Abstract

The optical properties of polymer liquid crystal cell exhibiting polymer blue phases (PBPs) have been determined using ultraviolet-visible spectrophotometry, polarizing optical microscopy (POM), differential scanning calorimetry (DSC), X-ray measurements, FTIR imaging and optical rotation technique. PBPs are thermodynamically stabile mesophases, which appear in chiral systems between isotropic and liquid crystal phases. A series of cyclosiloxane-based blue phase polymers were synthesized using a cholesteric LC monomer and a nematic LC monomer, and some of the polymers exhibit PBPs in temperature range over 300 degrees in cooling cycles. The unique property based on their structure and different twists formed and expect to open up new photonic application and enrich polymer blue phase contents and theory.

© 2007 Optical Society of America

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References

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    [CrossRef]
  2. G. H. Hsiue and J. H. Chen, "Synthesis and thermal properties of ferroelectric side chain liquid crystalline polysiloxanes based on the phenyl ester mesogen and oligo(oxyethylene)spacers. 1.Phenyl benzoate and biphenyl benzoate mesogenic groups," Macromolecules 28, 4366 (1995).
    [CrossRef]
  3. P. R. Gerber, "Electro-optical effects of a small-pitch blue -phase system," Mol. Cryst. Liq. Cryst. 116, 197 (1985).
    [CrossRef]
  4. P. Etchegoin, "Blue phases of cholesteric liquid crystals as thermotropic photonic crystals," Phys. Rev. E62, 1435 (2000).
  5. U. Lhitaro, "Optical properties of lyotropic poly(-benzyl L-glutamate) liquid crystals," Mol. Cryst. Liq. Cryst. 116, 21 (1984).
    [CrossRef]
  6. F. Lcivvoland, "Precholesteric liquid crystalline states of DNA," Journal de physique(pairs) 48, 1051 (1987).
  7. H. Grebl, "Landau theory of helical liquid-crystalline phases," Phys. Rev. A28, 1114 (1983).
  8. H. Kikuchi, M. Yokota, Y. Hisakado, H. Yang and T. Kajiyama, "Polymer-stabilized liquid crystal blue phases," Nature Mater. 1, 64 (2002).
    [CrossRef]
  9. H. J. Coles and M. N. Pivnenko, "Liquid crystal "blue phases’ with a wide temperature range,"Nature 436, 997 (2005).
    [CrossRef] [PubMed]
  10. J. M. Gilli, "Phases bleues "figees" dans un polysiloxane mesomorph" J. de Phys. France  50, 2911 (1989).
    [CrossRef]
  11. B. Y. Zhang, F. B. Meng, X. Z. He and D. Lin, "Synthesis and characterization of side chain liquid crystalline polymers exhibiting Cholesteric and bule phases," Liq. Cryst. 32, 1161 (2005).
    [CrossRef]
  12. D. Seyferth, C. PrudHomme and G. H.Wiseman, "Cyclic Polysiloxanes from the Hydrolysis of Dichlorosilane," Inorg. Chem. 22, 2163 (1983).
    [CrossRef]
  13. F. B. Meng, B. Y. Zhang, L. M. Liu and B. L. Zang, "Liquid-crystalline elastomers produced by chemical crosslinking agents containing sulfonic acid groups," Polymer 44, 3935 (2003).
    [CrossRef]
  14. W.Y. Cao, A. Munoz, P. Palffy-Muhoray and B. Taheri, "Lasing in a three-dimensional photonic crystal of the liquid crystal blue phase II," Nature Mater. 1, 111 (2002).
    [CrossRef]

2005

H. J. Coles and M. N. Pivnenko, "Liquid crystal "blue phases’ with a wide temperature range,"Nature 436, 997 (2005).
[CrossRef] [PubMed]

B. Y. Zhang, F. B. Meng, X. Z. He and D. Lin, "Synthesis and characterization of side chain liquid crystalline polymers exhibiting Cholesteric and bule phases," Liq. Cryst. 32, 1161 (2005).
[CrossRef]

