Abstract

A new method is presented to generate and to fixate compositional gradients in blends of two miscible and amorphous polymers. A compositional gradient is introduced into a solution of a polymer in a monomer by use of a centrifugal field, and this gradient is subsequently fixated by polymerization of the solvent–monomer. It is shown that substantial compositional and refractive-index gradients can be generated in miscible, highly transparent, amorphous polymer blends by a proper selection of materials and processing conditions. Moreover, it is shown that these materials and processes are potentially useful for producing optical components such as self-focusing lenses.

© 1999 Optical Society of America

Full Article  |  PDF Article

References

  • View by:
  • |
  • |
  • |

  1. R. W. Wood, Physical Optics (Macmillan, New York, 1905).
  2. A. I. Mahan, “Astronomical refraction—some history and theories,” Appl. Opt. 1, 497–511 (1962).
    [CrossRef]
  3. D. S. Falk, D. R. Brill, D. G. Stork, Seeing the Light: Optics in Nature, Photography, Color, Vision, and Holography (Harper & Row, London, 1986).
  4. A. Fletcher, T. Murphy, A. Young, “Solutions of two optical problems,” Proc. R. Soc. London Ser. A 223, 216–225 (1954).
    [CrossRef]
  5. D. T. Moore, “Design of singlets with continuously varying indices of refraction,” J. Opt. Soc. Am. 61, 886–894 (1971).
    [CrossRef]
  6. D. T. Moore, P. J. Sands, “Third-order aberrations of inhomogeneous lenses with cylindrical index distributions,” J. Opt. Soc. Am. 61, 1195–1201 (1971).
    [CrossRef]
  7. P. J. Sands, “Inhomogeneous lenses. V. Chromatic paraxial aberrations of lenses with axial or cylindrical index distributions,” J. Opt. Soc. Am. 61, 1495–1500 (1971).
    [CrossRef]
  8. E. W. Marchand, “Third-order aberrations of the photographic Wood lens,” J. Opt. Soc. Am. 66, 1326–1330 (1976).
    [CrossRef]
  9. D. Gloge, “Dispersion in weakly guiding fibers,” Appl. Opt. 10, 2442–2445 (1971).
    [CrossRef] [PubMed]
  10. A. D. Pearson, W. G. French, E. G. Rawson, “Preparation of a light focusing glass rod by ion-exchange techniques,” Appl. Phys. Lett. 15, 76–77 (1969).
    [CrossRef]
  11. E. W. Marchand, Gradient Index Optics (Academic, London, 1978).
  12. Y. Ohtsuka, T. Sugano, Y. Terao, “Studies on the light-focusing plastic rod. 8. Copolymer rod of diethyl glycol bis(allyl carbonate) with methacrylic ester of fluorine containing alcohol,” Appl. Opt. 20, 2319–2323 (1981).
    [CrossRef] [PubMed]
  13. Y. Ohtsuka, Y. Koike, H. Yamazaki, “Studies on the light-focusing plastic rod. 6. The photocopolymer rod of methyl methacrylate with vinyl benzoate,” Appl. Opt. 20, 280–285 (1981).
    [CrossRef] [PubMed]
  14. Y. Koike, Y. Kimoto, Y. Ohtsuka, “Studies on the light-focusing plastic rod. 12. The GRIN fiber lens of methyl methacrylate–vinyl phenylacetate copolymer,” Appl. Opt. 21, 1057–1062 (1982).
    [CrossRef] [PubMed]
  15. Y. Koike, “High-bandwidth, low-loss polymer fibres,” in Proceedings of the 18th European Conference on Optical Communication (Institute of Electrical and Electronic Engineers, Berlin, 1992), Vol. 2, pp. 679–686.
  16. Y. Koike, T. Ishigure, E. Nihei, “High-bandwidth graded-index optical fiber,” J. Lightwave Technol. 13, 1475–1489 (1995).
    [CrossRef]
  17. L. L. Blyler, C. S. Koeppen, H. E. Bair, “GI-POF in telecommunications: opportunity and reliability,” in Proceedings of the 1996 Plastic Optical Fibres Asia-Pacific Forum (Plastic Optical Fibres Consortium Japan, Tokyo, 1996), pp. 58–61.
  18. L. L. Blyler, C. A. Ronaghan, C. S. Koeppen, T. Salamon, “Dopant diffusion and long term reliability characteristics of graded-index polymer optical fibers,” in Proceedings of the Plastic Optical Fibres Conference ’97 (Plastic Optical Fibres Consortium Japan, Kauaii, Japan, 1997), pp. 42–43.
  19. F. G. H. van Duijnhoven, C. W. M. Bastiaansen, “Polymeric graded-index preforms,” in Proceedings of the 5th International Conference on Plastic Optical Fibres & Applications (Institute of Communications Geneva, Paris, 1996), pp. 46–49.
  20. F. G. H. van Duijnhoven, C. W. M. Bastiaansen, “Method for producing an optical rod-shaped graded-index polymer preform, preform obtained in accordance with this method and optical lens and optical fibre obtained by using same,” The Netherlands patentPCT/NL97/00055 (12February1997).
  21. C. H. Emes, “Introduction to the theory and practices of centrifugation,” in Centrifugation: A Practical Approach, D. Rickwood, ed. (Information Retrieval, London, 1978), pp. 1–14.
  22. O. Olabisi, L. M. Robeson, M. T. Shaw, Polymer–Polymer Miscibility (Academic, New York, 1969), pp. 4–15.
  23. D. R. Paul, S. Newman, eds., Polymer Blends (Academic, New York, 1978).
  24. T. G. Fox, “Influence of diluent and of copolymer composition on the glass temperature of a polymer system,” Bull. Am. Phys. Soc. 1, 123–125 (1956).
  25. J. R. Partington, ed., Physicochemical Optics, Vol. 4 of An Advanced Treatise on Physical Chemistry (Longmans, Green, London, 1960), p. 8.
  26. F. P. Kapron, “Geometrical optics of parabolic index-gradient cylindrical lenses,” J. Opt. Soc. Am. 60, 1433–1436 (1970).
    [CrossRef]
  27. An ultracentrifuge with a maximum rotational speed of 60,000 rpm and a diameter of 5 cm was recently constructed. Hence the centrifugal field varies from 0 at the center of the tube to approximately 100,000 g at its inner wall.
  28. C. Tanford, Physical Chemistry of Macromolecules (Wiley, London, 1961), pp. 364–390.

