Article(id=1322276028035223791, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1322276007797702769, articleNumber=null, orderNo=null, doi=10.11868/j.issn.1001-4381.2024.000510, pmid=null, cstr=32421.14.j.issn.1001-4381.2024.000510, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1721059200000, receivedDateStr=2024-07-16, revisedDate=null, revisedDateStr=null, acceptedDate=1724342400000, acceptedDateStr=2024-08-23, onlineDate=1793184771784, onlineDateStr=2026-10-28, pubDate=1789833600000, pubDateStr=2026-09-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793184771784, onlineIssueDateStr=2026-10-28, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793184771784, creator=13701087609, updateTime=1793184771784, updator=13701087609, issue=Issue{id=1322276007797702769, tenantId=1146029695717560320, journalId=1220038251117760515, year='2026', volume='54', issue='9', pageStart='1', pageEnd='252', issueExtLink='null', onlineDate='null', pubDate='1789833600000', pubDateStr='2026-09-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=0, createTime=1793184766959, creator='13701087609', updateTime=1793185369041, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1322278533200728093, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1322276007797702769, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1322278533200728094, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1322276007797702769, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=183, endPage=191, ext={EN=ArticleExt(id=1322276029817802992, articleId=1322276028035223791, tenantId=1146029695717560320, journalId=1220038251117760515, language=EN, title=Preparation and anticorrosive properties of waterborne epoxy composite coating with stearic acid/chitosan modified multi-wall carbon nanotubes, columnId=1220689384450478826, journalTitle=Journal of Materials Engineering, columnName=RESEARCH ARTICLE, runingTitle=null, highlight=null, articleAbstract=

To improve the corrosion resistance of waterborne epoxy coating, chitosan is adsorbed onto the surface of multi-walled carbon nanotubes via surface-deposition crosslinking with glutaraldehyde as the crosslinking agent. Then, stearic acid has been grafted using a water-soluble coupling agent,1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl),to synthesize stearic acid/chitosan-modified multi-walled carbon nanotubes (SA/CS-CNTs). Aqueous epoxy anticorrosive coatings are prepared by blending SA/CS-CNTs with aqueous epoxy resin. The structure of SA/CS-CNTs has been characterized, and the corrosion resistance performances of the coatings have been explored. The results show that the epoxy resin with 0.5% (mass fraction)SA/CS-CNTs filler has the best corrosion resistance. Compared with the pure waterborne epoxy coating, its low-frequency impedance modulus is increased by about 5 orders of magnitude, the corrosion inhibition efficiency increases to 99.66%, and the water contact angle reaches 104.2°. The corrosion potential increases by 0.39 V,and the corrosion current density decreases from 4.17×10-6 A·cm-2 to 1.44×10-8 A·cm-2. After being immersed in 3.5% NaCl solution for 96 h, its impedance modulus is still above 107 Ω·cm2.

, authors=Qingling TONG, Bao CUI, Jianjun YANG, Qingyun WU, Mingyuan WU, Jian’an ZHANG, Jiuyi LIU, authorsList=Qingling TONG, Bao CUI, Jianjun YANG, Qingyun WU, Mingyuan WU, Jian’an ZHANG, Jiuyi LIU, authorCompany=null, correspAuthors=Jianjun YANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1322276032011424007, articleId=1322276028035223791, tenantId=1146029695717560320, journalId=1220038251117760515, language=CN, title=硬脂酸/壳聚糖修饰多壁碳纳米管制备水性环氧复合涂层及防腐性能, columnId=1220689384622445292, journalTitle=材料工程, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

为提高环氧树脂防腐涂层对金属基材防护的持久性,以戊二醛为交联剂,采用表面沉积交联法将壳聚糖吸附包裹在多壁碳纳米管表面,然后通过水溶性偶联剂1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC·HCl)接枝硬脂酸,合成出硬脂酸/壳聚糖修饰的多壁碳纳米管(SA/CS-CNTs)。将SA/CS-CNTs与水性环氧树脂共混制备出水性环氧防腐涂料。对SA/CS-CNTs结构进行了表征,对涂层的耐腐蚀性能进行探究。结果表明,添加0.5%(质量分数)SA/CS-CNTs的环氧树脂防腐性能最佳。与纯水性环氧树脂相比,其低频阻抗值提高了约5个数量级,缓蚀效率可达99.66%,水接触角可达104.2°;腐蚀电流密度从4.17×10-6 A·cm-2减小到1.44×10-8 A·cm-2,腐蚀电位增加了0.39 V;在3.5%的NaCl溶液中浸泡96 h后,低频阻抗模量值仍高于107 Ω·cm2。

