Dry oxidizing methods have been widely used to modify surface properties of polymer and ceramic substrates. Compared to other dry oxidizing methods, ultraviolet light/ozone (UV/O3) treatment has hitherto attracted less attention, mainly due to relatively weak oxidizing power. With optimized processing conditions, however, UV/O3 treatment can be better capable of offering desired effects associated with appropriate surface modifications. Incorporation of nanoscale reinforcements, e.g., carbon nanotubes (CNTs) and graphite, into a polymer matrix creates a new class of composites that possess unique mechanical and functional capabilities. A proper surface treatment is critical to dispersing the reinforcements in the matrix, hence to provide adequate adhesion between the reinforcements and the matrix. In this article, a review is provided on the underlying mechanisms of and the advantages arising from UV/O3 treatment of polymer substrates and nanoscale carbon materials. Special focus is placed on the relationship between the changes in chemical composition, morphology, functional groups of the treated surface and the corresponding improvements in adhesion and wettability of the substrate, dispersion of nano-reinforcements, as well as the properties of the nanocomposites made therefrom.
Sun, C. , Zhang, D. and Wadsworth, L.C. (1999). Corona Treatment of Polyolefin Films - A Review , Advanced Polymer Technology , 18: 171-180.
3.
Strobel, M., Lyons, C.S. and Mittal, K.L. (1994). Plasma Surface Modification of Polymers: Relevance to Adhesion, VSP BV Publ., Utrecht , The Netherlands.
4.
Liston, E.M. (1991). Plasma Modification of Polymer Surfaces, In: Pireaux, J.J., Bertrand, P. and Bredas, J.L. (eds), Polymer-Solid Interfaces, pp. 429-442, Institute of Physics, Belgium.
5.
Wertheimer, M.R., Martinu, L., Klemberg-Sapieha, J.E. and Czeremuszkin, G. (2002). Plasma Treatment of Polymers to Improve Adhesion, In: Mittal, K.L. and Pizzi, A. (eds), Adhesion Promotion Techniques, Marcel Dekker Inc. Publ. , New York.
6.
Choi, B. and Heon, H. (1998). Removal of Cu Impurities on a Si Substrate by using (H2O2 + HF) and (UV/O3 + HF), Journal of Korean Physics Society, 33: 579-583.
7.
Choi, K., Hong, K.P. and Lee, C. (2002). Cu Contaminant Removal using UV/O3 and Remote Hydrogen Plasma, Surface Review and Letters, 9: 255-259.
8.
Choi, K., Ghosh, S., Lim, J. and Lee, C.M. (2003). Removal Efficiency of Organic Contaminants on Si Wafer by Dry Cleaning Using UV/O and ECR Plasma, Applied Surface Science, 206: 355-364.
9.
Luo, S.J. and Wong, C.P. (2001). Effects of UV/Ozone Treatment on Surface Tension and Adhesion in Electronic Packaging , IEEE Transactions on Components and Packaging Technologies , 24: 43-49.
10.
Sham, M.L. and Kim, J.K. (2004). Improved Underfill Adhesion in Flip Chip Packages by Means of Ultraviolet Light/Ozone Treatment, IEEE Transactions on Advanced Packaging, 27: 179-187.
11.
Hong, Y.T., He, Z.Q., Lennhoff, N.S., Banach, D.A. and Kanicki, J. (2004). Transparent Flexible Plastic Substrates for Organic Light-emitting Devices, Journal of Electronics Materials, 33: 312-320.
12.
Li, C.N. , Kwong, C.Y., Djurisic , A.B., Lai , P.T., Chui, P.C., Chan, W.K. and Liu , S.Y. (2005). Improved Performance of Oleds with ITO Surface Treatments, Thin Solid Films, 477: 57-62.
13.
Kim, S.Y. , Lee, J.L., Kim , K.B. and Tak , Y.H. (2004). Effect of Ultraviolet-Ozone Treatment of Indium-Tin-Oxide on Electrical Properties of Organic Light Emitting Diodes, Journal of Applied Physics , 95: 2560-2563.
14.
Manaka, T., Lim, E., Tamura, R. and Iwamoto, M. (2006). Control of the Nano Electrostatic Phenomena at a Pentacene/Metal Interface for Improvement of the Organic FET Devices, Thin Solid Film, 499: 386-391.