1995 (1)

Y. Koike, T. Ishigure, E. Nihei, “High-bandwidth graded-index optical fiber,” J. Lightwave Technol. 13, 1475–1489 (1995).
[CrossRef]

1982 (1)

1981 (2)

1976 (1)

1971 (4)

1970 (1)

1969 (1)

A. D. Pearson, W. G. French, E. G. Rawson, “Preparation of a light focusing glass rod by ion-exchange techniques,” Appl. Phys. Lett. 15, 76–77 (1969).
[CrossRef]

1962 (1)

1956 (1)

T. G. Fox, “Influence of diluent and of copolymer composition on the glass temperature of a polymer system,” Bull. Am. Phys. Soc. 1, 123–125 (1956).

1954 (1)

A. Fletcher, T. Murphy, A. Young, “Solutions of two optical problems,” Proc. R. Soc. London Ser. A 223, 216–225 (1954).
[CrossRef]

Bair, H. E.

L. L. Blyler, C. S. Koeppen, H. E. Bair, “GI-POF in telecommunications: opportunity and reliability,” in Proceedings of the 1996 Plastic Optical Fibres Asia-Pacific Forum (Plastic Optical Fibres Consortium Japan, Tokyo, 1996), pp. 58–61.

Bastiaansen, C. W. M.

F. G. H. van Duijnhoven, C. W. M. Bastiaansen, “Method for producing an optical rod-shaped graded-index polymer preform, preform obtained in accordance with this method and optical lens and optical fibre obtained by using same,” The Netherlands patentPCT/NL97/00055 (12February1997).

F. G. H. van Duijnhoven, C. W. M. Bastiaansen, “Polymeric graded-index preforms,” in Proceedings of the 5th International Conference on Plastic Optical Fibres & Applications (Institute of Communications Geneva, Paris, 1996), pp. 46–49.

Blyler, L. L.

L. L. Blyler, C. S. Koeppen, H. E. Bair, “GI-POF in telecommunications: opportunity and reliability,” in Proceedings of the 1996 Plastic Optical Fibres Asia-Pacific Forum (Plastic Optical Fibres Consortium Japan, Tokyo, 1996), pp. 58–61.

