Liquid crystalline cellulose derivatives for mirrorless lasing

In this thesis cholesteric films made of liquid crystalline cellulose derivatives with improved optical properties were prepared. The choice of the solvent, hydrogen bond influencing additives, the synthetic realization of a very high degree of substitution on the cellulosic polymer and the use of mechanical stirring at the upper concentration limit of the liquid crystalline range were the basis for an improved alignment of the applied cellulose tricarbamates. In combination with a tuned substrate treatment and film preparation method, cholesteric films were obtained, with optical properties that were theoretically predicted and only known from low molecular weight liquid crystals so far. Subsequent polymerization allowed a permanent fixing of the alignment and the fabrication of free standing and insensitive films.rnThe incorporation of inorganic nanorods into the cholesteric host material was mediated with tailored block copolymers, available via controlled radical polymerization methods. In addition to the shape match between the rodlike mesogens of the host and the nanorods it was possible to increase the miscibility of both materials. Nevertheless, the size of the nanorods, in comparison to the mesogens, in these densely packed liquid crystalline phases as well as their long equilibration times were the reasons for phase separation. Nanorods are, in principle, valuable substitutes for organics, but their utilization in cellulosic CLC was not to be combined with a high quality alignment of the cholesteric structure.rnA swelling process of polymerized films in a dye solution or dissolving dyes in non-polymerized CLC was used for incorporation of the organic chromophores. With the first method the CLC could be aligned and polymerized without any disturbance due to dye molecules. The optical properties of dye and CLC were matched, with regard to mirrorless lasing devices. The dye was optically excited and laser emission supported by the cholesteric cavity was obtained. The polarization and wavelength of the emitted radiation as well as its bandwidth, the obtained interference pattern and threshold behavior of the emission proofed the feedback mechanism that was not believed to be realizable in liquid crystalline polymers. rnUtilization of a microfluidic co-flow injection device enabled us to transfer the properties of cellulosic CLC from the planar film shape to spherical micrometer sized particles. The pure material yielded particles with distorted mesogen alignment similar to films prepared by capillary flow. Dilution of the CLC with a solvent that migrated into the carrier phase during particle preparation provided the basis for particles with well ordered areas. rnAlthough cellulose derivatives were known for their liquid crystalline behavior for decades and synthesized in mass production, their application as feedback material was affected by bad optical properties. In comparison to low molar mass compounds, the low degree of order in the CLC phase was the cause. With the improved material, defined lasing emission was shown and characterized. Derivatives of cellulose are desirable materials, because, as a renewable resource, they are available in large amounts for a low price and need only simple derivatization reactions. The fabrication of CLC films with tunable lasing emission, for which this thesis can provide a starting point, is in good agreement with today's requirements of modern technology and its miniaturization.rn

Integration von Heizern in thermotrope flüssigkristalline Elastomer-Aktoren und deren Anwendung beim technischen Nachbau eines menschlichen Auges

Flüssigkristalline Elastomere (LCE) zeigen eine reversible Kontraktion und werden in der Literatur auch als „künstliche Muskeln“ bezeichnet. In dieser Arbeit werden sie mit einem integrierten Heizer versehen, um eine schnelle und präzise Ansteuerung zu ermöglichen. Anschließend werden diese als Aktoren zur Realisierung eines technischen Nachbaus des menschlichen Auges verwendet. rnDas einzigartige Verhalten der flüssigkristallinen Elastomere beruht auf der Kombination der Entropie Elastizität des Elastomers mit der Selbstorganisation der flüssigkristallinen Einheiten (Mesogene). Diese beiden Eigenschaften ermöglichen eine reversible, makroskopische Verformung beim Phasenübergang des Flüssigkristalls in die isotrope Phase. Hierbei ist es wichtig eine homogene Orientierung der Mesogene zu erzeugen, was in dieser Arbeit durch ein Magnetfeld erreicht wird. Da es sich um ein thermotropes flüssigkristallines Elastomer handelt, werden in dieser Arbeit zwei Ansätze vorgestellt, um den LCE intern zu heizen. Zum einen werden Kohlenstoffnanoröhren integriert, um diese über Strahlung oder Strom zu heizen und zum anderen wird ein flexibler Heizdraht integriert, welcher ebenfalls über Strom geheizt wird. rnUm den technischen Nachbau des menschlichen Auges zu realisieren, ist die Herstellung einer flüssigkristallinen Iris gezeigt. Hierzu wird ein radiales Magnetfeld aufgebaut, welches eine radiale Orientierung des Mesogene ermöglicht, wodurch wiederum eine radiale Kontraktion ermöglicht wird. Außerdem sind zwei Konzepte vorgestellt, um eine Elastomer Linse zu verformen. Zum einen wird diese mit einem ringförmigen LCE auseinandergezogen und somit abgeflacht. Zum anderen sind acht Aktoren über Anker an einer Linse angebracht, welche ebenfalls eine Vergrößerung der Linse bewirken. In beiden Fällen werden LCE mit dem zuvor präsentierten integrierten Heizdraht verwendet. Abschließend ist das Zusammensetzen des technische Nachbaus des menschlichen Auges dargestellt, sowie Aufnahmen, welche mit diesem erzeugt wurden.

