Tribology study of PVA contact lens in ionic aqueous environments

Jinping Dong and Greg D. Haugstad Characterization Facility, Institute of Technology, University of Minnesota, Minneapolis, MN

INTRODUCTION Because of their high water content, high oxygen permeability, 1 high optical clarity, and low protein adsorption, crosslinked Polyvinyl Alcohol (PVA) hydrogels find new applications in the manufacturing of 2 soft contact lenses, especially for low cost daily disposable lenses. Study of the mechanical properties such as the stiffness, friction and adhesion of the PVA hydrogel surface therefore becomes essentially important for understanding its biological interactions. Scanning probe microscopy (SPM) has been proved to be a promising technique to 3 image the surface topography, and to probe the mechanical responses of the contact lens surface. Extensive studies have been done to understand the surface stiffness, adhesion, and viscoelastic properties of poly(2-hydroxyethyl methacrylate) (pHEMA) type contact lenses as a function of saline, polymer additives, and environmental 4 humidity. In this work, we employed SPM to probe the surface mechanical behavior of daily disposable PVA contact lenses in ionic aqueous environments. Although little or even no special care is needed for wearing daily disposal contact lenses comparing to the traditional reusable ones, to understand their surface behavior in different aqueous environments is of great scientific and practical interest for their biomedical applications. EXPERIMENTAL Commercial Focus DAILIES PVA contact lens and Softwear lens care saline are provided by Ciba Vision Co. Scanning probe microscopy was performed with Molecular Imaging PicoScan SPM and PicoPlus SPM. Topography and friction imaging in contact mode were accomplished using V-shaped, gold-coated silicon nitride cantilevers with nominal spring constant of 0.12 N/m. Scanning was performed in a homemade stainless steel well filled with ionic solutions. Contact lens was placed on a stainless steel arbor and then secured to the bottom of the well by a cover plate with small orifice in the center. Load ramping was achieved by adding a triangle wave to the deflection signal through a homemade adder circuit. The ramping cycles and magnitude are controlled by the frequency and the amplitude of the waveform from the external function generator. SPM measurements on the lenses were carried out on the following 4 steps: (1) tested right after the lens was removed from storage package using package saline; (2) lens was transferred into Softwear saline and tested after 5 hours of soaking; (3) tested after 17 hours of soaking in Softwear saline; (4) lens was returned to the package saline and tested within 2 hours. RESULTS AND DISCUSSION Friction force images at a particular load were acquired and analyzed as histograms to provide a spectroscopic lineshape of friction comparable between saline types.
1000 900 Friction force (arb. units) 800 700 600 500 400 300 200 100 0 0 500 1000 Pixel number 1500 2000

Figure 1 shows the friction force measured with cantilever deflection of 75nm. Friction force increased after the lens was moved to Softwear saline. A much wider friction distribution was also observed. Upon moved back to package saline, friction behavior of the lens surface was almost restored, which indicated a possible reversible change of the lens surface in different saline solutions. Surface roughness, adhesion and stiffness extracted from force volume measurements were also recorded under four conditions. Friction images with continuous change of the normal force were recoded to show the friction coefficient of the surface. Each set of data was normalized with the reference of the data from the first experimental step. Figure 2 compares the surface behavior in different saline conditions. It is shown that the surface roughness, friction coefficient, friction force, adhesion and stiffness of the PVA lens are increased 1.5-4 times as the lens is moved from its storage package to the commercial lens care saline (Softwear ).
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roughness slope of load ramping friction force Adhesion (FV) Stiffness (FV)

Experimental steps

Figure 2. Comparison of the surface properties of PVA contact lens in four experimental steps. Same measurements were carried out with Softwear saline replaced by pure water or freshly prepared package saline, and no significant change of the above properties were observed. Examination of the compositions in Focus DAILIES package saline and Softwear saline indicated that it contains large amount of borate ions (Sodium Borate, boric acid), which induce crosslinking of the free PVA chains at the surface. PVA network formed by borate ions is harder than the bulk network structure. The surface was therefore rougher than the brush like structure before the network is formed. It was then expected that the friction coefficient and friction force were increased. It can be concluded from the results that the formation of the PVA network at the lens surface by borate ions was a reversible process. ACKNOWLEDGEMENTS Funding support from Ciba Vision Co. and instrumentation support from Molecular Imaging Co. are acknowledged by authors. REFERENCS Finch, C.A. Polyvinyl AlcoholProperties and Applications, John Wiley & Sons, London, 1973; Finch, C. A. Polyvinyl Alcohol Developments, John Wiley& Sons, London, 1992. Goldenberg, M. U.S. patent 1986 US 4598122 A19860701; Devlin, B.G.; Tena, M.; Medina, N.A. U.S. Pat. Appl. Publ. 2005, US 2005056954 A1 2005031. Grobe, G.L.; Valint, P.L.; Ammon, D.M. J Biomed Mater Res 1996, 32, 45. Kim, S.H.; Marmob, C.; Somorjai, G.A. Biomaterials 2001, 22, 3285; Kim, S.H.; Opdahl, A.; Marmob, C.; Somorjai, G.A. Biomaterials 2002, 23, 1657; Opdahl, A.; Kim, S.H.; Koffas, T.S.; Marmob, C.; Somorjai, G.A. Journal of Biomedical Materials Research, Part A 2003, 67A(1), 350; Koffas, T.S.; Opdahl, A.; Marmob, C.; Somorjai, G.A. Langmuir 2003, 19, 3453.

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Figure 1. Friction force histograms from four steps of measurements on the PVA lens surface