L. L. Blyler, C. A. Ronaghan, C. S. Koeppen, T. Salamon, “Dopant diffusion and long term reliability characteristics of graded-index polymer optical fibers,” in Proceedings of the Plastic Optical Fibres Conference ’97 (Plastic Optical Fibres Consortium Japan, Kauaii, Japan, 1997), pp. 42–43.

Brill, D. R.

D. S. Falk, D. R. Brill, D. G. Stork, Seeing the Light: Optics in Nature, Photography, Color, Vision, and Holography (Harper & Row, London, 1986).

Emes, C. H.

C. H. Emes, “Introduction to the theory and practices of centrifugation,” in Centrifugation: A Practical Approach, D. Rickwood, ed. (Information Retrieval, London, 1978), pp. 1–14.

Falk, D. S.

D. S. Falk, D. R. Brill, D. G. Stork, Seeing the Light: Optics in Nature, Photography, Color, Vision, and Holography (Harper & Row, London, 1986).

Fletcher, A.

A. Fletcher, T. Murphy, A. Young, “Solutions of two optical problems,” Proc. R. Soc. London Ser. A 223, 216–225 (1954).
[CrossRef]

Fox, T. G.

T. G. Fox, “Influence of diluent and of copolymer composition on the glass temperature of a polymer system,” Bull. Am. Phys. Soc. 1, 123–125 (1956).

French, W. G.

A. D. Pearson, W. G. French, E. G. Rawson, “Preparation of a light focusing glass rod by ion-exchange techniques,” Appl. Phys. Lett. 15, 76–77 (1969).
[CrossRef]

Gloge, D.

Ishigure, T.

Y. Koike, T. Ishigure, E. Nihei, “High-bandwidth graded-index optical fiber,” J. Lightwave Technol. 13, 1475–1489 (1995).
[CrossRef]

Kapron, F. P.

Kimoto, Y.

Koeppen, C. S.

L. L. Blyler, C. S. Koeppen, H. E. Bair, “GI-POF in telecommunications: opportunity and reliability,” in Proceedings of the 1996 Plastic Optical Fibres Asia-Pacific Forum (Plastic Optical Fibres Consortium Japan, Tokyo, 1996), pp. 58–61.

L. L. Blyler, C. A. Ronaghan, C. S. Koeppen, T. Salamon, “Dopant diffusion and long term reliability characteristics of graded-index polymer optical fibers,” in Proceedings of the Plastic Optical Fibres Conference ’97 (Plastic Optical Fibres Consortium Japan, Kauaii, Japan, 1997), pp. 42–43.

Koike, Y.

Y. Koike, T. Ishigure, E. Nihei, “High-bandwidth graded-index optical fiber,” J. Lightwave Technol. 13, 1475–1489 (1995).
[CrossRef]

Y. Koike, Y. Kimoto, Y. Ohtsuka, “Studies on the light-focusing plastic rod. 12. The GRIN fiber lens of methyl methacrylate–vinyl phenylacetate copolymer,” Appl. Opt. 21, 1057–1062 (1982).
[CrossRef] [PubMed]

Y. Ohtsuka, Y. Koike, H. Yamazaki, “Studies on the light-focusing plastic rod. 6. The photocopolymer rod of methyl methacrylate with vinyl benzoate,” Appl. Opt. 20, 280–285 (1981).
[CrossRef] [PubMed]

Y. Koike, “High-bandwidth, low-loss polymer fibres,” in Proceedings of the 18th European Conference on Optical Communication (Institute of Electrical and Electronic Engineers, Berlin, 1992), Vol. 2, pp. 679–686.

Mahan, A. I.

Marchand, E. W.

Moore, D. T.

Murphy, T.

A. Fletcher, T. Murphy, A. Young, “Solutions of two optical problems,” Proc. R. Soc. London Ser. A 223, 216–225 (1954).
[CrossRef]

Nihei, E.

Y. Koike, T. Ishigure, E. Nihei, “High-bandwidth graded-index optical fiber,” J. Lightwave Technol. 13, 1475–1489 (1995).
[CrossRef]

Ohtsuka, Y.

Olabisi, O.

O. Olabisi, L. M. Robeson, M. T. Shaw, Polymer–Polymer Miscibility (Academic, New York, 1969), pp. 4–15.

Pearson, A. D.

