C = K’Dp

Table 2: Units for Henry’s Law for Polymers Below Their Glass Transition Temperature15,16

Fick’s law for glassy polymers is given as:

N = -DD (dCD/dx) – DH (dCH/dx)

This can be simplified as follows:

N = -D’D(d/dx)(C D + CH)

N = -D’D (dC’/dx)

Table 3: Symbols used in Fick’s for Glassy Polymers15, 17

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These equations yield results that are reasonable, and that are in good agreement when applied to hard contact lenses.To gain the necessary data however one must know the free volume fraction of the polymer. 15, 16, 17Diffusion is heavily dependent upon the free volume because it is a measure of the polymers porosity.One possible way of finding this is by positron annihilation spectroscopy.This paper will not discuss this in depth, but more can be found in the references. 15
Research in the 1970’s found that the impermeability of PMMA lenses could be overcome by copolymerizing MMA with silicone acrylate.A scientist by the name Norman Gaylord copolymerised methacryloxypropyl tris(trimethysiloxy silane), (TRIS),with MMA.The result was a polymer that had the strength of MMA, but also the oxygen permeability of silicone.Silicone is hydrophobic however, so the wetting agent methacrylic acid (MAA) was added to increase lens wetability.The PMMA-TRIS lens was the first RPG lens and was highly successful. Several lenses received FDA approval for daily wear, and are still used today. 2

Figure 5:Methacrylic Acid

PMMA-TRIS lenses were problematic because TRIS is hydrophobic, and lipophilic.In addition, the lenses still did not have the permeability’s required for extended wear.This caused many complications in the push to develop extended wear lenses, and increase biocompatibility.Looking for a solution, researchers began looking into doping MMA-TRIS lenses with Fluoromethacrylates. 23Recent research has shown that doping lenses with Fluoromethacrylates increases the free volume fraction. 2,15Increasing the free volume fraction is like adding lanes to the diffusion expressway.It gives oxygen and carbon dioxide more room to penetrate the lens.Thus, it efficiently increases the polymers permeability, hence increasing comfort and decreasing ocular strain. 15This increase in the polymers permeability along with varying the thickness of the lens created a RGP lenses that were approved for extended wear for up to seven days. 2
While hard contacts are not the most the most convenient they are very cost effective.They are polymerized in bulk, and then cut with a precision lathe.This allows them to be made very cheaply.In addition, their relative impermeability makes then very resistant to environment of the eye.They typically repel proteins and lipids very effectively.With proper maintenance the lenses can be used for several years.Hard lenses are also very durable, and their strength helps them resist scratching, and protect the cornea. 2
Soft Contact Lenses
The most popular type of contact lens is a soft lens.Soft contact lenses are made of thermo-set polymer hydrogels.Like hard contacts lens polymers, these gels are made up of a three dimensional, amorphous network with cross-links.The lenses are soft because the polymer is above its glass transition temperature.Soft contacts are typically formed using cast molding or the spin cast method.They can be produced by the lath cutting process, but this is less common.23
In soft contact lenses the water content affect many things. The permeability of the lens is proportional to the amount of water in the lens.As the percent weight of water increases in the lens, the permeability increases relatively linearly.The lenses ability to absorb various amounts of water also makes them highly hydrophilic. These attributes gives soft contact lenses the ability to achieve permeability’s that allows them to be used for extended wear without damage to the eye.The increased permeability does not come freely however.As the water content is increased the polymers loose their strength.This can lead to tearing or scratching of the lens.A softer lens also offers the cornea less protection. 2
The first hydrogel contacts consisted of HEMA that was cross-linked with either ethylene dimethacrylate (EDMA) or ethylene glycol monogethacrylate (EGDMA).Future models of hydrogel lenses added the surfactants, methacrylic acid (MAA) and N vinyl pyrollidone (NVP) to increase water content.MMA is undesirable however because it makes the polymer ionic, which attracts proteins. 2,8,18HEMA has also been substituted with such monomers as glycerol methacrylate (GMA) that shows a higher resistance biofilm formation.Typical HEMA/MAA soft contact lenses have oxygen permeabilties of about 15-25 Barrers.2, 23

