Substituted Septithiophenes with End Groups of Different Size: Packing and Frustration in Bulk and Thin Films.

We report on three different liquid crystalline compounds with a central septithiophene core and alkylated end groups of strongly increasing bulkiness. In principle, the thiophene cores prefer to pack parallel to optimize their π-π interactions, which becomes sterically impossible for the bulkier end groups. Using X-ray diffraction, we find that the way out of this packing dilemma is toward liquid-crystal phases of higher dimensionality in the order smectic → columnar ↔ bicontinuous cubic. For the smectic phase, packing in a monolayer is no problem; for the other ones packing considerations become more stringent in films due to the boundaries. Surface X-ray techniques and atomic force microscopy indicate an appreciable difference between monolayer and three-layer films, in which the monolayers appear to escape from packing frustration by generating superstructures. We propose a basic structure of columns parallel to the substrate that provides a compromise between preserving some π-π interactions and packing the bulky alkyl groups.

Thinning and thickening of free-standing smectic films revisited.

We present a theoretical explanation of the remarkable thickness instabilities that occur in free-standing smectic films (FSSF) upon changing the external conditions: i) upon heating the film above the bulk smectic disordering temperature, generally the film does not rupture but instead shows successive layer-by-layer thinning transitions; ii) thickening of FSSF, which occurs within the thermal range of the smectic phase upon local heating. All observations reported so far can be explained on the basis of the Landau-de Gennes theory of the smectic state in combination with nucleation theory. In overheated smectic films (thinning) or locally heated FSSF (thickening) an additional normal tensile force appears due to a change of the mean density of the film. In the case of an overheated FSSF the free energy has oscillatory character, and upon heating the balance of tensile and elastic forces breaks down spontaneously. This leads to thinning of the film, which proceeds via thermal nucleation and growing of dislocation loops in the middle plane of the film. The expression for the envelope of the points of thinning as well as estimates of the dynamics of growth of dislocation loops, are in good agreement with experiments. Local heating of a FSSF within the smectic temperature range induces thermal expansion, which shifts the system to a metastable state. This favors nucleation and growth of dislocation loops of excess smectic layers in the middle plane of the film. The activation energy of such dislocation loops attains values below the threshold energy and decreases upon further heating. This leads to local film thickening by many tens of layers. Realization of this scenario depends crucially on the energy dissipated locally in the film. Estimates of the thickness of the growing "island" in the film and of the velocity of the dislocation loop growth are in reasonable agreement with experiments.

Monolayer properties of asymmetrically substituted sexithiophene.

We present a structural comparison of monolayers on a SiO2 substrate of two asymmetrically substituted sexithiophenes (6T). Molecule 1 consists of 6T with a branched alkyl chain at one end only and shows a crystalline structure. In molecule 2, the bifunctional 6T has in addition at the other end a linear alkyl chain. It displays thermotropic liquid crystalline (LC) behavior. Both compounds form readily single molecular layers from solution. Remarkably, full monolayer coverage can be achieved before multilayer growth starts. LC properties promote preordering near the interface as well as exchange of molecules between the growing domains, thus regulating the domain sizes. As a result, the LC compound 2 forms single-molecule islands with larger domain sizes compared to compound 1. Surface X-ray investigations indicate that the 6T cores are tilted relative to the layer normal. The tilt angle is as large as 54° for compound 2 compared to 28° for compound 1. For molecule 2, interfacial constraints and packing requirements because of the asymmetric substitution cause a rather loosely organized core structure.

Random disorder and the smectic-nematic transition in liquid-crystalline elastomers.

We report effects of disorder due to random cross-linking on the nematic to smectic-A phase transition in smectic elastomers. Thermoelastic data, stress-strain relations and high-resolution x-ray scattering profiles have been analyzed for two related compounds with a small and a larger nematic range, respectively, each for 5% as well as 10% cross-links. At 5% cross-link density the algebraic decay of the positional correlations of the smectic layers survives in finite-size domains, providing a sharp smectic-nematic transition. At an increased cross-link concentration of 10% the smectic order disappears and gives way to extended short-range layer correlations. In this situation neither a smectic-nematic nor a nematic-isotropic transition is observed anymore. The occurrence of disorder at a relatively large cross-link concentration only, indicates that smectic elastomers are rather resistant to a random field. The temperature dependence of the correlation lengths and thermoelastic behavior suggest a shift to a "parasmectic" regime of a first-order smectic-isotropic transition.

Thermotropic phase behavior of trialkyl cyclohexanetriamides.

