Liquid crystal alignment property of polystyrene derivatives containing dual photoreactive side groups

We synthesized a series of polystyrene derivatives having the dual photoreactive side moieties, 4-(4-cyanophenylazo)phenoxymethyl and methyl cinnamate-4-oxymethyl, for the application of photoalignment materials. Stable and homogeneous planar LC cells having pretilt angles adjustable from 0.5° to 5° were obtained from these polymer films having molar contents of cinnamate and azobenzene groups in the ranges of 100-80 and 0-20 mol%, respectively, through the irradiation of linearly polarized ultraviolet (LP-UV) light to crosslink the cinnamate groups, followed by the irradiation of linearly polarized visible (LP-Vis) light to induce the isomerization of the azobenzene groups. The electro-optical and LC alignment properties of the LC cells were found to be affected by the molar composition of the photoreactive side groups and the exposure energies of LP-UV and LP-Vis light.     

Catalytic effect of nickel under carbonization of polyimide films

In attempt to produce graphite films with high crystallinity by heat-treatment at temperatures lower than 3000 °C, the catalytic effect of nickel was investigated for carbonization of polyimide films prepared by mixing polyamic acid with nickel particles. The three-layered polyimide film was prepared to obtain graphite films with thickness beyond 100 μm. The middle layer composed of polyimide with nickel particles. The thickness of each layer was 50 μm and the film thickness became 150 μm. The carbonization was done at ca. 1600 °C for 5 h. The morphology of the carbonized films was observed by scanning electron microscopy. The graphitization degree was investigated on the basis of X-ray diffraction intensity distribution from the (0 0 2) plane. The analysis was done in terms of the comparison between the experimental and theoretical diffraction intensity curves. The theoretical calculation was carried out by using a concept for the para-crystalline theory proposed by Hoseman and Bagchi from the viewpoint of the lattice fluctuation of the c-axis.     

Zenithal alignment of liquid crystal on homeotropic polyimide film irradiated by ion beam

We investigate the pretilt characteristics of a nematic liquid crystal [LC] in terms of ion beam exposure conditions on the homeotropic polyimide alignment layer. The pretilt angle of LCs in the case of high-energy ion beam treatment was decreased considerably almost the same to that of the homogenous alignment layer though we used homeotropic polyimide film at first. Increasing irradiating energy, we could control the pretilt from 90° to 1° with several steps. We believe that this is because the side chain with hydrophobicity in the used polyimide is broken by ion beam exposure. To confirm it, contact angle measurement was carried out. With this result, we can easily control the LC pretilt in the pixel with appropriate exposure conditions which is critical to achieve excellent electrooptic characteristics and good image quality.     

Synthesis and characterization of novel fluorinated polyimides derived from 4,4′-[2,2,2-trifluoro-1-(3,5-ditrifluoromethylphenyl)ethylidene]diphthalic anhydride and aromatic diamines

A novel fluorinated aromatic dianhydride, 4,4′-[2,2,2-trifluoro-1-(3,5-ditrifluoromethylphenyl) ethylidene] diphthalic anhydride (9FDA), was synthesized, which was employed to polycondense with various aromatic diamines, including 4,4′-oxydianiline, 1,4-bis(4-aminophenoxy) benzene, 3,4′-oxydianiline and 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene to produce a series of fluorinated aromatic polyimides. The fluorinated polyimides obtained had inherent viscosities ranged of 0.61-1.14 dL/g and were easily dissolved both in polar aprotic solvents and in low boiling point common solvents. High quality polyimide films could be prepared by casting the polyimide solution on glass plate followed by thermal baking to remove the organic solvents and volatile completely. Experimental results indicated that the fluorinated polyimides exhibited good thermal stability with glass transition temperature ranged of 245-283 °C and temperature at 5% weight loss of 536-546 °C. Moreover, the polyimide films showed outstanding mechanical properties with the tensile strengths of 87.7-102.7 MPa and elongation at breaks of 5.0-7.8%, good dielectric properties with low dielectric constants of 2.71-2.97 and low dissipation factor in the range of 0.0013-0.0028.     