, authors=童庆玲, 崔豹, 杨建军, 吴庆云, 吴明元, 张建安, 刘久逸, authorsList=童庆玲, 崔豹, 杨建军, 吴庆云, 吴明元, 张建安, 刘久逸, authorCompany=null, correspAuthors=杨建军, authorNote=null, correspAuthorsNote=
杨建军(1960—),男,教授,研究方向为水基高分子纳米杂化材料,联系地址:安徽省合肥市经开区九龙路111号安徽大学化学化工学院(230601),E-mail:
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waterborne epoxy coatings, refAbstract=null), Reference(id=1322276044078436721, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, doi=null, pmid=null, pmcid=null, year=2021, volume=179, issue=null, pageStart=109143, pageEnd=null, url=null, language=null, rfNumber=[24], rfOrder=23, authorNames=Aghili M, Yazdi M K, Ranjbar Z, journalName=Corrosion Science, refType=null, unstructuredReference=Aghili M, Yazdi M K, Ranjbar Z,et al.Anticorrosion performance of electro-deposited epoxy/amine functionalized graphene oxide nanocomposite coatings[J].Corrosion Science,2021,179:109143., articleTitle=Anticorrosion performance of electro-deposited epoxy/amine functionalized graphene oxide nanocomposite coatings, refAbstract=null)], funds=[Fund(id=1322276040597164376, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, awardId=51973001, language=CN, fundingSource=国家自然科学基金项目(51973001), fundOrder=null, country=null), 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language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=安徽大学 化学化工学院 安徽省水基高分子材料高性能化工程实验室,合肥 230601)])], figs=[ArticleFig(id=1322276036839067964, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, language=EN, label=Fig.1, caption=Synthesis route diagram of SA/CS-CNTs composites, figureFileSmall=nMQEQ5P2W/tAFctmSKpuBA==, figureFileBig=tUQzP+OZLa4nm/kIpDpIbg==, tableContent=null), ArticleFig(id=1322276036901982525, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, language=CN, label=图1, caption=SA/CS-CNTs复合材料合成示意图, figureFileSmall=nMQEQ5P2W/tAFctmSKpuBA==, figureFileBig=tUQzP+OZLa4nm/kIpDpIbg==, tableContent=null), ArticleFig(id=1322276038697144638, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, language=EN, label=Fig.2, caption=SEM photographs of samplesMorphology:(a),(b)CNTs;(c),(d)SA-CS/CNTs;fracture 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figureFileSmall=YI2xiBVqtCzzMPqC067lKQ==, figureFileBig=62OK4tjqPdG6A2dVtnZ9Og==, tableContent=null), ArticleFig(id=1322276039414370632, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, language=EN, label=Fig.7, caption=Polarization curves of coatings immersed in 3.5% NaCl solution for 96 h, figureFileSmall=6yND466Jy/fbetu772nGqA==, figureFileBig=MYO8SW3CJgixt5eVRaTheQ==, tableContent=null), ArticleFig(id=1322276039477285193, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, language=CN, label=图7, caption=涂层在3.5% NaCl中浸泡96 h的极化曲线, figureFileSmall=6yND466Jy/fbetu772nGqA==, figureFileBig=MYO8SW3CJgixt5eVRaTheQ==, tableContent=null), ArticleFig(id=1322276039548588362, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, language=EN, label=Fig.8, caption=Nyquist(1) and Bode(2) plots of coatings immersed in 3.5% NaCl solution for 2,24,48,96 h 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Formula of waterborne epoxy coating

, figureFileSmall=null, figureFileBig=null, tableContent=
SampleCNT categoryEP/gCuring agent/gFiller/gH2O/gAnhydrous ethanol/mLDefoamer/g
EP420000.1
CCNTs/EP0.5%CS-CNTs420.031.500.1
SCCNTs/EP10.3%SA/CS-CNTs420.01800.90.1
SCCNTs/EP20.5%SA/CS-CNTs420.0301.50.1
SCCNTs/EP30.7%SA/CS-CNTs420.04202.10.1
), ArticleFig(id=1322276040177733971, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, language=CN, label=表1, caption=

水性环氧涂料配方

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SampleCNT categoryEP/gCuring agent/gFiller/gH2O/gAnhydrous ethanol/mLDefoamer/g
EP420000.1
CCNTs/EP0.5%CS-CNTs420.031.500.1
SCCNTs/EP10.3%SA/CS-CNTs420.01800.90.1
SCCNTs/EP20.5%SA/CS-CNTs420.0301.50.1
SCCNTs/EP30.7%SA/CS-CNTs420.04202.10.1
), ArticleFig(id=1322276040261620052, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, language=EN, label=Table 2, caption=

Physical properties of EP,CCNTs/EP,and SCCNTs/EP coatings

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SampleAdhesion/gradeHardnessImpact resistance/(kg·cm)Water absorption/%
EP12H4011.34
CCNTs/EP02H405.96
SCCNTs/EP103H404.78
SCCNTs/EP203H453.75
SCCNTs/EP303H454.04
), ArticleFig(id=1322276040353894741, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, language=CN, label=表2, caption=