15.
Moser, N., Fitch, R.C., Crespo, A., Gillespie, J.K., Jessen, G.H., Via, G.D., Luo, B., Ren, F., Gila, B.P., Abernathy, C.R. and Pearton, S.J. (2004). Dramatic Improvements in Algan/Gan HEMT Device Isolation Characteristics After UV-ozone Pretreatment, Journal of the Electrochemical Society, 151: G915-G918.
16.
Lu, D., Qiu, T. and Wu, X.L. (2004). Influence of Polar Solvent on Light-emitting Property of Siox (X=1.2-1.6) Nanoparticles Irradiated by Ultraviolet Ozone, European Physical Journal B, 41: 49-53.
17.
Chi, D. and McIntyre, P.X. (2004). Film and Interface Layer Properties of Ultraviolet-Ozone Oxidized Hafnia and Zirconia Gate Dielectrics on Silicon Substrates, Applied Physics Letters , 85(20): 4699-4701.
18.
Ramanathan, S., McIntyre, P.C., Guha , S. and Gusev, E. (2004). Charge Trapping Studies on Ultrathin Zro2 and Hfo2 High-K Dielectrics Grown by Room Temperature Ultraviolet Ozone Oxidation, Applied Physics Letters, 84(3): 389-391.
19.
Chui, C.O., Kim, H., Chi, D., McIntyre, P.C. and Saraswat, K.C. (2006). Nanoscale Germanium MOS Dielectrics - Part II: High-kappa Gate Dielectrics, IEEE Transactions on Electron Devices, 53(7): 1509-1516.
20.
Sugai, H., Iijima, T. and Masumoto, H. (1999). Preparation of Lead Titanate Ultrathin Film using Langmuir-Blodgett Film as Precursor, Japanese Journal of Applied Physics Part 1 Regular Papers Short Notes & Review Papers, 38(9B): 5322-5325.
21.
Poulis, J.A. , Cool, J.C. and Logtenberg , E.H.P. (1993 ). UV Ozone Cleaning, a Convenient Alternative for High Quality Bonding Preparation , International Journal of Adhesion and Adhesives, 13: 89-96.
22.
Bai, G.J. , Weng, Y.X. and Hu , X.Z. (1996). Surface Modification of Polyolefine by UV Light/ Ozone Treatment, Journal of Applied Polymer Science, 60(13): 2397-2402.
23.
Oiseth, S.K. , Krozer, A., Lausmaa , J. and Kasemo, B. (2004). Ultraviolet Light Treatment of Thin High-density Polyethylene Films Monitored with a Quartz Crystal Microbalance , Journal of Applied Polymer Science, 92: 2833-2839.
24.
Teare, D.O.H. , Ton-that, C. and Bradley, R.H. (2000). Surface Characterization and Ageing of Ultra-violet Ozone Treated Polymers using Atomic Force Microscopy and X-ray Photoelectron Spectroscopy , Surface and Interface Analysis, 29: 276-283.
25.
Ton-That, C. , Teare, D.O.H., Campbell, P.A. and Bradley, R.H. (1999). Surface Characterisation of Ultraviolet-Ozone Treated PET Using Atomic Force Microscopy and X-ray Photoelectron Spectroscopy, Surface Science , 433-35: 278-282.
26.
Macmanus, L.F. , Walzak, M.J. and McIntyre, N.S. (1999). Study of Ultraviolet Light and Ozone Surface Modification of Polypropylene , Journal of Polymer Science Part A: Polymer Chemistry, 27: 2489-2501.
27.
Mathieson, I. and Bradley, R.H. (1996). Improved Adhesion to Polymers by UV/Ozone Surface Oxidation, International Journal of Adhesion and Adhesives, 16(1): 29-31.
28.
Efimenko, K. , Wallace, W.E. and Genzer, J. (2002). Surface Modification of Sylgard-184 Poly(Dimethylsiloxane) Networks by Ultraviolet and Ultraviolet/Ozone Treatment, Journal of Colloid and Interface Science, 254: 306-315.
29.
Berdichevsky, Y., Khandurina, J., Guttman , A. and Lo , Y.H. (2004). UV/Ozone Modification of Poly(Dimethylsiloxane) Microfluidic Channels, Sensors Actuators B-chemical, 97: 402-408.