2003

F. B. Meng, B. Y. Zhang, L. M. Liu and B. L. Zang, "Liquid-crystalline elastomers produced by chemical crosslinking agents containing sulfonic acid groups," Polymer 44, 3935 (2003).
[CrossRef]

2002

W.Y. Cao, A. Munoz, P. Palffy-Muhoray and B. Taheri, "Lasing in a three-dimensional photonic crystal of the liquid crystal blue phase II," Nature Mater. 1, 111 (2002).
[CrossRef]

H. Kikuchi, M. Yokota, Y. Hisakado, H. Yang and T. Kajiyama, "Polymer-stabilized liquid crystal blue phases," Nature Mater. 1, 64 (2002).
[CrossRef]

J. W. Goodby, "Twist grain boundary and frustrated liquid crystal phases," Current opinion in colloid and interface science 7, 326 (2002).
[CrossRef]

2000

P. Etchegoin, "Blue phases of cholesteric liquid crystals as thermotropic photonic crystals," Phys. Rev. E62, 1435 (2000).

1995

G. H. Hsiue and J. H. Chen, "Synthesis and thermal properties of ferroelectric side chain liquid crystalline polysiloxanes based on the phenyl ester mesogen and oligo(oxyethylene)spacers. 1.Phenyl benzoate and biphenyl benzoate mesogenic groups," Macromolecules 28, 4366 (1995).
[CrossRef]

1987

F. Lcivvoland, "Precholesteric liquid crystalline states of DNA," Journal de physique(pairs) 48, 1051 (1987).

1985

P. R. Gerber, "Electro-optical effects of a small-pitch blue -phase system," Mol. Cryst. Liq. Cryst. 116, 197 (1985).
[CrossRef]

1984

U. Lhitaro, "Optical properties of lyotropic poly(-benzyl L-glutamate) liquid crystals," Mol. Cryst. Liq. Cryst. 116, 21 (1984).
[CrossRef]

1983

H. Grebl, "Landau theory of helical liquid-crystalline phases," Phys. Rev. A28, 1114 (1983).

D. Seyferth, C. PrudHomme and G. H.Wiseman, "Cyclic Polysiloxanes from the Hydrolysis of Dichlorosilane," Inorg. Chem. 22, 2163 (1983).
[CrossRef]

Current opinion in colloid and interface science

J. W. Goodby, "Twist grain boundary and frustrated liquid crystal phases," Current opinion in colloid and interface science 7, 326 (2002).
[CrossRef]

Inorg. Chem.

D. Seyferth, C. PrudHomme and G. H.Wiseman, "Cyclic Polysiloxanes from the Hydrolysis of Dichlorosilane," Inorg. Chem. 22, 2163 (1983).
[CrossRef]

Journal de physique

F. Lcivvoland, "Precholesteric liquid crystalline states of DNA," Journal de physique(pairs) 48, 1051 (1987).

Liq. Cryst.

B. Y. Zhang, F. B. Meng, X. Z. He and D. Lin, "Synthesis and characterization of side chain liquid crystalline polymers exhibiting Cholesteric and bule phases," Liq. Cryst. 32, 1161 (2005).
[CrossRef]

Macromolecules

G. H. Hsiue and J. H. Chen, "Synthesis and thermal properties of ferroelectric side chain liquid crystalline polysiloxanes based on the phenyl ester mesogen and oligo(oxyethylene)spacers. 1.Phenyl benzoate and biphenyl benzoate mesogenic groups," Macromolecules 28, 4366 (1995).
[CrossRef]

Mol. Cryst. Liq. Cryst.

P. R. Gerber, "Electro-optical effects of a small-pitch blue -phase system," Mol. Cryst. Liq. Cryst. 116, 197 (1985).
[CrossRef]

U. Lhitaro, "Optical properties of lyotropic poly(-benzyl L-glutamate) liquid crystals," Mol. Cryst. Liq. Cryst. 116, 21 (1984).
[CrossRef]

Nature

H. J. Coles and M. N. Pivnenko, "Liquid crystal "blue phases’ with a wide temperature range,"Nature 436, 997 (2005).
[CrossRef] [PubMed]

Nature Mater.

