丙烯酸酯紫外光固化材料表面的XPS研究

doi:10.7517/j.issn.1674-0475.2006.06.428

影像科学与光化学 ›› 2006, Vol. 24 ›› Issue (6): 428-435.DOI: 10.7517/j.issn.1674-0475.2006.06.428

丙烯酸酯紫外光固化材料表面的XPS研究

骆燕, 王德海, 蔡延庆

浙江工业大学, 化学工程与材料学院, 浙江, 杭州, 310014

收稿日期:2006-05-25 修回日期:2006-07-13 出版日期:2006-11-23 发布日期:2006-11-23
通讯作者: 王德海(1963-), 男, 博士, 教授, 主要从事光固化材料方面的研究.
基金资助:
浙江省自然科学基金资助项目(Z503236).

XPS Study of the Surface of UV Cured Acrylates

LUO Yan, WANG De-hai, CAI Yan-qing

College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, P.R. China

Received:2006-05-25 Revised:2006-07-13 Online:2006-11-23 Published:2006-11-23

摘要/Abstract

摘要： 分别在不同的固化氛围(空气和氮气)下对配方相同的双酚A环氧丙烯酸树脂进行紫外光固化,得到了具有不同表面能的固化膜.利用X射线光电子能谱(XPS),在不同的掠射角(60°和90°)下表征了固化膜样品的元素组成、电子结合能、相对含量以及表面官能团类型.结果表明:不同的固化环境会导致材料表面能的差异.与空气下固化的材料相比,氮气下固化的材料表面C_1s和O_1s原子的结合能均向低结合能方向位移,且低结合能的C—C/C—H含量大于前者的含量,而相对高结合能的CO和C—O含量均小于前者.在空气下固化时,其表面高结合能的单键氧含量大于氮气下固化的材料表面.材料表面与基材所形成的界面间的原子结合能以及原子各种结合状态的相对含量也不同.如在氮气下固化时,材料表面C_1s原子的结合能为286.62eV,而玻璃界面的结合能为287.48eV,且两面中C_1s和O_1s原子5种结合状态的相对含量都有差异.材料自身组分在固化过程中的迁移,使固化膜中C_1s和O_1s的原子浓度由表及里存在一定的梯度分布.CO和C—O等基团含量从表面到本体逐渐增多,而C—C/C—H含量从表面到本体逐渐减少.

关键词: 表面能, XPS, 结合能, 原子浓度

Abstract: The epoxy acrylate resins were UV cured under different atmospheres (air and N₂) and characterized with X-ray photoelectron spectroscopy at two different take-off angles, namely 60° and 90°. The results obtained indicate that different curing environments result in the change of surface energy of the films. Compared with the film cured in the air, the binding energies of C1s and O1s on the surface of the film cured in N₂ move to lower ones. The content of C—C/C—H is higher than that cured in the air, whereas the contents of CO and C—O are lower in both cases. As for the film cured in the air, the content of the single-bond oxygen with high binding energy is higher than that cured in N₂. Both the binding energy of C1s and O1s and the atomic contents are different between the surface and substrate interface of the films. For example, the binding energy of C1s on the surface and glass interface of the film cured in N₂ are 286.62 eV and 287.48 eV, respectively. Besides, the atomic concentration in the films presents gradient distribution from the most external surface toward the bulk. The contents of CO and C—O increase from surface to bulk, and the content of C—C/C—H decreases from surface to bulk, which is caused by the migration of the compositions during the curing process.

Key words: surface energy, XPS, binding energy, atom concentration

中图分类号:

骆燕, 王德海, 蔡延庆. 丙烯酸酯紫外光固化材料表面的XPS研究[J]. 影像科学与光化学, 2006, 24(6): 428-435.

LUO Yan, WANG De-hai, CAI Yan-qing. XPS Study of the Surface of UV Cured Acrylates[J]. Imaging Science and Photochemistry, 2006, 24(6): 428-435.