The thermotropic phase behavior of symmetric cyclohexanetriamides carrying various linear and branched alkyl chains was investigated using calorimetry, microscopy, solid-state NMR, dielectric relaxation spectroscopy, and X-ray scattering techniques. Cyclohexanetriamides carrying C(6) or longer linear alkyl chains formed columnar plastic phases with a pseudocentered rectangular lattice. Those with C(8) or longer alkyl chain also showed a nematic liquid crystalline phase. Cyclohexanetriamides carrying branched octyl chains displayed columnar phases with rectangular lattices, except for the triamide with the highly branched tetramethylbutyl group. The occurrence of less symmetrical columnar phases is ascribed to the mode of stacking of cyclohexanetriamides which leads to noncylindrical columns. Dielectric relaxation spectra also featured highly cooperative relaxation processes related to reorientation of the macrodipolar columns in the mesophase, showing the potential of these molecules as building blocks in responsive materials.

Lyomesophases of C3-symmetrical bipyridine-based discs in alkanes: an X-ray diffraction study.

The importance of the role of alkane solvents in the self-assembly process of pi-conjugated molecules is well recognized but hardly understood. Here we present our results on the X-ray diffraction studies that we conducted to gain insight into the supramolecular structure of mixtures of a bipyridine-based molecule (1) with alkanes. Independent of the alkane used (linear or branched), above x(w) > 0.06 (with x(w) being the weight fraction of 1) the mixtures show lyotropic liquid-crystalline behavior. The nature of the lyomesophase depends only on x(w) and not on the nature of the alkane (linear or branched). A columnar rectangular phase is present when x(w) > 0.66. Upon dilution of 1, a columnar hexagonal phase is assigned first (0.50 < x(w) < 0.65), and finally a columnar nematic phase is observed when x(w) < 0.50. Concentration-dependent SAXD measurements revealed that the dilution of 1 can be viewed as a swelling process. First, solvent molecules occupy space between the columns formed by 1, which are not disrupted. This process can quantitatively be described by a 2D swelling model. Only at lower concentrations does 3D swelling start as the columns start breaking into shorter fragments.

Road to disorder in smectic elastomers.

We present a high-resolution x-ray study of the effects of disorder induced by random cross-linking side-chain smectic elastomers. The influence of variation of the concentration and stiffness of the cross-link units on the disruption of the one-dimensional translational order is reported in detail. Precise analysis of the line shape of the quasi-Bragg peaks associated with the smectic layering indicates a transition from algebraic decaying ordering to disorder. The smectic line shapes can be described by the Caillé correlation function convoluted with a finite-size factor represented by a stretched Gaussian (compressed exponential). The transition to disorder is signaled by a change in the exponent of the stretched Gaussian from 1 (simple Gaussian describing finite-size domains) via 0.5 (Lorentzian describing exponentially decaying short-range correlations) to <0.5 (stretched exponential correlations). For a flexible cross linker the changeover occurs for concentration between 0.15 and 0.20, for a stiff cross linker below about 0.10. Broadening of the higher harmonics of the x-ray peak indicates strong nonuniform strain within finite-size domains and local deformations induced by randomly distributed dislocations.

Capillary wrinkling of floating thin polymer films.

A freely floating polymer film, tens of nanometers in thickness, wrinkles under the capillary force exerted by a drop of water placed on its surface. The wrinkling pattern is characterized by the number and length of the wrinkles. The dependence of the number of wrinkles on the elastic properties of the film and on the capillary force exerted by the drop confirms recent theoretical predictions on the selection of a pattern with a well-defined length scale in the wrinkling instability. We combined scaling relations that were developed for the length of the wrinkles with those for the number of wrinkles to construct a metrology for measuring the elasticity and thickness of ultrathin films that relies on no more than a dish of fluid and a low-magnification microscope. We validated this method on polymer films modified by plasticizer. The relaxation of the wrinkles affords a simple method to study the viscoelastic response of ultrathin films.

Morphology of a highly asymmetric double crystallizable poly(epsilon-caprolactone-b-ethylene oxide) block copolymer.

The morphology of a highly asymmetric double crystallizable poly(epsilon-caprolactone-b-ethylene oxide) (PCL-b-PEO) block copolymer has been studied with in situ simultaneously small and wide-angle x-ray scattering as well as atomic force microscopy. The molecular masses Mn of the PCL and PEO blocks are 24,000 and 5800, respectively. X-ray scattering and rheological measurements indicate that no microphase separation occurs in the melt. Decreasing the temperature simultaneously triggers off a crystallization of PCL and microphase separation between the PCL and PEO blocks. Coupling and competition between microphase separation and crystallization results in a morphology of PEO spheres surrounded by PCL partially crystallized in lamella. Further decreasing temperature induces the crystallization of PEO spheres, which have a preferred orientation due to the confinements from hard PCL crystalline lamella and from soft amorphous PCL segments in different sides. The final morphology of this highly asymmetric block copolymer is similar to the granular morphology reported for syndiotactic polypropylene and other (co-) polymers. This implies a similar underlying mechanism of coupling and competition of various phase transitions, which is worth further exploration.