Figure6:Ethylene glycol monogethacrylate

Figure 8:Hydroxyethyl Methacrylate, and N Vinyl Pyrollidone

Seeking to improve soft contact lens permeability scientist started to make hydrogels from silicone based polymers like polydimethylsiloxane (PDMS)..The silicone hydrogel contact lens, also known as siloxane lenses, show impressive permeability (PDMS has a DK of 600 Barres), while retaining the comfort, wetability, and biofilm resistance of non-silicon based hydrogels.24 Unlike hydrogel lenses however, the oxygen permeability of silicone hydrogels decreases exponentially as water content increases.As discussed in hard contact lenses, silicone is hydrophobic, so the wetablity decreases as water content decreases. This led scientist to researching ways of making siloxane based lenses more wetable. 2, 19
The use of fluorine doped side chains has also become increasingly popular as a method to further increase permeability.When coupled with siloxane, fluorine can effectively increase the permeability while also effectively resisting lipid deposits.The challenge scientist encounter with fluorine is that it repels water.This leads them to cap fluorine chains with methacrylate with is less hydrophobic.25
The surface chemistry of soft contact lenses is of great importance.While the soft contact lenses typically have acceptable diffusion rates, all methacrylic and acrylic hydrogels are hydrophobic to a certain extent.In fact, it has been shown that while the water content of a hydrogel helps its permeability, it not little or nothing to affect its wetability.21In the case of siloxane lenses it is because the surfaces tend to consist of siloxane.Siloxane migrates to the surface of the lens during polymerization because of its desire of air.While siloxane is successful at repelling proteins, but it is highly hydrophobic which results in lipid and protein deposition on the lens.19Initial research attempted to blend hydrophobic silicone based monomers with hydrophilic monomers.These attempts were unsuccessful however because the difference in hydrophilicity would cause phase seperation. 2, 20 Recently with it has been shown that by grafting polyoxyethylene to the surface, the lens effectively repels protein and lipids, and increased wetability.Improved surfactants consisting of random copolymers of lauryl-, hexyl-, and methyl-methacrylate and polyethylene glycol methacrylate, have also shown a lot of promise.19The surfactants are bound to the surface during the actual making of the lens.The surfactant monomers are added to the contact lens monomers, and the surfactants moved to the surface during lens the creation of the lens because they have a higher desire for air then siloxane.Covalent bonds are then formed as the silicones of the gel matrix appear.19Currently silicone hydrogel lenses have DK’s have about 50-200 Barrers, however none of these lenses currently in commercially availble.2
Attempts to improve the wetability of soft contact lenses have also been make on the manufacturing side of processing.Research has shown that by polymerizing the contact in polar molds effectively increased the wetability of the lens.This is because the charge distribution on the mold attracts charges to the surface of the lens while it is forming.Once the charges are at the surface of the lens, they are polymerized, and consequently forced to stay at the surface.24
The water in tears is then attracted to this polar surface of the lens.
Problems Caused by Contact Lens Use

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The biocompatibility of contact lenses is at the forefront of scientific and engineering research.This is in partly due to the push for an extended wear lens, and also due to health disorders that arise from contact lens use.While many advances have been made in the biocompatibility, and physical properties of lenses, significant problems still exist.Possible contact lens disorders are listed in table.These disorders must be taken into account when comparing contact lenses to eye glasses or laser correction surgery.While taking out and removing contacts on a daily or weekly basis can be stressful, the eye can typically heal from contact lens disorders.This should be compared to laser surgery where a mistake can be fatally hazardous to the eye.The debate between contacts and laser surgery will increase in the future as laser surgery becomes more successful and contact lens manufacturers develop cheaper, 30 day extended wear lenses that have little risk of infection.