Photoinduced electron transfer in nanostructures of ultrathin polyimide films containing porphyrin moieties

Photoinduced electron transfer between porphyrin moieties and pyromellitimide fragments has been investigated in multi-layered structures of ultrathin polyimide films prepared by the Langmuir-Blodgett (LB) technique. The LB films were composed of three kinds of polyimides, which contained zinc tetraphenylporphyrin (ZnTPP) unit as an electron donor (D-layer), no chromophoric groups (S-layer), and pyromellitimide fragments as an electron acceptor (A-layer). The layered structure and orientational distribution of porphyrin moieties in the LB films were evaluated by surface plasmon measurement and absorption dichroism measurement, respectively. The thickness of monolayer was estimated to be 0.9 nm for the polyamic acid films and 0.4 nm for the polyimide films. The molecular plane of porphyrin moieties was oriented in the direction parallel to the substrate plane. In the multi-layered structures of polyimide LB films, the efficiencies of photoinduced electron transfer from porphyrin moieties to pyromellitimide fragments varied sharply with the number of spacing layers, indicating that the short-range interactions such as electron transfer could be controlled by the fabric of ultrathin films. The rate of electron transfer observed by the fluorescence quenching measurements was numerically simulated for the nanostructure using the Monte Carlo method.     

Ion beam-induced positive imaging of polyimide via two step imidization

The preparation of ion track membranes of thermally stable polyimide films has been performed by ion beam irradiation of partially imidized polyamic acid (PAA) films followed by alkaline etching and final imidization. No discernible positive hole patterns were observed on the irradiated films of partially imidized PAA containing sulfonyl linkages, although sulfonyl group is known to be highly sensitive to ion beams. In contrast, positive hole patterns appeared on the irradiated films of the partially imidized PAA with 68-89% imidization degrees that contains sulfonyl linkages along with a methylene group in the main chain. The most contrasty hole patterns with 0.3 μm diameter were observed on the irradiated PAA films of 89% imidization degree. The irradiated PAA film with the hole patterns was then transformed to the corresponding polyimide film with curing at 350 °C for 1 h. From the structural comparison of the polyimides, the possible mechanism for the hole pattern formation is suggested.     

Effect of side chain structure of polyimides on a pretilt angle of liquid crystal cells

A series of poly(amic acid)s had been synthesized from cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) and 4,4′-diaminodiphenyl methane (DDM) and functional diamines with various side chain structures. The functional diamines, like 3,5-diamino benzoic acid hexadecane-1-yl ester which had long alkyl or rigid alicyclic side chains with different flexibility had been synthesized. Pretilt angles of liquid crystal cell fabricated with the poly(amic acid)s were measured and investigated factors affecting on the pretilt angles. The pretilt angles of the liquid crystal on the polyimide (5a) with rigid side group was 0.6°, on the other hand, the pretilt angle on the polyimide (5b) and (5c) with flexible side chains were very high above 89.6°. Furthermore, the pretilt angle of liquid crystal on the polyimide (5c) film having rigid cylindrical structure with 6-methylheptyl at the chain end was still high above 86.0° even after the rubbing process.     

Synthesis, characterization and liquid-crystal-aligning properties of novel aromatic polypyromellitimides bearing (n-alkyloxy)biphenyloxy side chains

Novel aromatic polypyromellitimides bearing (n-alkyloxy)biphenyloxy side chains were prepared by two-step polycondensation of 1,4-phenylenediamine (PDA) and biphenyl-4,4′-diamine (BZ) with 3,6-bis[4′-(n-alkyloxy)biphenyl-4-oxy]pyromellitic dianhydrides (C_mB-PMDAs, m = 6, 8, 10, 12), which had been synthesized by the nucleophilic substitution of N,N′-diphenyl-3,6-dibromopyromellitimides with sodium 4-(n-alkyloxy)biphenoxides. Inherent viscosities of the poly(amic acid)s were in the 0.26-0.62 dL/g range. Poly{1,4-phenylene-3,6-bis[4′-(n-alkyloxy)biphenyl-4-oxy]pyromellitimide}s (C_mB-PPIs) and poly{4,4′-biphenyl-3,6-bis[4′-(n-alkyloxy)biphenyl-4-oxy]pyromellitimide}s (C_mB-BPIs) obtained in films by thermal imidization of the corresponding poly(amic acid)s were characterized by FT-IR spectroscopy and elemental analysis, and their crystalline structure and thermal properties were measured and discussed with respect to the side chain length. After the polyimide films were surface-treated by rubbing with velvet fibers, standard liquid crystal (LC) cells containing 4-cyano-4′-n-pentylbiphenyl (5CB) were fabricated and their LC-aligning properties were investigated in terms of pretilt angle. The pretilt angles were remarkably affected by side chain length and on surface of the polyimides with m = 6 and 8 LCs aligned parallel to the rubbing direction while on surface of the polyimides with m = 10 and 12 they aligned nearly or completely vertical to the rubbing direction.     