参考文献

[1] 刘辉,罗英武,李宝芳溶胶-凝胶法制备紫外光固化纳米复合涂料[J].高校化学工程学报,2004,18(3):329-333.Liu H,Luo Y W,Li B F.Preparation of UV-curable nano-composite coating by the Sol-Gel process[J].Journal of Chemical Engineering of Chinese Universities,2004,18 (3):329-333.
[2] Bongiovanni R,Pollicino N,Gozzelino G.Surface properties of networks containing fluorinated acrylic monomers[J].Polymers for Advanced Technologies,1996,7(5-6):403-408.
[3] Huang Y M,Lan H Y.Dynamic reverse compensation to increase the accuracy of the rapid prototyping system[J].Journal of Materials Processing Technology,2005,167 (2-3):167-176.
[4] Luan B,Liu X Y,Nagata J.Residual stress analysis-an important consideration for coating of stereolithography polymers[J].Surface and Coatings Technology,2005,192 (2-3):323-330.
[5] Goss B.Bonding glass and other substrates with UV curing adhesives[J].International Journal of Adhesion and Adhesives,2002,22(5):405-408.
[6] Horigome K,Ebe K,Kuroda S I.UV curable pressure-sensitive adhesives for fabricating semiconductors.Ⅱ.the effect of functionality of acrylate monomers on the adhesive properties[J].Journal of Applied Polymer Science,2004,93(6):2889-2895.
[7] Scherzer T,Tauber A,Mehnert R.UV curing of pressure sensitive adhesives studied by real-time FTIR-ATR spectroscopy[J].Vibrational Spectroscopy,2002,29(1-2):125-131.
[8] Yebra D M,Kiil S,Dam-Johansen K.Antifouling technology-past,present and future steps towards efficient and environmentally friendly antifouling coatings[J].Progress in Organic Coatings,2004,50(2):75-104.
[9] Bierwagen G P,Tallman D E.Choice and measurement of crucial aircraft coatings system properties[J].Progress in Organic Coatings,2001,41(4):201-216.
[10] Ameduri B,Bongiovanni R,Lombardi V.Effect of the structural parameters of a series of fluoromonoacrylates on the surface properties of cured films[J].Journal of Polymer Science,Part A:Polymer Chemistry,2001,39 (24):4227-4235.
[11] Sangermano M,Bongiovanni R,Malucelli G.Fluorinated epoxides as surface modifying agents of UV-curable systems[J].Journal of Applied Polymer Science,2003,89(6):1524-1529.
[12] Bongiovanni R,Sangermano M,Malucelli G.Fluorinated vinyl ethers as new surface agents in the photocationic polymerization of vinyl ether resins[J].Journal of Polymer Science,Part A:Polymer Chemistry,2003,41(18):2890-2897.
[13] Roberta Bongiovanni GMAPCTGSAP.Perfluoropolyether structures as surface modifying agents of UV-curable systems[J].Macromolecular Chemistry and Physics,1998,199(6):1099-1105.
[14] Sangermano M,Bongiovauni R,Malucelli G.Surface properties of cationic ultraviolet-curable coatings containing a siloxane structure[J].Journal of Applied Polymer Science,2004,93(2):584-589.
[15] Sangermano M,Bongiovanni R,Malucelli G.Synthesis and cationic photopolymerization of a new fluorinated oxetane monomer[J].Polymer,2004,45(7):2133-2139.
[16] Al-Turaif H,Bousfield D W,LePoutre P.The influence of substrate absorbency on coating surface chemistry[J].Progress in Organic Coatings,2002,44(4):307-305.
[17] Al-Turaif H,Bousfield D W.The influence of substrate absorbency on coating surface energy[J].Progress in Organic Coatings,2004,49(1):62-68.
[18] Owens D,Wendt R.Estimation of the surface free energy of polymers[J].Journal of Applied Polymer Science,1969,13(8):1741-1747.
[19] Asif A,Huang C,Shi W.UV curing behaviors and hydrophilic characteristics of UV curable waterborne hyperbranched aliphatic polyesters[J].Polymers for Advanced Technologies,2003,14(9):609-615.
[20] 吴宁晶,黄礼侃,郑安呐,等.聚苯乙烯/聚二甲基硅氧烷嵌段与接枝共聚物表面聚集态的研究[J].高分子学报,2005,(1):137-141.Wu N J,Huang L K,Zheng A N,et al.Surface study of block and graft copolymers of polystyrene-polydimethylsiloxane[J].Acta Polymerica Sinica,2005,(1):137-141.
[21] Alov N,Kutsko D,Spirovova I.XPS study of vanadium surface oxidation by oxygen ion bombardment[J].Surface Science,2006,in press.
[22] Ferreira L,Evangelista M B,Martins M C L.Improving the adhesion of poly(ethylene terephthalate) fibers to poly (hydroxyethyl methacrylate) hydrogels by ozone treatment:Surface characterization and pull-out tests[J].Polymer,2005,46(23):9840-9850.
[23] Chattopadhyay D K,Panda S S,Raju K V S N.Thermal and mechanical properties of epoxy acrylate/methacrylates UV cured coatings[J].Progress in Organic Coatings,2005,54(1):10-19.
[24] Kassis C M,Steehler J K,Betts D E.XPS studies of fluorinated acrylate polymers and block copolymers with polystyrene[J].Macromolecules,1996,29 (9):3247 -3254.
[25] Yamamoto F,Y amakama S.Surface grafting of polyethylene by mutual irradiation in methyl acrylate vapor.Ⅲ.Quantitative surface analysis by X-ray photoelectron spectroscopy[J].Journal of Polymer Science,1979,17:1581-1590.
[26] 赵根祥,钱树安,杨章玄.聚酰亚胺基碳膜形成过程中表面结构的XPS研究[J].高分子材料科学与工程,1996,12(1):110-115.Zhao G X,Qian S A,Yang Z X.An XPS study of the surface structure of polyimide-based carbon film during the formarion[J].Polymer Materials Science & Engineering,1996,12 (1):110-115.

丙烯酸酯紫外光固化材料表面的XPS研究

XPS Study of the Surface of UV Cured Acrylates

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 4

编辑推荐

Metrics

本文评价

[1]	吴世康, 汪鹏飞. 功能染料在有机太阳能电池中的应用[J]. 影像科学与光化学, 2010, 28(3): 217-229.
[2]	马国杰, 王德海, 贺锡挺. 水介质对紫外光固化丙酸酯材料表面性能的影响[J]. 影像科学与光化学, 2008, 26(5): 377-384.
[3]	吴树新, 尹燕华, 何菲, 秦永宁. 掺铜TiO₂光催化剂光催化氧化还原性能的研究[J]. 影像科学与光化学, 2005, 23(5): 333-339.
[4]	毛立群, 冯彩霞, 金振声, 张治军, 党鸿辛. Au/TiO₂的制备及其光催化氧化丙烯的研究[J]. 影像科学与光化学, 2005, 23(1): 61-65.