Table 4:Some Common Contact lens Disorders14,22

Conclusion
All contact lenses consist of amorphous, three-dimensional, polymer matrixes.Hard contacts consist of polymers that are below their glass transition temperature, and typically contain little or no water.Soft contact lenses consist of polymers that are above their glass transition temperature, and typically have a relatively high water content.
Hard Contact lenses have increased their permeability by thinning the lens, and doping MMA with TRIS and/or fluorine based monomers.Soft contact lenses have sought to increase their permeability in different ways.Hydrogel lenses has sought to increase water content, while siloxane hydrogels have tried to find ways of decreasing their water content.Some examples of the
Contact lens science has increased rapidly in the 20th century.While significant progress has been made, the most challenging aspect await to be solved in the 21st century.As we begin the new millennium polymer scientist are working in collaboration with biologist, chemist, and medical doctors to produce the extended wear lens.This lens will be able to be used for up to thirty days without removal, and be almost completely resistive to biofilm deposition.
References
1. Salvatori, P.L. The story of contact lenses.Obrig Laboratories: New York,
1960.pg. 19-24.
2. Kunzler, J.F. McGee, J.A. Contact Lens Materials Chemistry in Britian
3. Heitz, R.F. ‘Contact Lenses’. (2nd Edition, Volume 1) Dabazies, O.H. Little
Brown and Company, 1989.1.1-1.9.
4. Lubick, N. ‘The Hard and the Soft.’ Scientific American. 10/2000
http://www.sciam.com/2000/1000issue/working.html
5. Hamano, H., Kaufman, H.E. The Physiology of the Cornea and Contact Lens
Applications.Churchill Livingstone: New York, 1987.Pages 69-74.
6. Larke, J. The Eye in Contact Lens Wear.Butterworths:Toronto, 1985. Page 24-27, 40-47.
7 Friends, G., Kunzler, J., Ozark, R., J. Biomedical Materials Research, 1992, 26, 59-67
8 ‘Biomedical Materials’.Juniper, R., Read, P.London: Elsevier, Novermber 1994,2
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9.Holden, B., Mertz, G. McNally, J., Invest. Ophthalmol. Vis. Sci., 1983, 24, 218-22
10. Holden, B., Mertz, G., ibid, 1984, 25, 1161-7
11.Schoessler, J., International Contact Lens Clinic, 1983, 10, 148-51
12. Sarver, M., Baggett, D., harris, M. Louie, K., Am. J. Optom. & Physiol. Optics, 1981, 58, 386-
92
13.White, P., Contact Lens Spectrum, February 1990, 46-63
14.Rao, J.B., Saini, J.S. “Complications of Contant Lenses.” Contact Lenses.
Aquavella, J. V., Rao, G. N.Lippincott Company. Philidelphia, 1987.pg. 48, 49, 71, 76-
77,195-225.
15. Singh, J. J., et. Al. “An Investigation of Microstructural Characteristics of Contact-Lens
Polymers” NASA Technical Paper, 3034. December 1990.
16. Paul, D. R. “Gas Sorption and Transport in Glassy Polymers.” Ber. Bunsenges.Phys. Chem.,
vol. 83, no. 4, 1979, Pages 294-302.
17. Petropoulos, J. H. “Qualitative Analysis of Gaseous Diffusion in Glassy Polymers.”J.
Polymer Sci.: Pt A-2, vol. 8, no. 10. October, 1970. Pages 1797-1801.
18. Lai, Y., Wilson, A., Zantos, S., ‘Contact lenses’ in ‘Kirk-Othmer encylopedia of chemical
technology’, Volume 7, John Wiley, 1993, 191-213.
19. Ammon, D. M., Castner, D. G., Ratner, B.D.“In-Situ Surface Modifications ofContact
LensPolymers.”Surface modifications of Polymeric Biomaterials.
Grobe, G. L., McGee, J. A., Valint, P. L.Plenum Press. New York, 1997.pg. 21-26.
20. Mueller, K.F., Kleiner, E.K., US Patent No. 4740553, 1998
21. Holly, F. J.,Refojo, M. F. “Water Wetability of Hydrogels” Hydrogels for
Medical and Related Applications.Andrade, J. D.American Chemical
Society.1976pg 252-256.
22. Slatt B. J., Stein, H.A., Stein, R.M. Fitting Guide For Rigid and Soft Contact
Lenses.A Pratical Approach (3rd edition).C. V. Mosby Company, Toronto1990. pg. xvii-
xxiv, 477-488
23.Bennett E. S.“Material Selection.” Clinical Manual of Contact Lenses.
Bennett, E. S.,Henry V. A.J. B. Lippincott Company Philidelphia,1994. pg.
27-40, 143-170, 197-217.
24. Friends. G. D., Lai, Y.C. “Surface Wettability Enhancement of Silicone Hydrogel Lenses by
Processing with Polar Plastic Molds.”J. Biomed. Mater. Res., 35, 349-356, 1997.
25. Kunzler, J., Ozark, R. “Methacrylate-Capped Fluoro Side Chain Siloxanes:Synthesis,
Characterization, and Their Use in the Design of Oxygen-Permeable Hydrogels.”J Appl
Polym Sci. 65: 1081-1089, 1997.