Morphological self-control of a phase-separated polymer during photopolymerization in a liquid-crystalline medium

An acrylate monomer having a cyanobiphenyl mesogen (1) was photopolymerized in a liquid-crystalline (LC) ordering field of 4-hexyloxybenzoic acid (2). A blend of (1) and (2) (molar ratio: 1:4), containing a photoinitiator, an inhibitor and a crosslinker, was irradiated with UV light at 120 and 137 °C in order to investigate the effect of an LC phase on the resulting polymer. Here, both temperatures are in the nematic temperature range of the blend, however, the former is in the LC temperature range of the polymer, whereas the latter is in the isotropic temperature range. Scanning electron microscopy of the obtained polymers revealed that the polymer prepared at 120 °C consisted of oriented fine fibers, measuring ca. 400 nm in diameter, while that obtained at 137 °C had a fused bead-like morphology. In addition, we investigated the effect of crosslinking on the morphology by comparing the results from the blends with and without a crosslinker. We found that the LC phase of the phase-separated polymer is one of the necessary conditions for the formation of the fine fiber structures.     

Polyimide nanocomposites prepared from high-temperature, reduced charge organoclays

Montmorillonite clays modified with the dihydrochloride salt of 1,3-bis(3-aminophenoxy)benzene (APB) were used in the preparation of polyimide/organoclay hybrid films. Organoclays with varying surface charge based upon APB were prepared and examined for their dispersion behavior in the polymer matrix. High molecular weight poly(amide acid) solutions were prepared in the presence of the organoclays. Films were cast and subsequently heated to 300 °C to cause imidization. The resulting nanocomposite films, containing 3 wt% of organoclay, were characterized by transmission electron microscopy and X-ray diffraction. The clay's cation exchange capacity (CEC) played a key role in determining the extent of dispersion in the polyimide matrix. Considerable dispersion was observed in some of the nanocomposite films. The most effective organoclay was found to have a CEC of 0.70 meq/g. Nanocomposite films prepared with 3-8 wt% of this organoclay were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and thin-film tensile testing. High levels of clay dispersion could be achieved even at the higher clay loadings. Results from mechanical testing revealed that while the moduli of the nanocomposites increased with increasing clay loadings, both strength and elongation decreased.     

Flexible clear coats—Effect of curing conditions

The effect of curing at different conditions was investigated for flexible model clear coat films for coil coating applications. Based on a commercial polyester binder two formulations with isocyanate based crosslinking agents (hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI)) were prepared. The clear coats were baked at laboratory (145 °C) and industrial processing (300 °C) conditions. While for high temperature curing the baking time was kept constant at 30 s, the curing time at 145 °C, which is above the deblocking temperature of the crosslinking agents, was varied from 10 to 90 min. The clear coat films were characterized as to their thermomechanical and mechanical properties by dynamic mechanical analysis (DMA) and by tensile testing. Regarding DMA loading in tensile and penetration mode was performed.     

Molecular Orientation of Liquid Crystal on Polymer Blends of Coumarin and Naphthalenic Polyimide

Photo-induced liquid crystal alignment layers were prepared by blending polyimides and photoreactive polymers followed by polarized UV irradiation. Polyimides are selected for the purpose of improving the thermal stability of the molecular orientation of the photoreactive groups. The thermal stability of the LC alignment layer was enhanced regardless of the type of the polyimide while the direction of LC orientation was dependent on the type of polyimide. The photoreactivity of the polyimide governs the LC orientation in the blend alignment layers.     

Preparation of highly crystalline nanofibers on Fe and Fe-Ni catalysts with a variety of graphene plane alignments

The present study confirmed that highly crystalline nanofibers with controlled structure may be prepared over Fe and Fe-Ni alloy catalysts. The degree of graphitization of various carbon nanofibers (CNFs) was analyzed by using C(0 0 2) peaks from the XRD profiles. The C(0 0 2) peaks of CNFs over Fe catalyst shifted to higher angle and became narrower as the preparation temperature increased from 560 to 620 °C. Tubular CNFs prepared at temperature higher than 630 °C showed lower 2θ angles compared to those of platelet fibers. CNFs prepared over Fe-Ni catalysts tended to resemble those prepared over Fe catalysts. The degree of graphitization of platelet CNFs resembled natural graphite, while d_0 0 2 of the tubular CNFs showed values below the 3.39 Å reported as a theoretical minimum for a cylindrical alignment. Lc_0 0 2 of platelet and tubular CNFs increased by heat treatment at 2000 and 2800 °C though d_0 0 2 changed little. A transverse section of platelet and tubular CNFs had a hexagonal shape, not a round shape. The hexagonal column allows AB stacking of hexagonal planes that can give perfect hexagonal alignment.     