W.Y. Cao, A. Munoz, P. Palffy-Muhoray and B. Taheri, "Lasing in a three-dimensional photonic crystal of the liquid crystal blue phase II," Nature Mater. 1, 111 (2002).
[CrossRef]

H. Kikuchi, M. Yokota, Y. Hisakado, H. Yang and T. Kajiyama, "Polymer-stabilized liquid crystal blue phases," Nature Mater. 1, 64 (2002).
[CrossRef]

Phys. Rev.

H. Grebl, "Landau theory of helical liquid-crystalline phases," Phys. Rev. A28, 1114 (1983).

P. Etchegoin, "Blue phases of cholesteric liquid crystals as thermotropic photonic crystals," Phys. Rev. E62, 1435 (2000).

Polymer

F. B. Meng, B. Y. Zhang, L. M. Liu and B. L. Zang, "Liquid-crystalline elastomers produced by chemical crosslinking agents containing sulfonic acid groups," Polymer 44, 3935 (2003).
[CrossRef]

Other

J. M. Gilli, "Phases bleues "figees" dans un polysiloxane mesomorph" J. de Phys. France  50, 2911 (1989).
[CrossRef]

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Figures (4)

Scheme 1.
Scheme 1.

General structure of the polymers.

Fig. 1.
Fig. 1.

The probable blue phase textures of the polymer P4 (200×). Pictures (a), (b) and (c) were on the first cooling taken by LEICA DMLP Polarizing Optical Microscope in Nov. 1st, 2002: (a), 150 °C; (b), -174.5 °C; (c), the sample of (b) covered with λ/4 plate; (d), the same sample of November 2002 after 2 times heating to more than 180 °C and cooling to -180 °C, then has been setting in room temperature more than 3 years taken by LEICA, DMRX Polarizing Optical Microscope, with heating platform-THMSE 600 in Nov. 25, 2005.

Fig. 2.
Fig. 2.

Optical properties of polymer P4. (a) On heating cycles, the λmax increased from 25 °C to 96 °C; but the λmax decreased when the temperature continually rised from 96 °C to 181 °C. On the cooling, the λmax changed slightly, stabled around 500 nm as the temperature decreased from 181 °C down to the room temperature. (b) The biggest selective reflective wavelength (λmax) of P4 at different reflective angle at room temperature. The data of a and b were got by PE, Lambda 950 UV/VIS spectrophotometer. (c) On the heating cycle, α is negative below 80 °C, decreasing with increase of temperature, but it gets a maximum at 98 °C. On the cooling cycle, α remained almost the same, suggesting stable optical activity of the PBPs. This test was finished using PE, Model 341 Polarimeter. (d) WAXD of polymer P4 cooled from 230 °C (15.16°) to 10 °C (16.48°) then heating from 10 °C to 210 °C (15.58°). The intensity and the location of peaks changed little. The data were measured with a Rigaku DMAX-3A X-ray diffractometer (Rigaku, Japan) using Cu Kα (λ=1.542 Å).

Fig. 3.
Fig. 3.

Infrared images and spectra of polymer P4. (a) Spectra of P4 at at different temperature on the first cooling rate 1 °C/min. The C=O stretching absorbance intensity of sample changed slightly on first cooling from isotropic state to RT and all the morphologies showed similar shape on cooling cycle. The intensities of peaks in the 170 °C, 110 °C and 30 °C were same, meanwhile the locations of the peaks were 1712.5 cm-1, 1711.9 cm-1 and 1710.9 cm-1 corresponding the above temperatures. (b) Infrared images (3D Surface Projection) of P4 at different temperature on the first cooling rate 1 °C/min. From the comparison of spectra at different temperature, the differences in absorbance intensities in the C=O stretching modes were used as probes for FT-IR imaging contrasts. This experiment was carried out using PE, Spectrum spotlight 300 FT-IR imaging system

Tables (1)

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Table 1. Polymerization some properties of the series of polymers

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