30.
Olah, A., Hillborg, H. and Vancso, G.J. (2005). Hydrophobic Recovery of UV/Ozone Treated Poly(Dimethylsiloxane): Adhesion Studies by Contact Mechanics and Mechanism of Surface Modification , Applied Surface Science, 239: 410-423.
31.
Efimenko, K. , Crowe, J.A., Manias , E., Schwark, D.W., Fischer, D.A. and Genzer, J. (2005). Rapid Formation of Soft Hydrophilic Silicone Elastomer Surfaces, Polymer, 46: 9329-9341.
32.
Ye, H.K. , Gu, Z.Y. and Gracias, D.H. (2006). Kinetics of Ultraviolet and Plasma Surface Modification of Poly(Dimethylsiloxane) Probed by Sum Frequency Vibrational Spectroscopy, Langmuir , 22(4): 1863-1868.
33.
Childs, W.R. , Motala, M.J., Lee , K.J. and Nuzzo, R.G. (2005). Masterless Soft Lithography: Patterning UVO-induced Adhesion on Poly(dimethylsiloxane) Surfaces, Langmuir, 21: 10096-10105.
34.
Callen, B.W. , Ridge, M.L., Lahooti , S., Neumann, A.W. and Sodhi, R.N.S. (1995). Remote plasma and Ultraviolet-Ozone Modification of Polystyrene, Journal of Vacuum Science and Technology A, A13: 2023-2029.
35.
Davidson, M.R. , Mitchell, S.A. and Bradley, R.H. (2005). Surface Studies of Low Molecular Weight Photolysis Products from UV-Ozone Oxidized Polystyrene , Surface Science, 581: 169-177.
36.
Yu, C.H. , Parikh, A.N. and Groves, J.T. (2005). Direct Patterning of Membrane-derivatized Colloids Using In-Situ UV-Ozone Photolithography, Advanced Materials, 17: 1477-1480.
37.
Loo, Y.L. , Willet, R.L., Baldwin , K.W. and Rogers, J.A. (2002). Interfacial Chemistries for Nanoscale Transfer Printing, Journal of the American Chemical Society, 124: 7654-7655.
38.
Park, J. and Hammond, P.T. (2004). Multilayer Transfer Printing for Polyelectrolyte Multilayer Patterning: Direct Transfer of Layer-by-Layer Assembled Micropatterned Thin Films, Advanced Materials, 16: 520-525.
39.
Teare, D.O.H. , Emmison, N., Ton-That , C. and Bradley, R.H. (2001). Effects of Serum on the Kinetics of CHO Attachment to Ultraviolet-ozone Modified Polystyrene Surfaces , Journal of Colloid and Interface Science , 234: 84-89.
40.
Ton-That, C. , Campbell, P.A. and Bradley, R.H. (2000). Frictional Force Microscopy of Oxidized Polystyrene Surfaces Measured Using Chemically Modified Probe Tips, Langmuir , 16: 5054-5058.
41.
Michael, M.N. , El-Zaher, N.A. and Ibrahim, S.F. (2004). Investigation into Surface Modification of Some Polymeric Fabrics by UV/Ozone Treatment, Polymer-plastics Technology and Engineering , 43: 1041-1052.
42.
Li, J., Kim, J.K. and Sham, M.L. (2005). Conductive Graphite Nanoplatelet/Epoxy Nanocomposites: Effects of Exfoliation and UV/Ozone Treatment of Graphite, Scripta Materialia, 53: 235-240.
43.
Li, J., Sham, M.L., Kim, J.K. and Marom, G. (2007). Morphology and Properties of UV/Ozone Treated Graphite Nanoplatelet/Epoxy Nanocomposites, Composites Science and Technology, 67: 296-305.
44.
Geng, Y., Li, J. and Kim, J.K. (2008). Amino Functionalization of Graphite Nanoplatelet , Journal of Nanoscience and Nanotechnology, 8: 6238-6246.
45.
Sham, M.L. and Kim, J.K. (2006). Surface Functionalities of Multi-wall Carbon Nanotubes after UV/Ozone and TETA Treatments, Carbon, 44: 768-777.
46.
