Optical Properties of 4-nitro-phenyl 4-alkoxybenzoates Liquid Crystal Mixtures using Speckle Interferometry

Abstract: In this work, an experimental approach of speckle photography was used to measure the refractive indices of individual components as well as their binary and ternary mixtures of 4-nitro-phenyl 4-alkoxy

benzoates thermotropic liquid crystals at different wavelengths in the

visible light region. The measurements extend from isotropic phase to the liquid crystalline one. The dispersion relations were also investigated. The effect of the end group of the tested LCs on the birefringent values .was investigated and discussed Keywords: Speckle Interferometry, Birefringence, Interference, Mixtures .of thermotropic liquid crystals

Introduction .1 Liquid crystal technology has had a major effect in many fields of science and engineering, as well as device technology. Applications for this special kind of material are still being discovered and continue to provide effective solutions to many different problems. Thermotropic transactions occur in most liquid crystals, and they are defined by the fact .that the transitions to the liquid crystalline state are induced thermally The ability of thin films of polymer dispersed liquid crystals to operate as electro-optic devices has been investigated. The complex optical properties of the polymer component of the films, and the real component of the refractive indices of the liquid crystals, have been determined [1]. Another work describing a convenient and accurate technique for measuring the optical path difference induced by a
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birefringent crystal was given. Birefringence measurements at the wavelength 0.6328 m for some common nematic liquid crystal cells were presented [2]. Refractive indices (ne, no( and birefringence ( n) for cholesteric and isotropic phases of cholesteryl carbonate, cholesteryl .[stearate at varying temperature was measured [3 Transmittance spectra of a mica film and 4-cyano 49-pentyl biphenyl liquid crystal were acquired in the visible spectral region by using a monochromator, and the dispersion curves of the refractive index and the birefringence were deduced [4]. New guidelines for selecting or synthesizing the liquid crystals with the desired birefringence were established. Novel applications of liquid crystals in the infrared region were obtained [5]. The thermotropic liquid crystal (N-4methoxybenzilidene-4-butylaniline), entrapped on hydrogels, based on cross-linked polyacrylamide was studied by polarized optical microscopy, refractive index, optical transmittance, scanning electron microscopy and water loss. It was verified the presence of birefringence .[on hydrogel + liquid crystal [6 The birefringence of the liquid crystal as functions of the temperature was measured with and without the power supply. It was shown that the birefringence reduces while the temperature increases and the change magnitude of the birefringence have an exponential decay .[relation with the applied voltage for different temperature intervals [7 The tilt angle distribution of a nematic liquid crystal mixture doped with two anthraquinone derivatives having different molecular shapes was measured as a function of an external ac applied voltage. The voltage dependence of the birefringence, absorbances and linear absorption coefficients of the samples were predicted from the tilt angle distribution .[and were also determined experimentally [8 A new scanning conoscopic method which, by rotating the sample and analyzing the ellipticity of transmitted light provides an accurate tool
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to measure the temperature dependence of the two indices ne, no and of the optical activity for uniaxial liquid crystals was reported [9]. The processes of mesogen ordering in nematic and cholesteric side-chain polymer systems were studied by polarized optical spectroscopy [10]. Properties of anodic aluminum oxide (AAO) film as a liquid crystal (LC) .[alignment material was studied [11 This work deals with the study of the effect of terminal chain length on the optical parameters. For such study, four thermotropic LCs compounds, Ine, were used. The pure components were kindly supplied by M. M. Naoum, Chemistry Department, Faculty of Science, University .of Cairo ClH2l+1O-C6H4-COO-C6H4-NO2 Where, l is an integer number. In this work l took 6, 14, and 16 numbers respectively. After that a mixture of liquid crystal of l equal 6 and 14, and other of l equal 6, 14 and 16 were used, where the composition per percentage mole was as in table (1). Each material used is represented by the value of l with a symbol 'e' after each number .referring to the end group NO2 Table (1) shows transition temperatures in Celsius degree for the compounds used in this work. The symbols C-A, C-N, A-N, A-I, and N-I means the transition from, solid crystal to semictic A, solid crystal to nematic, semictic A to nematic, semictic A to isotropic and nematic to .isotropic respectively