Studies on syntheses and properties of novel CeO2/polyimide nanocomposite films from Ce(Phen)3 complex

A series of cerium dioxide (CeO₂)/polyimide (PI) nanocomposites were successfully prepared from Ce(Phen)₃ and polyamic acid (PAA) via the solution direct-dispersing method, followed by a step thermal imidization process. TGA and XPS studies showed that the cerium complex decomposed to form CeO₂ during the thermal imidization process at 300 °C. SEM observation showed that the formed CeO₂ as nanoparticles was well dispersed in polyimide matrix with a size of about 50-100 nm for samples with different contents of CeO₂. Thermal analysis indicated that the introduction of CeO₂ decreased the thermal stability of nanocomposite films due to the decomposition of Ce(Phen)₃ in the imidization process, while the glass transition temperature (T_g) increased obviously, especially nanocomposite films with high loading of CeO₂ exhibited a trend of disappearance of T_g. DMTA and static tensile measurements showed that the storage modulus of nanocomposite films increased, while the elongation at break decreased with increasing CeO₂ content.     

Characteristics of polyimide/barium titanate composite films

In this study, the characteristics of the polyimide/BaTiO₃ composite films with various amounts of BaTiO₃ were evaluated. Modifier 1-methoxy-2-propyl acetate was added during composite preparation to disperse the BaTiO₃ particles in polyimide matrix. Conversion of polyamic acid (PAA) to polyimide was not completed for the composite film with a high BaTiO₃ loading (90 wt%). Dielectric constant of the film increases from 3.53 to 46.50, at the sweep frequency of 10 kHz, as the BaTiO₃ content increases from 0 to 90 wt% (0–67.5 vol.%), which is mainly due to the relatively high dielectric constant of BaTiO₃ particles in the polyimide matrix. The dielectric losses at 10 kHz is ranging from 0.005 to 0.015, which is due to the switching of the domain wall. Water absorption decreases considerably with increasing BaTiO₃ content. With 10 wt% (2.5 vol.%) BaTiO₃ addition, the water absorption of the composite film reduces 45% from that of pure polyimide. Also, high loading of BaTiO₃ is not beneficial to reduce the water absorption of the composite film.     

Double phase separation in preparing polyimide/silica hybrid films by sol-gel method

In this paper, the phase separation process of the polyimide/silica hybrid films made from polyamic acid (PAA) and precursor (TEOS-A) hydrolyzed tetraethoxysilane under acidic condition in N-methyl-2-pyrrolidone (NMP) through sol-gel method was investigated by the scanning electron microscope (SEM). A double phase separation was discovered for the preparation of the hybrid films. With evaporation of the solvent NMP at lower than 100 °C, the component miscibility of TEOS-A and PAA decreases so that the first phase separation took place and a larger particle phase of TEOS-A precursor with size around 2.0 μm was formed. The second phase separation from the matrix phase appeared, as PAA was imidized at elevated temperature, which destroyed the interaction between carboxyl group of PAA and hydroxyl group of TEOS-A, and a nanoscale SiO₂ particle phase formed. The formation mechanism of the double phase separation was explained by the “capture-release” model. According to the model, the second phase separation can be controlled by synthesizing amic acid-imide copolymer with different contents of carboxyl group.     

A chemically amplified positive-working photosensitive polyimide based on a blend of poly(amic acid ethoxymethyl ester) and poly(amic acid)

We prepared a novel chemically amplified photosensitive polyimide based on a blend of poly(amic acid ethoxymethyl ester) (PAAE) and poly(amic acid); this blend produces polyimide (PI) films with improved mechanical properties after imidization with photoacid generator (PAG). PAAE and poly(amic acid) were end-capped with 5-norbornene-2,3-dicarboxylic dianhydride and 2,3-dimethyl maleic anhydride, respectively, to lower their molecular weights without compromising the properties of the resulting PI films. As a result of the blending of these PI precursors, the mechanical properties of the PI films were found to be less affected by the strong acid generated from the PAG than PI films fabricated by imidization of PAAE alone. The relatively high solubility of the blended PI precursor film in basic aqueous solutions was found to be effectively controlled by the use of a high-temperature post-exposure bake process to partially imidize the end-capped PAA. It was found that a 10-μm-thick film of the PSPI precursor system containing 13 wt% PAGs exhibits a sensitivity (D⁰) of 700 mJ/cm² when developed with 2.38 wt% aqueous tetramethyl ammonium hydroxide solution at room temperature. A fine positive pattern was fabricated in a 12 μm thick film with 1000 mJ/cm² of i-line exposure. The resultant PI film was also found to exhibit excellent mechanical and thermal properties, which are critical to its practical use as a stress buffer layer in semiconductor packaging.     