Liquid-Crystalline Dendrimers Designed by Click Chemistry

Liquid-crystalline dendrimers have been prepared from second-generation Percec-type poly(benzyl ether) dendrons or second-generation poly(aryl ester) dendrons carrying cyanobiphenyl mesogens. The Janus dendrimer, which combines the two types of dendromesogens, has also been synthesized. Those compounds have been prepared under copper-catalyzed azide–alkyne cycloaddition conditions. The mesomorphic properties have been studied by thermal analysis (POM, DSC) and small-angle X-ray scattering. Smectic A, nematic, and columnar phases have been observed depending on the dendritic building blocks. The click reaction has proven to be a powerful and elegant synthetic tool for the design of complex dendritic liquid-crystalline architectures.

L'orientation et la propriété de mémoire de forme des polymères cristallins liquides à chaînes latérales covalents et supramoléculaires

In many studies of the side-chain liquid crystalline polymers (SCLCPs) bearing azobenzene mesogens as pendant groups, obtaining the orientation of azobenzene mesogens at a macroscopic scale as well as its control is important, because it impacts many properties related to the cooperative motion characteristic of liquid crystals and the trans-cis photoisomerization of the azobenzene molecules. Various means can be used to align the mesogens in the polymers, including rubbed surface, mechanical stretching or shearing, and electric or magnetic field. In the case of azobenzene-containing SCLCPs, another method consists in using linearly polarized light (LPL) to induce orientation of azobenzene mesogens perpendicular to the polarization direction of the excitation light, and such photoinduced orientation has been the subject of numerous studies. In the first study realized in this thesis (Chapter 1), we carried out the first systematic investigation on the interplay of the mechanically and optically induced orientation of azobenzene mesogens as well as the effect of thermal annealing in a SCLCP and a diblock copolymer comprising two SCLCPs bearing azobenzene and biphenyl mesogens, respectively. Using a supporting-film approach previously developed by our group, a given polymer film can be first stretched in either the nematic or smectic phase to yield orientation of azobenzene mesogens either parallel or perpendicular to the strain direction, then exposed to unpolarized UV light to erase the mechanically induced orientation upon the trans–cis isomerization, followed by linearly polarized visible light for photoinduced reorientation as a result of the cis–trans backisomerization, and finally heated to different LC phases for thermal annealing. Using infrared dichroism to monitor the change in orientation degree, the results of this study have unveiled complex and different orientational behavior and coupling effects for the homopolymer of poly{6-[4-(4-methoxyphenylazo)phenoxy]hexyl methacrylate} (PAzMA) and the diblock copolymer of PAzMA-block- poly{6-[4-(4-cyanophenyl) phenoxy]hexyl methacrylate} (PAzMA-PBiPh). Most notably for the homopolymer, the stretching-induced orientation exerts no memory effect on the photoinduced reorientation, the direction of which is determined by the polarization of the visible light regardless of the mechanically induced orientation direction in the stretched film. Moreover, subsequent thermal annealing in the nematic phase leads to parallel orientation independently of the initial mechanically or photoinduced orientation direction. By contrast, the diblock copolymer displays a strong orientation memory effect. Regardless of the condition used, either for photoinduced reorientation or thermal annealing in the liquid crystalline phase, only the initial stretching-induced perpendicular orientation of azobenzene mesogens can be recovered. The reported findings provide new insight into the different orientation mechanisms, and help understand the important issue of orientation induction and control in azobenzene-containing SCLCPs. The second study presented in this thesis (Chapter 2) deals with