A. D. Pearson, W. G. French, E. G. Rawson, “Preparation of a light focusing glass rod by ion-exchange techniques,” Appl. Phys. Lett. 15, 76–77 (1969).
[CrossRef]

Rawson, E. G.

A. D. Pearson, W. G. French, E. G. Rawson, “Preparation of a light focusing glass rod by ion-exchange techniques,” Appl. Phys. Lett. 15, 76–77 (1969).
[CrossRef]

Robeson, L. M.

O. Olabisi, L. M. Robeson, M. T. Shaw, Polymer–Polymer Miscibility (Academic, New York, 1969), pp. 4–15.

Ronaghan, C. A.

L. L. Blyler, C. A. Ronaghan, C. S. Koeppen, T. Salamon, “Dopant diffusion and long term reliability characteristics of graded-index polymer optical fibers,” in Proceedings of the Plastic Optical Fibres Conference ’97 (Plastic Optical Fibres Consortium Japan, Kauaii, Japan, 1997), pp. 42–43.

Salamon, T.

L. L. Blyler, C. A. Ronaghan, C. S. Koeppen, T. Salamon, “Dopant diffusion and long term reliability characteristics of graded-index polymer optical fibers,” in Proceedings of the Plastic Optical Fibres Conference ’97 (Plastic Optical Fibres Consortium Japan, Kauaii, Japan, 1997), pp. 42–43.

Sands, P. J.

Shaw, M. T.

O. Olabisi, L. M. Robeson, M. T. Shaw, Polymer–Polymer Miscibility (Academic, New York, 1969), pp. 4–15.

Stork, D. G.

D. S. Falk, D. R. Brill, D. G. Stork, Seeing the Light: Optics in Nature, Photography, Color, Vision, and Holography (Harper & Row, London, 1986).

Sugano, T.

Tanford, C.

C. Tanford, Physical Chemistry of Macromolecules (Wiley, London, 1961), pp. 364–390.

Terao, Y.

van Duijnhoven, F. G. H.

F. G. H. van Duijnhoven, C. W. M. Bastiaansen, “Method for producing an optical rod-shaped graded-index polymer preform, preform obtained in accordance with this method and optical lens and optical fibre obtained by using same,” The Netherlands patentPCT/NL97/00055 (12February1997).

F. G. H. van Duijnhoven, C. W. M. Bastiaansen, “Polymeric graded-index preforms,” in Proceedings of the 5th International Conference on Plastic Optical Fibres & Applications (Institute of Communications Geneva, Paris, 1996), pp. 46–49.

Wood, R. W.

R. W. Wood, Physical Optics (Macmillan, New York, 1905).

Yamazaki, H.

Young, A.

A. Fletcher, T. Murphy, A. Young, “Solutions of two optical problems,” Proc. R. Soc. London Ser. A 223, 216–225 (1954).
[CrossRef]

Appl. Opt. (5)

Appl. Phys. Lett. (1)

A. D. Pearson, W. G. French, E. G. Rawson, “Preparation of a light focusing glass rod by ion-exchange techniques,” Appl. Phys. Lett. 15, 76–77 (1969).
[CrossRef]

Bull. Am. Phys. Soc. (1)

T. G. Fox, “Influence of diluent and of copolymer composition on the glass temperature of a polymer system,” Bull. Am. Phys. Soc. 1, 123–125 (1956).

J. Lightwave Technol. (1)

Y. Koike, T. Ishigure, E. Nihei, “High-bandwidth graded-index optical fiber,” J. Lightwave Technol. 13, 1475–1489 (1995).
[CrossRef]

J. Opt. Soc. Am. (5)

Proc. R. Soc. London Ser. A (1)

A. Fletcher, T. Murphy, A. Young, “Solutions of two optical problems,” Proc. R. Soc. London Ser. A 223, 216–225 (1954).
[CrossRef]

Other (14)

R. W. Wood, Physical Optics (Macmillan, New York, 1905).

E. W. Marchand, Gradient Index Optics (Academic, London, 1978).

Y. Koike, “High-bandwidth, low-loss polymer fibres,” in Proceedings of the 18th European Conference on Optical Communication (Institute of Electrical and Electronic Engineers, Berlin, 1992), Vol. 2, pp. 679–686.

J. R. Partington, ed., Physicochemical Optics, Vol. 4 of An Advanced Treatise on Physical Chemistry (Longmans, Green, London, 1960), p. 8.