EP、CCNTs/EP、SCCNTs/EP涂层的物理性能

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SampleAdhesion/gradeHardnessImpact resistance/(kg·cm)Water absorption/%
EP12H4011.34
CCNTs/EP02H405.96
SCCNTs/EP103H404.78
SCCNTs/EP203H453.75
SCCNTs/EP303H454.04
), ArticleFig(id=1322276040433586518, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, language=EN, label=Table 3, caption=

Polarization parameters of EP,CCNTs/EP,and SCCNTs/EP coatings

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SampleEcorr/VIcorr/(A·cm-2)Ka/(V·dec-1)Kc/(V·dec-1)Rp/(Ω·cm2)η/%
EP-0.604.17×10-60.1078-0.11065.69×103
CCNTs/EP-0.454.38×10-70.1218-0.12856.20×10489.50
SCCNTs/EP1-0.312.17×10-70.1371-0.12782.32×10594.80
SCCNTs/EP2-0.211.44×10-80.1273-0.11391.81×10699.66
SCCNTs/EP3-0.246.42×10-80.1321-0.12224.29×10598.46
), ArticleFig(id=1322276040500695383, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276028035223791, language=CN, label=表3, caption=

EP、CCNTs/EP、SCCNTs/EP涂层的极化参数

, figureFileSmall=null, figureFileBig=null, tableContent=
SampleEcorr/VIcorr/(A·cm-2)Ka/(V·dec-1)Kc/(V·dec-1)Rp/(Ω·cm2)η/%
EP-0.604.17×10-60.1078-0.11065.69×103
CCNTs/EP-0.454.38×10-70.1218-0.12856.20×10489.50
SCCNTs/EP1-0.312.17×10-70.1371-0.12782.32×10594.80
SCCNTs/EP2-0.211.44×10-80.1273-0.11391.81×10699.66
SCCNTs/EP3-0.246.42×10-80.1321-0.12224.29×10598.46
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硬脂酸/壳聚糖修饰多壁碳纳米管制备水性环氧复合涂层及防腐性能
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童庆玲 , 崔豹 , 杨建军 , 吴庆云 , 吴明元 , 张建安 , 刘久逸
材料工程 | 研究论文 2026,54(9): 183-191
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材料工程 |研究论文 2026 , 54 (9) : 183 -191
硬脂酸/壳聚糖修饰多壁碳纳米管制备水性环氧复合涂层及防腐性能
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童庆玲, 崔豹, 杨建军 , 吴庆云, 吴明元, 张建安, 刘久逸
作者信息
  • 安徽大学 化学化工学院 安徽省水基高分子材料高性能化工程实验室,合肥 230601
通讯作者:
杨建军(1960—),男,教授,研究方向为水基高分子纳米杂化材料,联系地址:安徽省合肥市经开区九龙路111号安徽大学化学化工学院(230601),E-mail:
Preparation and anticorrosive properties of waterborne epoxy composite coating with stearic acid/chitosan modified multi-wall carbon nanotubes
Qingling TONG, Bao CUI, Jianjun YANG , Qingyun WU, Mingyuan WU, Jian’an ZHANG, Jiuyi LIU
Affiliations
  • Anhui High Performance Engineering Laboratory of Water-based Polymer Materials,College of Chemistry and Chemical Engineering,Anhui University,Hefei 230601,China
出版时间: 2026-09-20 doi: 10.11868/j.issn.1001-4381.2024.000510
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为提高环氧树脂防腐涂层对金属基材防护的持久性,以戊二醛为交联剂,采用表面沉积交联法将壳聚糖吸附包裹在多壁碳纳米管表面,然后通过水溶性偶联剂1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC·HCl)接枝硬脂酸,合成出硬脂酸/壳聚糖修饰的多壁碳纳米管(SA/CS-CNTs)。将SA/CS-CNTs与水性环氧树脂共混制备出水性环氧防腐涂料。对SA/CS-CNTs结构进行了表征,对涂层的耐腐蚀性能进行探究。结果表明,添加0.5%(质量分数)SA/CS-CNTs的环氧树脂防腐性能最佳。与纯水性环氧树脂相比,其低频阻抗值提高了约5个数量级,缓蚀效率可达99.66%,水接触角可达104.2°;腐蚀电流密度从4.17×10-6 A·cm-2减小到1.44×10-8 A·cm-2,腐蚀电位增加了0.39 V;在3.5%的NaCl溶液中浸泡96 h后,低频阻抗模量值仍高于107 Ω·cm2。