supramolecular side-chain liquid crystalline polymers (S-SCLCPs), in which side-group mesogens are linked to the chain backbone through non-covalent interactions such as hydrogen bonding. Little is known about the mechanically induced orientation of mesogens in S-SCLCPs. In contrast to covalent SCLCPs, free-standing, solution-cast thin films of a S-SCLCP, built up with 4-(4’-heptylphenyl) azophenol (7PAP) H-bonded to poly(4-vinyl pyridine) (P4VP), display excellent stretchability. Taking advantage of this finding, we investigated the stretching-induced orientation and the viscoelastic behavior of this S-SCLCP, and the results revealed major differences between supramolecular and covalent SCLCPs. For covalent SCLCPs, the strong coupling between chain backbone and side-group mesogens means that the two constituents can mutually influence each other; the lack of chain entanglements is a manifestation of this coupling effect, which accounts for the difficulty in obtaining freestanding and mechanically stretchable films. Upon elongation of a covalent SCLCP film cast on a supporting film, the mechanical force acts on the coupled polymer backbone and mesogenic side groups, and the latter orients cooperatively and efficiently (high orientation degree), which, in turn, imposes an anisotropic conformation of the chain backbone (low orientation degree). In the case of the S-SCLCP of P4VP-7PAP, the coupling between the side-group mesogens and the chain backbone is much weakened owing to the dynamic dissociation/association of the H-bonds linking the two constituents. The consequence of this decoupling is readily observable from the viscoelastic behavior. The average molecular weight between entanglements is basically unchanged in both the smectic and isotropic phase, and is similar to non-liquid crystalline samples. As a result, the S-SCLCP can easily form freestanding and stretchable films. Furthermore, the stretching induced orientation behavior of P4VP-7PAP is totally different. Stretching in the smectic phase results in a very low degree of orientation of the side-group mesogens even at a large strain (500%), while the orientation of the main chain backbone develops steadily with increasing the strain, much the same way as amorphous polymers. The results imply that upon stretching, the mechanical force is mostly coupled to the polymer backbone and leads to its orientation, while the main chain orientation exerts little effect on orienting the H-bonded mesogenic side groups. This surprising finding is explained by the likelihood that during stretching in the smectic phase (at relatively higher temperatures) the dynamic dissociation of the H-bonds allow the side-group mesogens to be decoupled from the chain backbone and relax quickly. In the third project (Chapter 3), we investigated the shape memory properties of a S-SCLCP prepared by tethering two azobenzene mesogens, namely, 7PAP and 4-(4'-ethoxyphenyl) azophenol (2OPAP), to P4VP through H-bonding. The results revealed that, despite the dynamic nature of the linking H-bonds, the supramolecular SCLCP behaves similarly to covalent SCLCP by exhibiting a two-stage thermally triggered shape recovery process governed by both the glass transition and the LC-isotropic phase transition. The ability for the supramolecular SCLCP to store part of the strain energy above T[subscript g] in the LC phase enables the triple-shape memory property. Moreover, thanks to the azobenzene mesogens used, which can undergo trans-cis photoisomerization, exposure the supramolecular SCLCP to UV light can also trigger the shape recovery process, thus enabling the remote activation and the spatiotemporal control of the shape memory. By measuring the generated contractile force and its removal upon turning on and off the UV light, respectively, on an elongated film under constant strain, it seems that the optically triggered shape recovery stems from a combination of a photothermal effect and an effect of photoplasticization or of an order-disorder phase transition resulting from the trans-cis photoisomerization of azobenzene mesogens.