Miko, C., Milas, M., Seo, J.W., Gaal, R., Kulik, A. and Forro, L. (2006). Effect of Ultraviolet Light Irradiation on Macroscopic Single-walled Carbon Nanotube Bundles, Applied Physics Letters , 88: 151905.1-151905.3.
47.
Najafi, E., Kim, J.Y., Han, S.H. and Kwanwoo, S. (2006). UV-Ozone Treatment of Multi-walled Carbon Nanotubes for Enhanced Organic Solvent Dispersion, Colloids and Surfaces A, 284: 373-378.
48.
Qin, S.H. , Qin, D.Q., Ford , W.T., Zhang, Y.J. and Kotov, N.A. (2005). Covalent Cross-linked Polymer/Single-wall Carbon Nanotube Multilayer Films , Chemistry of Materials, 17: 2131-2135.
49.
Valentini, L., Armentano, I., Kenny , J.M., Bidali, S. and Mariani, A. (2005). Interaction of Oxygen with Nanocomposites Made of n-Type Conducting Polymers and Carbon Nanotubes: Role of Charge Transfer Complex Formation Between Nanotubes and Poly(30 octylthiophene) , Thin Sold Films, 476: 162-167.
50.
Ma, P.C. , Kim, J.K. and Tang, B.Z. (2006). Functionalization of Carbon Nanotubes Using a Silane Coupling Agent , Carbon, 44: 3232-3238.
51.
Ma, P.C. , Kim, J.K. and Tang, B.Z. (2007). Effects of Silane Functionalization on the Properties of Carbon Nanotube/Epoxy Nanocomposites, Composites Science and Technology, 67: 2965-2972.
52.
Li, J., Ma, P.C., Sze, C.W., Kai, T.C., Tang, B.Z. and Kim, J.K. (2007). Correlations Between Percolation Threshold, Dispersion State and Aspect Ratio of Carbon Nanotube, Advanced Functional Materials, 17: 3207-3215.
53.
Ma, P.C. , Wang, S.Q., Kim , J.K. and Tang, B.Z. (2009). In-Situ Amino Functionalization of Carbon Nanotubes Using Ball Milling , Journal of Nanoscience & Nanotechnology, 9: 749-753.
54.
Li, J., Wong, P.S. and Kim, J.K. (2008). Hybrid Nanocomposites Containing Carbon Nanotubes and Graphite Nanoplatelets, Materials Science and Engineering: A, 483-484: 660-663.
55.
Mishchuk, N.A. , Goncharuk, V.V. and Vakulenko , V.F. (2008). Theoretical Analysis of Physicochemical Processes Occurring During Water Treatment by Ozone and Ultraviolet Radiation, Advances in Colloid and Interface Science, 139: 62-73.
56.
Summerfelt, S.T. (2003). Ozonation and UV Irradiation - An Introduction and Examples of Current Applications, Aquacultural Engineering, 28: 21-36.
57.
Vig, J.R. (1987). UV/Ozone Cleaning of Surfaces, In: Mittal, K.L. (ed.), Treaties on Clean Surface Technology, Plenum Press, New York.
58.
Lim, J.K. and Park, Y.P. (2003). Analysis of Ozone Concentration for Superconductor Thin Film, Current Applied Physics, 3: 331-335.
59.
Eipel, C., Jeroschewski, P. and Steinke, I. (2003). Determination of Ozone in Ambient Air with a Chemiluminescence Reagent Film Detector, Analytica Chimica Acta, 491: 145-153.
60.
Romero-Sanchez, M.D., Pastor-Blas, M.M., Martin-Martinez , J.M., Zhdan, P.A. and Watts, J.F. (2001). Surface Modifications of a Vulcanized Rubber Using Corona Discharge and Ultraviolet Radiation Treatments, Journal of Materials Science, 36: 5789-5799.
61.
Woo, R.S.C. , Zhu, H.G., Leung , C.K.Y. and Kim , J.K. (2008). Environmental Degradation of Epoxy-Organoclay Nanocomposites Due to UV Exposure: Part II Residual Mechanical Properties, Composites Science and Technology, 68: 2149-2155.
62.
Yosomiya, R., Morimoto, K., Nakajima, A., Ikada, Y. and Suzuki, T. (1989). Adhesion and Bonding in Composites, Ch. 3. Marcel Dekker Inc. Publ., New York.