多壁碳纳米管  /  壳聚糖  /  硬脂酸  /  水性环氧树脂  /  金属防腐

To improve the corrosion resistance of waterborne epoxy coating, chitosan is adsorbed onto the surface of multi-walled carbon nanotubes via surface-deposition crosslinking with glutaraldehyde as the crosslinking agent. Then, stearic acid has been grafted using a water-soluble coupling agent,1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl),to synthesize stearic acid/chitosan-modified multi-walled carbon nanotubes (SA/CS-CNTs). Aqueous epoxy anticorrosive coatings are prepared by blending SA/CS-CNTs with aqueous epoxy resin. The structure of SA/CS-CNTs has been characterized, and the corrosion resistance performances of the coatings have been explored. The results show that the epoxy resin with 0.5% (mass fraction)SA/CS-CNTs filler has the best corrosion resistance. Compared with the pure waterborne epoxy coating, its low-frequency impedance modulus is increased by about 5 orders of magnitude, the corrosion inhibition efficiency increases to 99.66%, and the water contact angle reaches 104.2°. The corrosion potential increases by 0.39 V,and the corrosion current density decreases from 4.17×10-6 A·cm-2 to 1.44×10-8 A·cm-2. After being immersed in 3.5% NaCl solution for 96 h, its impedance modulus is still above 107 Ω·cm2.