Table (1): Composition and Transition temperatures (C) for compounds ClH2l+1O-C6H4-COO-C6H4-NO2. Values between parentheses are those .determined by the extrapolation method Mixture n= 6 6e 8e 14e 6/14e 6/14/16e 6/8/14/16e
pure -------60.0 47.03

(% Composition (mol n=8

----pure -----------------

(Transition Temp. (oC TC-A

--53.1 74.5 50 45.99

n=14
--------pure 37.5 30.73

n=16
-------------------22.22

TC-N TA-N
55.4 -------------62.6 --68.0 ---

TA-I
----87.9 --72.50

TN-I
68.0 69.2 -----

Refractive Index Measurements .2 Two different methods were used for measuring refractive indices of the materials used; one was Abbe refractometer equipped with hot water bath around the prisms with different wavelengths at different degrees of temperature. The temperature of water was controlled by a thermostat within 0.1C . A white light source was used with interference filters of wavelengths (640 nm, 577nm, 546nm, 435.8nm), and a sodium lamp of wavelength (589.3nm). The dispersion relations between refractive indices and wavelengths at certain temperature in isotropic and liquid crystal phase were shown in figs.(1-4), for (6e), .((14e), (6/14e) and (6/14/16e Another method for measuring the values of refractive indices of the thermotropic LC materials used were by using the spectrophotometer device at different wavelengths of white light source. The value of refractive index was determined by measuring the reflectance values of material . A slight difference in the accuracy of the values of refractive indices was noticed between 0.001 to 0.01 when comparing results between the measurements obtained from Abbe refractometer and the .spectrophotometric technique
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Fig. 1: The relation between refractive index (n) and wavelength ( ) at certain
temperature, T= 65C in isotropic phase, and 55oC in LC phase for .(6e) liquid crystal

Fig. 2: The relation between refractive index (n) and wavelength ( ) at certain
temperature, T= 85C in isotropic phase, and 75C in LC phase for .(14e) liquid crystal

Fig. 3: The relation between refractive index (n) and wavelength ( ) at certain
temperature, T= 78C in isotropic phase, and 70oC in LC phase for .(6/14e) liquid crystal

Fig. 4: The relation between refractive index (n) and wavelength ( ) at certain
temperature, T= 78C in isotropic phase, and 65oC in LC phase for .(6/14/16e) liquid crystal

Birefringence Measurement .3

Birefringence of the liquid crystals was measured by using speckle interferometry technique. The optical setup used is shown in fig.(5). The samples were put into an electric oven for measuring birefringence at a certain degrees of temperature in order to obtain the LC phase as shown in table(1). The interference pattern for both ordinary and extraordinary components were magnified by (q/p), where p was the distance from the lens (L3) to the diffuser (D), and q is the distance from the lens (L3) to the image (H); t was the thickness of the liquid crystal whose refractive index is n. The photographs were taken while the samples temperatures were heated and when they cooled. The setup of the optical arrangement in Fourier plane for observing the Young fringes from the specklegram was used [13]. Plate (1) shows the interference Youngs fringes from the specklegrams of (6e, 14e, 6/14e and 6/14/16e) thermotropic liquid .crystals at wavelength 632.8nm

P L O q

C L

Fig. 5: Optical set-up for measuring the birefringence of an anisotropic optical material.
O: monochromatic source, L1, L2 & L3: converging lenses, C: diaphragm, D: diffuser, .S: Liquid crystal inside the oven and H: holographic plate