63.
Kim, J.K. and Mai, Y.W. (1991). High Strength, High Fracture Toughness Fibre Composites with Interface Control - A Review , Composites Science and Technology, 41: 333-378.
64.
Kim, J.K. and Mai, Y.W. (1998). Engineered Interfaces in Fibre Reinforced Composites, Elsevier Publ. , Oxford, UK.
65.
Scolar, D.A. (1974). Interfaces in Polymer Matrix Composites, In: Plueddemann, E.P. (ed.), Composite Materials, Academic Press, New York .
66.
Donnet, J.B. and Bansal, R.C. (1984). Surface Properties of Carbon Fibers, Carbon Fibers, Marcel Dekker Publ., New York.
67.
Kelly, B.T. (1981). Physics of Graphite, Applied Science, London.
68.
Li, J., Vaisman, L., Marom, G. and Kim, J.K. (2007). Br Treated Graphite Nanoplatelets for Improved Electrical Properties of Conducting Polymer Composites, Carbon , 45: 744-750.
69.
Popov, V.N. (2004). Carbon Nanotubes: Properties and Application, Materials Science and Engineering R, 43: 61-102.
70.
Coleman, J.N. , Khan, U. and Gunko, U.K. (2006). Mechanical Reinforcement of Polymers Using Carbon Nanotubes, Advanced Materials, 18: 689-706.
71.
Thostenson, E.T., Ren, Z. and Chou, T.W. (2001). Advances in the Science and Technology of Carbon Nanotubes and Their Composites: A Review, Composites Science and Technology, 61: 1899-1912.
72.
Thostenson, E.T., Li, C. and Chow, T.W. (2005). Nanocomposites in Context , Composites Science and Technology , 65: 491-516.
73.
Esumi, K., Ishigami, M., Nakajima, A., Sawada, K. and Honda, H. (1996). Chemical Treatment of Carbon Nanotube, Carbon, 34: 279-281.
74.
Gojny, F.H. , Nastalczyk, J., Roslaniec , Z. and Schulte, K. (2003). Surface Modified Multi-walled Carbon Nanotubes in CNT/Epoxy-composites , Chemical Physics Letters, 370: 820-824.
75.
Yu, R., Chen, L., Liu, Q., Lin, J., Tan, K.L., Ng, S.C., Xu, G.Q. and Hor, T.S. (1998). Platinum Deposition on Carbon Nanotubes via Chemical Modification, Chemistry of Materials, 10: 718-722.
76.
Kukovecz, A. , Kramberger, C.H., Holznger , M., Kuzmony, H., Schalka, J., Mannsberger, M. and Hirsh, A. (2002). On the Stacking Behavior of Functionalized Single-wall Carbon Nanotubes, Journal of Physical Chemistry B, 106: 6374-6380.
77.
Zhu, J. , Peng, H., Rodriguez-Macias , F., Margrave, J.L., Khabashesku, V.N., Imam, A.M., Lozano, K. and Barrera, E.V. (2004). Reinforcing Epoxy Polymer Composites Through Covalent Integration of Functionalized Nanotubes, Advanced Functional Materials , 14: 643-648.
78.
Gojny, F.H. , Wichmann, M.H.G., Köpke, U., Fiedler, B. and Schulte, K. (2004). Carbon Nanotube-reinforced Epoxy-composites: Enhanced Stiffness and Fracture Toughness at Low Nanotube Content, Composites Science and Technology, 64: 2363-2371.
79.
Touhara, H. and Okina, F. (2000). Property Control of Carbon Materials by Fluorination , Carbon, 38: 241-267.
80.
Stevens, J.L. , Huang, A.Y., Peng , H., Chiang, I.W., Khabashesku, V.N. and Margrave, J.L. (2003). Sidewall Amino-functionalization of Single-walled Carbon Nanotubes Through Fluorination and Subsequent Reactions with Terminal Diamines, Nano Letters, 3: 331-336.
81.
Deng, Y., Deng, C., Yang, D., Wang, C., Fu, S. and Zhang, X. (2005). Preparation, Characterization and Application of Magnetic Silica Nanoparticle Functionalized Multi-walled Carbon Nanotubes , Chemical Communications, 44: 5548-5550.