multi-walled carbon nanotubes  /  chitosan  /  stearic acid  /  waterborne epoxy resin  /  metal corrosion protection
童庆玲, 崔豹, 杨建军, 吴庆云, 吴明元, 张建安, 刘久逸. 硬脂酸/壳聚糖修饰多壁碳纳米管制备水性环氧复合涂层及防腐性能. 材料工程, 2026 , 54 (9) : 183 -191 . DOI: 10.11868/j.issn.1001-4381.2024.000510
Qingling TONG, Bao CUI, Jianjun YANG, Qingyun WU, Mingyuan WU, Jian’an ZHANG, Jiuyi LIU. Preparation and anticorrosive properties of waterborne epoxy composite coating with stearic acid/chitosan modified multi-wall carbon nanotubes[J]. Journal of Materials Engineering, 2026 , 54 (9) : 183 -191 . DOI: 10.11868/j.issn.1001-4381.2024.000510
金属腐蚀严重损害了金属材料的性能和使用寿命,给各行各业造成了经济和安全问题[1-2]。在金属表面应用聚合物涂层是一种有效、简单、常用的防腐方法[3]。环氧树脂(EP)具有良好的热机械性能、优越的防腐性能以及与金属/非金属基底的高黏附性,已被广泛应用于聚合物涂层[4]。研究人员将各种功能化的纳米材料与环氧涂层共混,制备了具有主动防腐性、疏水性、自愈合性和高力学性能的智能防腐涂层体系[5-8]。
碳纳米管(CNTs)具有出色的耐化学性、超高长径比和机械稳定性,在增强聚合物涂层的机械和腐蚀性能方面引起了人们的关注[9]。然而,CNTs表现出化学惰性,通过π-π相互作用和范德瓦耳斯力短时间内便会在溶液和涂层基质中团聚[10]。研究人员对CNTs进行改性处理,提高其分散性和与聚合物涂层的相容性。Xia等[11]通过偶氮二异丁腈的降解,将氰基共价接枝到多壁碳纳米管上,附着的氰基不仅显著提高了多壁碳纳米管与涂层的界面相容性,还增加了其防腐性能和机械强度。
壳聚糖(chitosan,CS)属于天然多糖中唯一的阳离子多糖,无毒且成膜性佳,与金属有强螯合能力,可用作高效绿色缓蚀剂[12-13]。此外,CS分子结构侧链上的氨基和羟基具有较强的化学活性,很容易通过这些活性位点修饰。Pourhashem等[14]通过水热法合成了TiO2纳米管,并用CS化学修饰,电化学结果表明CS不仅可以钝化金属表面,还增强了环氧树脂和纳米填料之间的化学相容性,提供更好的阻隔效果。硬脂酸(stearic acid,SA)是一种含有长碳链和低表面能的脂肪酸,广泛用于制备疏水涂层。在金属表面引入低表面能材料来制备疏水涂层也是增强耐腐蚀性的有效方法,以防止腐蚀性离子蚀刻金属[15]。
基于此,本工作采用绿色缓蚀剂CS通过静电吸附在CNTs表面,提高CNTs的分散性,延长腐蚀介质的扩散路径;再利用水溶性偶联剂1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC·HCl)将SA接枝在CS表面,降低CNTs复合材料的表面能。最后将SA/CS-CNTs复合材料与水性环氧树脂(epoxy resin,EP)共混,制备的环氧复合涂层具有长效耐腐蚀性能。
水性环氧树脂(E-51型)、水性环氧固化剂(628型),均为工业级,购自钱广化工公司;羧基化多壁碳纳米管(直径5~15 nm,长度10~30 µm)、CS、SA,均为化学纯,购自上海阿达玛斯贝塔化学试剂有限公司;戊二醛水溶液(glutaraldehyde,GA,50%(质量分数,下同))、EDC·HCl、丙酮、氯化钠、乙酸、无水乙醇、氨水,均为化学纯,购自上海国药集团化学试剂有限公司;超纯水,由实验室自制。
采用表面沉积交联法制备壳聚糖修饰的碳纳米管复合材料(CS-CNTs),称取0.8 g CS溶解在200 mL稀醋酸溶液中,搅拌12 h得透明色CS溶液;取0.2 g羧基化多壁碳纳米管分散于20 mL去离子水中,超声30 min后缓慢加入CS溶液中,冷凝回流的条件下,将混合溶液在98 ℃下磁力搅拌6 h。混合液冷却至室温后,用稀氨水调节溶液pH=10,将1 mL GA加入溶液中,60 ℃下磁力搅拌3 h,稀醋酸和去离子水洗涤离心数次,冷冻干燥得到CS-CNTs。
称取0.2 g CS-CNTs分散于20 mL去离子水中,超声30 min;称取0.2 g SA和0.67 g EDC‧HCl溶解于28 mL丙酮与12 mL无水乙醇的混合液中,加入CS-CNTs水溶液中,60 ℃下磁力搅拌反应24 h,产物用去离子水和乙醇洗涤离心,60 ℃下干燥得到SA/CS-CNTs复合材料。合成路线如图1所示。
称取适量SA/CS-CNTs于无水乙醇中进行分散,制备20 mg·mL-1的SA/CS-CNTs分散液,取4 g环氧树脂,向其中加入不同类型的CNT填料(如表1所示分别为0.5%CS-CNTs、0.3%SA/CS-CNTs、0.5%SA/CS-CNTs、0.7%SA/CS-CNTs),超声30 min后加入2 g环氧固化剂和少量消泡剂,搅拌20 min,得到水性环氧复合涂料,标记为CCNTs/EP、SCCNTs/EP1、SCCNTs/EP2、SCCNTs/EP3。按照上述方法制备纯EP涂料作为对照组,记为EP。采用砂纸对马口铁打磨处理,将环氧复合涂料用线棒涂布器均匀涂覆于马口铁上(涂膜厚度约100 µm),70 ℃烘箱内固化24 h。