Dynamic heterogeneity in hydrogen-bonded polymers.

We report on neutron spin echo experiments on hydrogen-bonded polymers and compare the experimentally found dynamical structure factor with theoretical predictions. Surprisingly, we find that in the melt phase the expected scaling of the Rouse dynamics is not satisfied. We propose an explanation based upon the large spatial volume occupied by the connecting groups. When the effects of these bulky groups on the local friction are taken into account, the usual scaling behavior is restored.

Dynamics of fluctuations in smectic membranes.

We present a comprehensive account of the dynamics of layer-displacement fluctuations in smectic liquid-crystal membranes as studied by x-ray photon correlation spectroscopy (XPCS) and neutron-spin echo (NSE). Combining these two techniques at fast relaxation times, three distinct relaxation regimes can be distinguished. For thin membranes, at the specular Bragg position oscillatory relaxation occurs, which transforms for thicker samples into exponential decay. Above a critical off-specular angle, in XPCS exponential relaxation is observed that does not depend on the scattering angle. This indicates relaxation times that are independent of the wavelength of the fluctuations. In this regime the relaxation of the fluctuations is dominated by the surface tension. Using NSE larger off-specular angles can be reached than by XPCS, for which the relaxation time decreases with the scattering angle. This regime is dominated by the bulk elasticity of the smectic membrane. The results are compared with theoretical models for the fluctuation behavior of smectic membranes, in which effects of the mosaic distribution and of the center of mass movement of the smectic membranes must be incorporated.

Self-assembly of the perfluoroalkyl-alkane F14H20 in ultrathin films.

Scanning force microscopy on monomolecular films of eicosylperfluorotetradecane, F(CF(2))(14)(CH(2))(20)H, on mica, silicon oxide, or water revealed spontaneous organization to well-defined nanoscopic ribbon and spiral or toroidal superstructures. Whether ribbons or nanospirals were formed depended on the solvent from which the molecular monofilm was cast. Ribbons were observed when a hydrocarbon or a perfluorocarbon solvent was used, e.g., decalin or perfluorodecalin. When the compound, however, was deposited from nonselective hexafluoroxylene, the molecules assembled into spirals of defined size. The spirals/toroids transformed to ribbons when exposed either to decalin or perfluorodecalin vapor, and the ribbons transformed to toroids when exposed to hexafluoroxylene vapor. These changes could be observed in situ. Scanning force microscopy yielded an identical height and width for the bands forming the spirals and for the parallel flat ribbons. X-ray reflectivity yielded a height of 3.61 +/- 0.05 nm, again identical for both morphologies. Yet, the length of the extended F(CF(2))(14)(CH(2))(20)H molecule, i.e., 4.65 nm, exceeds the layer thickness obtained from X-ray reflectometry. It is, however, consistent with an arrangement where the fluorinated chains are oriented normal to the surface layer and where the alkyl segments are tilted with a 122 degrees angle between the two segments. Within the plane defined by the tilt, this angle allows a dense packing of the alkyl segments compensating for the larger cross-section of the fluorocarbon segment. The tilt plane defines an "easy" direction along which the monolayer structure can preserve order. In the plane perpendicular to this axis, long-range ordered dense packing of the alkyl chains is not possible. Incommensurable packing can in principle explain the finite and regular width of the ribbons and the stepwise turn in the spirals.

Shear-induced smectic ordering and crystallisation of isotactic polypropylene.

Shear-induced smectic ordering and crystallisation of isotactic polypropylene (iPP) has been studied with in-situ small- and wide-angle X-ray scattering. Shear-induced smectic bundles with a periodicity of about 4 nm have been observed at temperatures below as well as above the melting point. This applies to iPP of different molecular weight and from different sources. An increase in the average molecular weight leads to a larger periodicity of the smectic layers. The smectic layers assemble in a fibrillar morphology with a length and a width up to 200 and 10 microm, respectively. After crystallisation, the smectic bundles show upon heating higher melting temperatures than their crystalline counterparts. In agreement with this behaviour, the correlation length along the smectic layer normal is of the order of tens of nanometers, much larger than the crystal thickness. We present an anisotropic drop model of smectic domains forming a conserved system in which the smectic layers can rotate. On the basis of this model we can explain the relative orientation of the smectic layers, the crystalline lamellae and the long axis of the drop, as well as the reversibility of the smectic periodicity during cooling and heating. In the supercooled melt, the smectic ordering is followed by crystallisation; during this process crystals grow epitaxially on the surface of the smectic bundles. This leads to a new picture of the shish-kebab structure in which smectic bundles rather than extended-chain crystals play the role of the shish. The crystallisation process of the smectic regions themselves indicates that the 'mesophase' previously reported in fast-quenched iPP, is a metastable state formed during the transition from the high-temperature smectic phase to a crystal. Moreover smectic domains rather than alpha crystallites form the nuclei for crystallisation of the beta phase. The high-temperature smectic phase presents an ideal model system to study the coupling between density and conformational ordering under shear flow. Our results support a nucleation and growth process for polymer crystallisation, in which smectic bundles or other mesophases are the primary nuclei.