An ultracentrifuge with a maximum rotational speed of 60,000 rpm and a diameter of 5 cm was recently constructed. Hence the centrifugal field varies from 0 at the center of the tube to approximately 100,000 g at its inner wall.

C. Tanford, Physical Chemistry of Macromolecules (Wiley, London, 1961), pp. 364–390.

L. L. Blyler, C. S. Koeppen, H. E. Bair, “GI-POF in telecommunications: opportunity and reliability,” in Proceedings of the 1996 Plastic Optical Fibres Asia-Pacific Forum (Plastic Optical Fibres Consortium Japan, Tokyo, 1996), pp. 58–61.

L. L. Blyler, C. A. Ronaghan, C. S. Koeppen, T. Salamon, “Dopant diffusion and long term reliability characteristics of graded-index polymer optical fibers,” in Proceedings of the Plastic Optical Fibres Conference ’97 (Plastic Optical Fibres Consortium Japan, Kauaii, Japan, 1997), pp. 42–43.

F. G. H. van Duijnhoven, C. W. M. Bastiaansen, “Polymeric graded-index preforms,” in Proceedings of the 5th International Conference on Plastic Optical Fibres & Applications (Institute of Communications Geneva, Paris, 1996), pp. 46–49.

F. G. H. van Duijnhoven, C. W. M. Bastiaansen, “Method for producing an optical rod-shaped graded-index polymer preform, preform obtained in accordance with this method and optical lens and optical fibre obtained by using same,” The Netherlands patentPCT/NL97/00055 (12February1997).

C. H. Emes, “Introduction to the theory and practices of centrifugation,” in Centrifugation: A Practical Approach, D. Rickwood, ed. (Information Retrieval, London, 1978), pp. 1–14.

O. Olabisi, L. M. Robeson, M. T. Shaw, Polymer–Polymer Miscibility (Academic, New York, 1969), pp. 4–15.

D. R. Paul, S. Newman, eds., Polymer Blends (Academic, New York, 1978).

D. S. Falk, D. R. Brill, D. G. Stork, Seeing the Light: Optics in Nature, Photography, Color, Vision, and Holography (Harper & Row, London, 1986).

Cited By

OSA participates in CrossRef's Cited-By Linking service. Citing articles from OSA journals and other participating publishers are listed here.

Alert me when this article is cited.


Figures (8)

Fig. 1
Fig. 1

Schematic representation of the experimental setup.

Fig. 2
Fig. 2

Composition of preforms versus the normalized radius produced from TFPMA–MMA copolymers (×) and a homogeneous blend of PTFPMA and PMMA (□) at 20,000 rpm.

Fig. 3
Fig. 3

Phase diagrams of PMMA–PTFPMA blends; temperature versus volume percentage PTFPMA [% v/v]: (■) Glass-transition temperature of the blends, (▲) cloud points (1 °C/min) of blends of PMMA with molar mass (M w ) 100 kg/mol and PTFPMA (M w = 217 kg/mol), (●) cloud points (1 °C/min) of blends of PMMA (M w = 100 kg/mol) and PTFPMA (M w = 100 kg/mol).

Fig. 4
Fig. 4

Compositional gradients in preforms: volume percentage PTFPMA in preforms (% v/v) versus the normalized radius (r/ R p , where r is the position in the radial direction and R p is the total radius of the preform) synthesized at 0 rpm (×, +), 15,000 rpm (□, ■), and 20,000 rpm (△, ▲).

Fig. 5
Fig. 5

Refractive-index distributions in preforms. Refractive-index gradient (n - n 0, where n is the refractive index in the radial direction and n 0 is the refractive index at r = 0) in preforms produced at 0 rpm (×), 15,000 rpm (□), and 20,000 rpm (△). Solid curve, the refractive-index profile as derived from interference microscopy data.

Fig. 6
Fig. 6

Refractive-index profiles of a preform produced at 20,000 rpm after annealing at 120 °C for 2 h (×), 12 h (□), and 24 h (△).

Fig. 7
Fig. 7

Light trajectory of a laser beam injected into a (dust-polluted) gradient-index preform.

Fig. 8
Fig. 8

Image formation of a gradient-index preform cut at a 1/4 pitch.

Tables (1)

Tables Icon

Table 1 Densities (ρ) and Refractive Indices (n) of the Monomers and Polymers

Metrics