采用Nexus-870傅里叶变换红外光谱仪对样品的主要化学结构进行分析,溴化钾压片法制样,波长范围:500~4000 cm-1。采用Via-Reflex激光拉曼光谱仪表征样品的碳结构分离程度,将样品研磨后均匀平铺于载玻片凹槽中,扫描范围500~3500 cm-1,激发波长为532 nm。采用Escalab-250型XPS表征样品表面元素的化学结合状态。采用Regulus-8230型SEM观察样品的微观形貌,将样品粘到导电胶带上,并溅射镀金10 s。采用DSA10-MK2接触角测量仪对表面平整的涂膜进行水接触角测试,每个涂膜测试3次,取其中间值。
按照标准GB/T 1732—1993、GB/T 6739—1996、GB/T 9286—1998,采用QHQ铅笔硬度计、KX-DB-501冲击实验机、QFH附着力测试仪对涂膜的耐冲击强度、铅笔硬度以及附着力测试。将一定质量的涂膜在超纯水中浸泡24 h后,取出分别称量其质量,根据公式(1)计算涂膜的吸水率:
Q=M-mM×100%
式中:Q代表吸水率,%;M代表吸水后涂膜样品的质量,g;m代表吸水前涂膜样品的质量,g。
采用CHI660E电化学工作站进行测试,运用三电极系统,即涂覆的钢板作为工作电极(表面积为1 cm2,背面用油溶性重防腐环氧树脂封装),饱和甘汞电极作为参比电极,铂电极作为对电极,在3.5% NaCl溶液中测试涂层的动电位极化(Tafel)曲线和电化学阻抗谱(EIS),并通过ZsimpWin软件拟合分析数据。
将制得的水性环氧涂料涂覆在打磨后的马口铁上,并进行画“×”处理,放置于盐雾测试箱中进行盐雾老化测试,测试温度保持在35 ℃左右,喷雾溶液为5%的NaCl溶液,采用连续性喷雾方式。
图2为样品的SEM图。图2(a)~(d)为CNTs、SA/CS-CNTs的微观形貌图。纯CNTs为规则的管状结构,表面较为光滑,管间紧密缠绕(图2(a))。经过CS沉积和SA接枝后,CNTs的分散性有了明显改善(图2(c)),这可能是由于CS和SA降低了管之间的范德瓦耳斯力。由SA/CS-CNTs的放大图(图2(d))可看出,CNTs管壁变得粗糙,与纯CNTs相比(图2(b)),SA/CS-CNTs的直径增加了约10~20 nm。
图2(e)~(i)为EP、CCNTs/EP、SCCNTs/EP的涂层断裂面SEM图。如图2(e)所示,交联固化后的EP涂层表面呈现出大量孔径不同的微孔,腐蚀介质可以穿透孔洞与金属基材直接接触。如图2(f)所示,CS的添加能够有效填补孔洞并缩小孔径,但涂层表面并不平整。如图2(g)~(i)所示,SCCNTs/EP1孔洞的填补较为有限,可能是填料添加量较少;SCCNTs/EP3涂层填料添加量较多,导致局部团聚,断面粗糙度增大,出现少量微孔缺陷,表明该涂层对腐蚀性介质的抵抗力较差;而SCCNTs/EP2涂层表面纹理清晰,平整致密,无明显孔隙。以上分析表明:SA-CS/CNTs复合材料可以对腐蚀性介质的渗透起到阻隔作用,可提高涂层的缓蚀效果,但过多或过少SA-CS/CNTs复合材料的添加都不利于环氧涂层防腐性能的提升。
图3是CNTs、CS、CS-CNTs、SA/CS-CNTs的红外光谱图。CNTs的特征峰出现在1380、1569、1795、3396 cm-1,分别代表C—OH伸缩振动、芳环C═C振动、C═O伸缩振动、—OH伸缩振动。CS的红外光谱,以3400 cm-1为中心的强波段和宽频带峰可归因于—OH基团与N—H伸缩振动重叠,1100~900 cm-1范围内的峰是由于多糖骨架,包括糖苷键、C—O和C—O—C伸缩振动,1383 cm-1的峰归因于C—N伸缩振动[16]。用CS修饰后,CS-CNTs在898、1402、3118 cm-1处出现新峰,分别归因于CS中C—O—C、C—N、N—H伸缩振动峰,且1560 cm-1出现C═N伸缩振动峰,这是由于CS与戊二醛发生席夫碱反应,表明CS成功沉积交联在CNTs表面。CS-CNTs复合材料接枝SA后,3118 cm-1处的N—H和1402 cm-1处C—N伸缩振动峰消失,1632 cm-1处出现酰胺Ⅰ带特征峰,表明SA成功接枝形成酰胺键。此外,2920、2853 cm-1处峰值增强,归因于SA长分子链中甲基和亚甲基的伸缩振动[17],证实了成功制备出SA/CS-CNTs。
图4为CNTs、CS-CNTs、SA/CS-CNTs的XPS谱图。由图4(a)可知,CNTs含有C、O元素,而CS-CNTs、SA/CS-CNTs均出现了新元素N,这与CS分子中的N原子有关。如图4(b)所示,CS-CNTs的C 1s谱可以拟合到284.8 eV(C═C)、285.1 eV(C—C)、285.7 eV(C—N)、286.4 eV(C—O—C)、287.2 eV(C═N/C═O)、288.7 eV(O—C═O),其中C—N,C—O—C源自CS分子[18];且图4(c)中CS-CNTs的N 1s可以拟合到399.7 eV(C—N)、400.1 eV(—NH2)、401.2 eV(C═N),C═N是由于CS分子与戊二醛发生席夫碱反应从而形成交联得到,这与FT-IR分析一致。由图4(d)可知,SA修饰后,C—C的含量增加,C—N的含量减少,且出现新拟合峰288.5 eV(O═C—N),表明SA接枝到CS上形成酰胺键;如图4(e)所示,SA/CS-CNTs的N 1s谱可以拟合出399.9 eV(O═C—N/C—N),进一步表明成功制备了该复合材料。