14e

6e

6/14/16e

6/14e

Plate 1: The interference Young's fringes from specklegram for 6e, 14e, 6/14e
and 6/14/16e thermotropic liquid crystals with laser source of .wavelength 632.8nm

The relationship of the shift D between ordinary and extraordinary :[images and the spacing of the Youngs fringes is given by [15 (1)

p D = f q
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Where, f is the focal length of the Fourier transform lens and is the wavelength of light used. In order to calculate birefringence n, the :[following equation was used [15 (2)

p n f . n t sin 2q
Where n is the refractive index of the LCs; t is the thickness of the sample and is the angle between the optic axis and the normal to the surface of the sample. The angle was determined by using the .[conoscopic measurement system [17 Table (2) shows the measuring data for LCs used where birefringence was calculated with laser sources of wavelengths, 632.8nm, 543.5nm, 514.5nm, and 488nm, and the thickness of each sample is .((150 m Table(2): The values of birefringence n at different wavelengths for the
.thermotropic liquid crystals used

Sample 6e 8e 14e 6/14e 6/14/16e 6/8/14/16e

)) ((632.8nm 0.01 0.21 0.01 0.23 0.01 0.27 0.01 0.20 0.01 0.16

n )) (543.5nm)
0.01 0.23

)) ((514.5nm
0.01 0.24 0.01 0.29

( ) (488nm)
0.01 0.25

0.01 0.24
0.01 0.28

0.01 0.256 0.01 0.22 0.01 0.19

0.01 0.26
0.01 0.30

0.01 0.21 0.01 0.18

0.01 0.24 0.01 0.21

The dispersion curves for birefringence of four LCs used in the visible region are shown in fig.(6). We noted from this table that the value of birefringence of LC (14e) is greater than that of LC (6e). Also the birefringence of LC mixture (6/14e) was greater than birefringence for (6/14/16e). In addition to that the values of the birefringence of the liquid crystal (6e) and (14e) were greater than the values of birefringence
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for the liquid crystal mixture (6/14e) and (6/14/16e).These results explain that the increasing the number of carbon and hydrogen atoms in the single chemical structure increasing the value of birefringence as in LCs (6e), (8e) and (14e). Besides, the mixture of LCs makes increase in the end group NO2 which decreases the value of birefringence as in LCs (6/14e) and (6/14/16e). This result can be explained as follows; the end of the structure of LCs (NO2) is an electron-withdrawing group called .Enantiotropy These results show that in order to increase birefringence, the number of carbon and hydrogen atoms in the single chemical structure must be increase, which can be used in many applications such as liquid crystal displays. But the mixture of these liquid crystals decreases the .birefringence which isnt preferable

Fig. 6: The dispersion relation between birefringence ( n) and the wavelength at a

certain temperature, in LC phase for 6e, 14e, 6/14e, and 6/14/16e, liquid .crystals

Conclusion .4 The experimental approach of speckle interferometry technique for measuring birefringence of liquid crystals and the dispersion relation was described. Also the values of refractive indices for these thermotropic liquid crystal materials were obtained with a high degree of accuracy. The experimental data shows that the values of birefringence increase by increasing the number of carbon and hydrogen atoms in the chemical structure and decrease by increasing the end group NO2 in the mixture of liquid crystals. The end group NO2 is an electrophile which is a species having electron deficient atom. So that it is a positive charged and accepting or withdrawing electrons, which decrease the stability of the chemical structure compound and then decrease the directionality of the molecules which decrease birefringence. These results become opposite when the end group is donating electrons called monotropic or nucleophiles which is a species having electrons rich atom, such as OCH3 . group The experimental errors in measuring birefringence of the liquid crystal materials used were within 1% to 2%, which are acceptable .[according to others [14, 17

References .5 L. McKenna, L.S. Miller, I.R. Peterson, "Polymer dispersed liquid [1] crystal films for modulating infra-red radiation", Polymer, 45, 6977 .(6984, (2004 Badr-Eddine Benkelfata,, El-Houssine Horachea, Qin Zoua, Bruno [2] Vinouzeb, "An Electro-Optic Modulation Technique For Direct And Accurate Measurement Of Birefringence", Optics .(Communication, 221, 271, (2003