Disorder by random crosslinking in smectic elastomers.

We present a high-resolution x-ray study of the effects of disorder due to random crosslinking on the one-dimensional translational ordering in smectic elastomers. At a small crosslink density of about 5%, the elastomer network stabilizes the smectic structure against layer-displacement fluctuations, and the algebraically decaying layer ordering extends up to several micrometers. With increasing concentration of crosslinks, the finite size of these domains is strongly reduced, indicating that disordering takes over. Finally, at a crosslink concentration of 20%, the structure factor can be described by a Lorentzian, which signals extended short-range correlations. The findings are discussed in terms of recent theories of randomly quenched disorder.

Shear-induced smectic ordering in the melt of isotactic polypropylene.

We report an unusual shear-induced smectic phase of high-molecular-mass isotactic polypropylene at temperatures well above its melting point. The necessary stiffness in the polymer chain is provided by shear-induced coil-helix transitions. Coupling between the conformational ordering and the density generates the smectic layering. The periodicity of about 4 nm is built up from a rigid helical sequence of at least 11 monomers and a random-coil part of about 1.4 nm. These results also provide new clues to the question of preordering before polymer crystallization.

Hydrophilic elastomers for microcontact printing of polar inks.

A moderately hydrophilic, thermoplastic elastomer (poly(ether-ester)) was investigated as a stamp material for microcontact printing of a polar ink: pentaerythritol-tetrakis-(3-mercaptopropionate). Stamps with a relief structure were produced from this polymer by hot embossing, and a comparison was made with conventional poly(dimethylsiloxane) (PDMS) and oxygen-plasma-treated PDMS. It is shown that the hydrophilic stamps can be used for the repetitive printing (without re-inking) of at least 10 consecutive patterns, which preserve their etch resistance, and this in rather sharp contrast to conventional and oxygen plasma-treated PDMS stamps. It is argued that these enhanced printing characteristics of the hydrophilic stamps originate from an improved wetting and solubility of polar inks in the hydrophilic stamp.

Surface and bulk elasticity determined fluctuation regimes in smectic membranes.

We report combined x-ray photon correlation spectroscopy (XPCS) and neutron spin echo (NSE) measurements of the layer-displacement fluctuations in smectic liquid-crystal membranes in the range from 10 ns to 10 micros. NSE reveals a new regime, determined by bulk elasticity, in which relaxation times decrease with the wave vector of the fluctuations. XPCS probes slower surface-tension-dominated relaxation times, independent of the wave vector. XPCS gives a difference in correlation times at specular and off-specular positions that can be related to different detection schemes.

Two-stage surface freezing of a single top layer in a smectic-A membrane.

The crystallization of a single liquid top layer of smectic membranes of the compound 4O.8 has been studied with grazing-incidence x-ray diffraction. As this process takes place in two steps, involving an intermediate hexatic smectic-B layer before the final crystalline-B surface structure is reached, it provides a model for melting in two dimensions. The positional order has been investigated quantitatively by measuring the scattering profiles and the associated correlation lengths. The surface liquid-hexatic phase transition is found to be continuous, while the hexatic-crystal transition is weakly first order with an abrupt change of the in-plane positional correlations. The surface phase transitions do not modify the liquid in-plane structure of the interior layers.

Smectic membranes in motion: approaching the fast limits of x-ray photon correlation spectroscopy.

The dynamics of the layer-displacement fluctuations in smectic membranes have been studied by x-ray photon correlation spectroscopy (XPCS). We report transitions from an oscillatory damping regime to simple exponential decay of the fluctuations, both as a function of membrane thickness and upon changing from specular to off-specular scattering. This behavior is in agreement with recent theories. Employing avalanche photodiode detectors and the uniform filling mode of the synchrotron storage ring, the fast limits of XPCS have been explored down to 50 ns.