图5为CNTs、CS-CNTs、SA/CS-CNTs的拉曼光谱,通过Raman光谱研究修饰前后CNTs的碳结构变化。由图5可知,1348、1588 cm-1为中心处的2个不同峰为D峰和G峰,分别代表官能团中sp3碳原子的振动和sp2碳原子的面内伸缩振动[19]。通常,用D峰和G峰波段积分面积之比ID/IG来评估碳材料缺陷的程度[20]。与CNTs相比,CS-CNTs和SA/CS-CNTs的D峰和G峰位置基本保持不变,CS-CNTs的ID/IG由原始的1.13降到0.88,表明CS通过静电作用沉积在CNTs表面后并没有引入缺陷;接枝SA后,ID/IG增加到了1.17,说明SA/CS-CNTs具有更高的无序水平,进一步提高了CNTs的分散性。以上分析表明经CS和SA共同修饰后,CNTs的基本结构几乎没有破坏。
图6为EP、CCNTs/EP、SCCNTs/EP涂层的水接触角图。由图6可知,纯EP涂层的水接触角为63.1°,涂层具有亲水性,腐蚀介质和水分子极易渗透;CCNTs/EP涂层因填料的加入改善了涂层缺陷,水接触角增大至78.1°。SCCNTs/EP复合涂层的水接触角均增大且都表现出疏水性(水接触角>90°),其中SCCNTs/EP2涂层的水接触角最大,为104.2°。这源于SA的长分子链结构能够降低涂层表面张力,使得疏水表面和腐蚀性介质的接触面积减少,有效阻止了腐蚀性介质的吸附,延缓其进入涂层内部的时间。
表2是EP、CCNTs/EP、SCCNTs/EP涂层的附着力、硬度、耐冲击、吸水率测试结果。由表2可知,CCNTs/EP、SCCNTs/EP涂层的附着力都为0级,填料的加入增强了涂层的交联密度,使涂层与金属基材连接更加牢固;SCCNTs/EP涂层的铅笔硬度都为3H,可抵抗外界划伤;SCCNTs/EP2和SCCNTs/EP3涂层的耐冲击效果最佳,确保涂层在受到巨大冲击时仍能保持涂层完整;SCCNTs/EP2涂层的吸水率从EP的11.34%降低到3.75%,对腐蚀性介质的屏蔽作用最强。综合来看,SCCNTs/EP2的物理性能最佳,附着力0级,耐冲击强度45 kg·cm。可改善涂层的分层和剥落现象,提高涂层的耐腐蚀性和力学性能。
利用外推法使得阴极和阳极曲线拟合后的2条直线相交,其交点的横纵坐标分别对应于Icorr和Ecorr。Rp可由式(2)Stream-Geary方程计算得到[21],缓蚀效率η计算如式(3)所示。
Rp=KaKc2.303Ka+KcIcorr
η=Icorr,EP-IcorrIcorr,EP×100%
式中:Icorr,EP为纯EP涂层的腐蚀电流密度;Icorr为待测样品的腐蚀电流密度;Rp为涂层极化电阻;Ka、Kc分别为阳极和阴极Tafel斜率。
图7是室温下EP、CCNTs/EP和SCCNTs/EP复合涂层在3.5%的NaCl溶液中浸泡96 h的极化曲线。表3是所有复合涂层的电化学参数的数据分析。一般涂层的腐蚀电流密度越低,腐蚀电位越高,涂层极化电阻越大,其耐腐蚀性越好。由表3可知,相较于纯EP涂层,CCNTs/EP和SCCNTs/EP涂层的Icorr均有所下降,而Ecorr和η均有所增加。其中,SCCNTs/EP2涂层的Icorr为1.44×10-8 A·cm-2,比纯EP涂层(4.17×10-6 A·cm-2)减小了约2.5个数量级;Ecorr为-0.21 V,比纯EP增加了0.39 V;缓蚀效率从89.50%增大到99.66%。Rp反映了涂层的物理阻隔性能,SCCNTs/EP2涂层的Rp值最大,为1.81×106 Ω·cm2,显著高于纯EP涂层(5.69×103 Ω·cm2)和CCNTs/EP涂层(6.20×104 Ω·cm2)。以上数据表明,与纯EP、CCNTs/EP复合涂层相比,SCCNTs/EP复合涂层在金属基材表面具有优异的防腐性能。
图8显示了不同浓度梯度的涂层样品在3.5%的NaCl溶液中浸泡不同时间的EIS测试结果。一般奈奎斯特图中容抗弧半径越大,伯德图中低频阻抗模量(|Z|0.01 Hz)越大,涂层耐腐蚀性能越好。由奈奎斯特图可看出,不同浸泡时间下,SCCNTs-EP2涂层的容抗弧半径最大,表明其对腐蚀性介质的阻挡作用最大。由伯德图可知,纯EP涂层的初始|Z|0.01 Hz为8.31×103 Ω·cm2,CCNTs-EP涂层的(|Z|0.01 Hz)为4.60×105 Ω·cm2,SCCNTs-EP2涂层的(|Z|0.01 Hz)为1.50×109 Ω·cm2,表明添加CS-CNTs和SA/CS-CNTs填料都可以显著提高涂层的防腐性能。
当浸泡时间延长至96 h后,所有涂层样品的容抗弧半径明显缩小,涂层的防护能力下降。EP涂层和CCNTs-EP涂层的|Z|0.01 Hz降至2.20×103、1.42×105 Ω·cm2,而SCCNTs-EP涂层在整个浸泡过程中|Z|0.01 Hz始终大于107 Ω·cm2,表现出对金属基材的长期防护性能。但过高或过低浓度SA/CS-CNTs的添加不利于提升涂层的防腐性能,由图8(d-2),(e-2)可明显看出,添加0.7%SA/CS-CNTs的涂层的|Z|0.01 Hz反而低于添加0.5%SA/CS-CNTs的涂层,这可能是因为SA/CS-CNTs严重团聚抑制其阻隔作用,且SA/CS-CNTs含量的增加为离子传导提供更多的路径[22]。上述结果表明,适当添加SA/CS-CNTs可以提高环氧复合涂层的抗腐蚀能力,而过量添加会导致材料团聚沉降,加速腐蚀进程。