Rajiv Manohar, J.P. Shukla, Refractive Indices, Order Parameter [3] And Principal Polarizability Of Cholesteric Liquid Crystals And Their Homogeneous Mixtures", J. of Physics and Chemistry of .(Solids, 65, 1643, (2004 Brugioni S. and Meucci R., "Mid-Infrared Interferometric [4] Measurement of Liquid Crystal Anisotropy", Optics .(Communication, 230, 19, (2004 Manaia M., Gharbia A., Marceroub J.P., Nguyenb H.T. and [5] Rouillonb J.C., Optic and Electro-Optic Investigations on Smq, Smc_A and L Phases in Highly Chiral Compounds", Physica B, 368, .(168, (2005 Fauze A. Aouada , Marcia R. de Moura, Paulo R.G. Fernandes , [6] Adley F. Rubira and Edvani C. Muniz, "Optical And Morphological Characterization Of Polyacrylamide Hydrogel And Liquid Crystal .(Systems", European Polymer Journal, 41, 2134, (2005 Zhaoliang Cao, Li Xuan, Lifa Hu, Xinghai Lu, Quanquan Mu, " [7] Temperature effect on the diffraction efficiency of the liquid crystal spatial light modulator", Optics Communications 267, 6973, .((2006 A. Jafari, A. Ghanadzadeh, H. Tajalli, M. Yeganeh, "Linear optical [8] parameters of a dyed nematic mixture in the presence of an ac (voltage", Optical Materials, 29, 1004-1009, (2007 N. Bitri, A. Gharbi, J.P. Marcerou, "Scanning conoscopy [9] measurement of the optical properties of chiral smectic liquid .(crystals", Physica B: Condensed Matter, 404, 3921-3927, (2008 Alexey Bobrovsky, Alexander Ryabchun, Alexey Medvedev, Valery [10] Shibaev, "Ordering phenomena and photoorientation processes in photochromic thin films of LC chiral azobenzene-containing polymer systems", Journal of Photochemistry and Photobiology A: .(Chemistry, 206, 46-52, (2009
2

Tsung-Ta Tang, Cheng-Ying Kuo, Ru-Pin Pan, Jia-Min Shieh, and [11] Ci-Ling Pan, Strong Vertical Alignment of Liquid Crystal on Porous Anodic Aluminum Oxide Film, JOURNAL OF DISPLAY .(TECHNOLOGY, VOL. 5, NO. 9, SEPTEMBER (2009 Hecht E. and Zajac A., Optics, Addison-Wesley, reading Mass., [12] .(p.282, 378, (1990 Francon M., Information Processing Using Speckle Patterns, in [13] Laser Speckle and Related Phenomena, J. C. Dainty, Ed., Springer.(Verlag, New York, (1975 Bernardo L. M., Soares O. D. D., "Birefringence Measurements by [14] .(Double Speckle Photography", Appl. Opt., 26, p. 769, (1987 Crossland W. A., Morrissy JH and Barbara Needham, "Tilt Angle [15] Measurements of Nematic Phases of Cyano-Biphenyls Aligned By .(Obliquely Evaporated Films", J. Phys. Appl. Phys., 9, 2001, (1976 Takayuki Fujikawa, Kazuyuki Hiraok, et al., Construction of [16] Dynamic Conoscope Observation System Using CCD Camera and .(Image Processor, Jpn. J. Appl. Phys. Vol. 32, p. 985, (1993 T.A. El-Dessouki, N.I. Hendawy, A.A. Zaki, "Measuring [17] birefringence of curved sheet and single crystals by double-exposure speckle photography", Optics and Lasers in Engineering, 47, 622 .(628, (2009