以看出液滴体积越小,咖啡环的宽度越窄。SEM表征也证明了这一点,当液滴体积为3.0 μL时,出现了明显的咖啡环现象。随着液滴体积的减小,咖啡环效应逐渐减弱,当液滴体积为0.5 μL时,未观察到明显的环形沉积。该现象可以归结为表面张力和布朗运动的影响,较大的液滴中液体表面积相对较大,表面张力会导致液滴蒸发过程中的颗粒更多地聚集在接触线附近,形成较宽的咖啡环,而当液滴体积较小时表面张力效应相对较弱,液体表面的压力差较小,从而减少了颗粒向接触线移动的情况。在液滴蒸发过程中,颗粒受到布朗运动的影响,会在液体表面上进行扩散。当液滴体积较大时,颗粒之间的距离相对较大,阻碍了颗粒之间的相互接触和扩散,导致颗粒沉积不均匀。当液滴体积较小时,颗粒之间的距离较小,颗粒更容易相互接触和扩散。因此,液滴体积越小,颗粒扩散的距离也相应减小,从而实现了更均匀的颗粒沉积。
图6所示为不同SDS质量分数下液滴蒸发后的沉积形貌,颗粒的质量分数均为0.20%,沉积图案的宽度约为1.2~2.3 mm,液滴体积为2.0 μL。液滴刚开始蒸发时,未添加SDS的颗粒均被携带至接触线边缘,但是当SDS存在于液滴中时,它可以显著降低液滴的表面张力,并产生不均匀的表面张力分布。这种不均匀性会导致液体在液滴内部产生Marangoni流动,从而抑制毛细流动,移动至液滴边缘的颗粒逐渐减少,随着蒸发结束,沉积图案由原先的窄环形态变为宽环。此外,液滴铺展面积增大,在蒸发末期可能局部蒸发不均匀,导致沉积图案最终并非圆形或椭圆形状,如1.00%SDS质量分数下颗粒沉积图案呈现“葫芦”状。从SEM表征也可以看到未添加SDS时,接触线处有明显的环状沉积,颗粒分布不均匀。但随着SDS质量分数的逐步增加,咖啡环的宽度逐渐扩展,而图案内部的沉积颗粒则相应减少。当SDS质量分数进一步增至1.00%时,环形沉积已经显著扩展至图案的内部区域,形成明显的密集沉积图案,颗粒分布较为均匀,这表明SDS质量分数的变化对咖啡环效应具有显著影响。添加SDS后颗粒并未显著发生聚集现象,而是呈现出较为均匀的分布,未添加SDS的沉积图案中间区域则呈现出明显的颗粒团聚现象,这是因为SDS离子在水中溶解并随后吸附于颗粒表面,导致颗粒间的排斥力增强,进而抑制了颗粒的团聚现象。
咖啡环宽度可以具体量化不同沉积图案的颗粒分布情况,图7所示为不同SDS质量分数下各沉积图案环宽度的变化,可以发现在低质量分数范围内,测得环的宽度随SDS质量分数的增加呈线性增长趋势。然而,当SDS质量分数超过0.2%时,环宽度的增加不再保持线性关系。进一步地,当SDS质量分数达到1.0%时,环宽度达到230 μm,环的边界已变得模糊不清,颗粒已经广泛分布在整个区域内,不再局限于特定的环状结构。
由上述实验结果可知,基板温度、液滴体积及SDS均会影响纳米流体液滴蒸发后形成的沉积图案,这主要与作用在纳米颗粒上的各种力有关。基于胶体稳定性理论,在咖啡环沉积和均匀沉积之间的转变主要受静电力和范德华力的影响。当液滴中的颗粒受到较大的径向驱动力或Marangoni环流受到抑制时,就越容易形成咖啡环图案,而当毛细流动受到抑制或Marangoni流动得到加强时更容易形成均匀的沉积图案,可见Marangoni环流对颗粒的沉积图案有重要影响。基于现有的数据,对含纳米颗粒悬浮液滴在基板蒸发时的Marangoni数(Ma)进行计算,从而定量分析Marangoni效应对液滴内部循环的影响,更好理解液滴蒸发和沉积图案形成的机制。根据式(1)给出的Ma计算式,查阅文献[23]得到表面张力-温度系数β=-0.165 7×10-3 N/(m·K);R在本实验中指液滴半径。去离子水和纳米流体的黏度以及导热系数取值如表1所示。
图8所示为Ma计算的结果,纳米颗粒的添加使得纳米流体液滴在相同温度下的Ma相较于纯液滴有所降低,这表明纳米颗粒的存在削弱了纳米流体中的Marangoni环流。然而,蒸发驱动外向毛细流动依然主导液滴内部流动,因此颗粒随内部流体的运动,更倾向于被带到液滴边缘的接触线处,从而形成咖啡环沉积。此外,随着纳米流体温度的上升,Ma进一步减小,导致Marangoni效应减弱;同时基板温度的升高也使液滴蒸发加快,在接触线处更为剧烈,这也导致外向的毛细流动得到加强,在二者共同影响下,咖啡环效应更加明显,表现为蒸发沉积图案中颗粒在边缘处的沉积更为密集,这与观察到的基板沉积图案结果相吻合。