采用2种不同的电化学等效电路模型来模拟涂层样品的不同腐蚀阶段,第1种模型(R(RQ))如图9(a)所示,第2种模型(R(Q(R(QR))))如图9(b)所示[23]。当腐蚀性介质在初始阶段渗入涂层时,采用图9(a)等效电路模型模拟腐蚀过程,其中Rs为溶液电阻,CPEc为涂层恒相元件。随着涂层腐蚀损伤的加剧,越来越多的腐蚀性介质渗入到金属基材和涂层之间的界面,导致基材表面开始腐蚀。在此阶段,所采用的等效电路模型对应于图9(b),其中Rct和CPEdl分别表示涂层/基板界面处的电荷转移电阻和双电层电容[24]。
图10是EP、CCNTs/EP、SCCNTs/EP涂料涂覆的马口铁在电解质溶液中浸泡不同时间的照片。盐雾实验240 h后,EP涂层在划痕周围出现大量腐蚀产物,涂层有发白起泡现象;盐雾测试720 h后,锈蚀痕迹蔓延至整个涂层表面,涂层出现脱落迹象。CCNTs/EP涂层在盐雾实验720 h后锈蚀痕迹较EP涂层大幅减少,涂层起泡现象得到明显改善。相较于EP和CCNTs涂层,SCCNTs/EP涂层在盐雾实验720 h后,划痕处及周围出现轻微的锈蚀痕迹,缓蚀效果明显增强,其中SCCNTs/EP2涂层表面锈蚀斑点最少,主要集中在划痕周围,涂层表面光滑且不起泡,具有最佳的阻隔性能。
图11是SCCNTs/EP复合涂层的缓蚀机理示意图。EP涂层表面具有亲水性,且固化后会产生孔隙,增加了腐蚀性介质的扩散路径。SCCNTs/EP涂层具有良好的防腐效果,一方面源于壳聚糖包裹的CNTs可以在EP中均匀分散,延长了腐蚀介质的穿透路径。此外,CS中的氨基可与EP交联,增强CNTs与EP基体之间的界面结合强度,交联后的EP涂层结构更致密,进一步减少了微孔缺陷的形成[14];另一方面源于SA的接枝,增强了涂层的疏水性,有效提高了涂层对腐蚀性电解液的屏蔽性能。SCCNTs/EP复合涂层这两方面的优势协同发挥作用,使得环氧涂层具有优异的耐腐蚀效果。
(1)以戊二醛为交联剂,将壳聚糖包覆在多壁碳纳米管表面,并和硬脂酸实现共价功能化,合成了SA/CS-CNTs复合材料,修饰后的CNTs表面粗糙,管径增加了约10~20 nm。
(2)将SA/CS-CNTs与水性环氧树脂共混,制备了水性环氧复合涂料SCCNTs/EP。SCCNTs/EP2涂层表面平整光滑,无明显孔隙,水接触角可达104.2°,吸水率为3.75%,铅笔硬度3H,附着力0级,耐冲击强度45 kg·cm。
(3)添加0.5%SA/CS-CNTs的SCCNTs/EP2复合涂层具有最佳的防腐效果,缓蚀效率可达99.66%,其低频阻抗值较EP涂层提高了约5个数量级;腐蚀电流密度从4.17×10-6 A·cm-2减小到1.44×10-8 A·cm-2,腐蚀电位增加了0.39 V;在3.5%的NaCl溶液中浸泡96 h后,低频阻抗模量值仍高于107 Ω·cm2。盐雾测试720 h后,涂层表面锈蚀斑点主要集中在划痕周围,涂层光滑且不起泡。
  • 国家自然科学基金项目(51973001)
  • 安徽省科技计划重点项目(1704a0902018)
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2026年第54卷第9期
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doi: 10.11868/j.issn.1001-4381.2024.000510
  • 接收时间:2024-07-16
  • 首发时间:2026-10-28
  • 出版时间:2026-09-20
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  • 收稿日期:2024-07-16
  • 录用日期:2024-08-23
基金
国家自然科学基金项目(51973001)
安徽省科技计划重点项目(1704a0902018)
作者信息
    安徽大学 化学化工学院 安徽省水基高分子材料高性能化工程实验室,合肥 230601

通讯作者:

杨建军(1960—),男,教授,研究方向为水基高分子纳米杂化材料,联系地址:安徽省合肥市经开区九龙路111号安徽大学化学化工学院(230601),E-mail:
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2种不同金属材料的力学参数
科
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属数
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genus
种数
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species
占总种数比例
Percentage of
total species (%)
属
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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