Electrochemically and electrochromically stable polyimides bearing tert-butyl-blocked N,N,N′,N′-tetraphenyl-1,4-phenylenediamine units

A new class of electrochemically active polyimides with di-tert-butyl-substituted N,N,N′,N′-tetraphenyl-1,4-phenylenediamine units was prepared from N,N-bis(4-aminophenyl)-N′,N′-bis(4-tert-butylphenyl)-1,4-phenylenediamine and various aromatic tetracarboxylic dianhydrides via a conventional two-step procedure that included a ring-opening polyaddition to give poly(amic acid)s, followed by chemical or thermal cyclodehydration. Most of the polyimides are readily soluble in many organic solvents and can be solution-cast into tough and amorphous films. They had useful levels of thermal stability, with relatively high glass-transition temperatures (276-334 °C), 10% weight-loss temperatures in excess of 500 °C, and char yields at 800 °C in nitrogen higher than 60%. Cyclic voltammograms of the polyimide films cast on the indium-tin oxide (ITO)-coated glass substrate exhibited two reversible oxidation redox couples at 0.70-0.74 V and 1.05-1.08 V vs. Ag/AgCl in acetonitrile solution. The polyimide films revealed excellent stability of electrochromic characteristics, with a color change from colorless or pale yellowish neutral form to green and blue oxidized forms at applied potentials ranging from 0.0 to 1.3 V. These anodically coloring polymeric materials exhibited high optical contrast of percentage transmittance change (Δ%T) up to 44% at 413 nm and 43% at 890 nm for the green coloration, and 98% at 681 nm for the blue coloration. After over 50 cyclic switches, the polymer films still exhibited good redox and electrochromic stability.     

Polyimides from 2,3,3′,4′-biphenyltetracarboxylic dianhydride and aromatic diamines

A series of new polyimides were prepared from the reaction of 2,3,3′,4′-biphenyltetracarboxylic dianhydride (a-BPDA) with various aromatic diamines. The properties of the a-BPDA polyimides were compared with those of polyimides prepared from the reaction of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) with the same aromatic diamines. Films of the a-BPDA polyimides had higher glass transition temperatures (T_gs) and less color than the corresponding s-BPDA polyimide films. Light transmission at 500 nm, solar absorptivity, and thermal emissivity were determined on certain films. Films of similar polyimides based upon a-BPDA and s-BPDA containing meta linkages and others containing para linkages were each cured at 250, 300, and 350 °C. The films were characterized primarily by T_g, color, optical transparency, tensile properties, dynamic mechanical thermal analysis, and coefficient of thermal expansion. The a-BPDA meta linked polyimide films had tensile strengths and moduli higher than films of the a-BPDA para linked polyimide. The same phenomenon was not observed for the s-BPDA meta and para linked polyimides. The chemistry, mechanical, and physical properties of the polymers and films are discussed.     

Organosoluble and light-colored fluorinated polyimides derived from 2,3-bis(4-amino-2-trifluoromethylphenoxy)naphthalene and aromatic dianhydrides

A novel fluorinated bis(ether amine) monomer, 2,3-bis(4-amino-2-trifluoromethylphenoxy)naphthalene, was prepared through the nucleophilic aromatic substitution reaction of 2-chloro-5-nitrobenzotrifluoride and 2,3-dihydroxynaphthalene in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C. A series of new fluorine-containing polyimides having inherent viscosities of 0.54 to 1.10 dl/g were synthesized from the diamine with various commercially available aromatic dianhydrides using a standard two-stage process with thermal imidization of poly(amic acid) films. These polyimides were highly soluble in a variety of organic solvents, and most of them afforded transparent, light-colored, and tough films with good tensile strengths. These polyimides exhibited glass transition temperatures (T_gs) of 247-300 °C and showed no significant decomposition below 500 °C under either nitrogen or air atmosphere. Except for the polyimide derived from pyromellitic dianhydride, the polyimide films were almost colorless, with an ultraviolet-visible absorption cutoff wavelength below 400 nm and low b∗ values (a yellowness index) of 10.7-41.9. These polyimides had dielectric constants of 3.09 to 3.65 (1 MHz) and moisture absorptions in the range of 0.2-0.3 wt%.