图9所示为Ma随液滴体积的变化。随着液滴体积的减小,Ma逐渐增加。虽然液滴体积的减小导致半径减小,对Ma有减小的趋势,但液滴尺度对Ma的影响是一个复杂且综合的效应,涉及多个因素的相互作用。根据Young-Laplace方程,液滴的形成受到液体表面张力的作用,随着液滴半径减小,表面张力对液滴的作用力逐渐增强,进而使表面张力系数β增大。综合各种因素,液滴尺度的减小最终导致Ma的增加,Marangoni对流效应逐渐增强,也在一定程度上抑制了咖啡环效应的形成,表现为蒸发沉积图案中的咖啡环宽度随液滴尺度的减小而降低。
根据前文研究可知,SDS对咖啡环影响显著。这是因为当表面活性剂存在于液滴内部时,它们会在液滴表面和内部形成浓度梯度差。这种浓度梯度差会进一步增大液滴内部的表面张力梯度,从而引发更强的Marangoni对流,导致Ma增大。随着表面活性剂浓度的进一步增大,浓度梯度和表面张力梯度也相应增大,使得Ma进一步增加,对咖啡环效应的抑制作用也变得更加显著。
本文使用粒径为20 nm,质量分数为0.20%的SiO2纳米流体在不同基板温度(20~70 ℃)、液滴体积(0.5~3.0 μL)及SDS质量分数(0.10%~1.00%)多种条件下的蒸发特性进行研究,并分析液滴蒸发后沉积形貌的形成,根据实验数据计算Ma及其变化趋势,对蒸发液滴内部流动方式及沉积图案的形成进行分析。相关研究为可控纳米颗粒沉积及自组装提供机理支撑。得到结论如下:
1)基板温度和液滴体积的变化对液滴蒸发模式和形态影响较小,液滴在整个蒸发过程内以恒定接触半径模式蒸发,接触角随时间基本呈现线性变化,而添加SDS显著改善了液滴的铺展程度,质量分数仅0.25%就使液滴的铺展半径从0.71 mm增至1.12 mm,初始接触角从83°降至54°,铺展面积增加了89%,且在蒸发过程中接触角随时间不再线性变化,表现出了更为复杂的动态行为。
2)基板温度和液滴体积显著影响液滴蒸发后的沉积图案。基板温度越高,液滴体积越大,液滴内部的毛细流动越剧烈,蒸发后形成更为明显的咖啡环图案;而当液滴内含有一定量SDS时,蒸发后的咖啡环宽度增加,SDS质量分数达到1.00%时,咖啡环宽度达到230 μm,环的边界模糊不清,颗粒已经广泛分布在整个区域内,不再是特定的环状结构。
3)通过Ma定量表征了温度、体积变化对Marangoni效应的影响,以及如何影响咖啡环的形成。纳米颗粒的加入使液滴Ma减小,液滴内主要存在由蒸发驱动的毛细流动,将颗粒携带至边缘形成咖啡环沉积;随着温度升高,边缘处液滴蒸发剧烈,引发更为强烈的毛细流动,也使Ma降低,咖啡环效应愈发剧烈;随着液滴体积减小,在液滴尺寸和表面张力共同作用下,Ma增大,沉积更加均匀。
  • 国家自然科学基金(52076074)
  • 国家自然科学基金(52376008)
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2025年第46卷第4期
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doi: 10.12465/j.issn.0253-4339.2025.04.097
  • 接收时间:2024-05-13
  • 首发时间:2026-03-13
  • 出版时间:2025-08-16
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  • 收稿日期:2024-05-13
  • 修回日期:2024-05-29
  • 录用日期:2024-05-30
基金
National Natural Science Foundation of China(52076074)
国家自然科学基金(52076074)
National Natural Science Foundation of China(52376008)
国家自然科学基金(52376008)
作者信息
    华北电力大学能源动力与机械工程学院 北京 102206

通讯作者:

李元媛,女,教授,华北电力大学大学能源动力与机械工程学院,15810949982,E-mail:。研究方向:热力学,工质热物性。
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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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