Crystallization kinetics of (S)-4'-(1-methylheptyloxycarbonyl)biphenyl-4-yl 4-[4-(2,2,3,3,4,4,4-heptafluorobutoxy)but-1-oxy]-2-fluorobenzoate.

Chiral liquid crystalline compounds belonging to the homologous series of (S)-4'-(1-methylheptyloxycarbonyl)biphenyl-4-yl 4-[m-(2,2,3,3,4,4,4-heptafluorobutoxy)alk-1-oxy]-2-fluorobenzoates show various behaviors on cooling depending on the length of the CmH2m chain. The homologue with m = 2 crystallizes, while for m = 5, 6, 7, and presumably also for m = 3, the glass of the anticlinic smectic CA* phase is formed. The previous results for m = 4 suggest that this homologue may also be a glassformer. This paper presents the study of the crystallization kinetics for the compound with m = 4 in isothermal conditions (by polarizing optical microscopy) and for the 5-40 K min-1 cooling rates (by differential scanning calorimetry). Microscopic observations enable estimation of the energy barrier for nucleation, which equals 409 kJ mol-1. The threshold cooling rate necessary for complete vitrification of the smectic CA* phase, obtained by extrapolating the enthalpy change during crystallization to zero, is equal to 81 K min-1 or 64 K min-1 for the linear and parabolic fits, respectively. The structural studies by X-ray diffraction show that crystal phases have lamellar structures both in the pristine sample and after crystallization from the melt but with different layer spacing. A weak relaxation process is detected in the sample after melt crystallization, revealing the presence of the conformational disorder. The dynamic glass transition temperature of the SmCA* phase, estimated from the relaxation time of the PH process (as the α-relaxation time could not be registered in a wide enough temperature range), is 244 K.

Effect of the linking bridge type on the self-assembly behaviour of 2',3'-difluoroterphenyl derivatives.

The self-assembly behaviour and the crystallization kinetics of two liquid crystal compounds containing 2',3'-difluorosubstituted terphenyl as the mesogenic core have been described. Calorimetric studies show that the linking bridge type affects the polymorphism of smectic phases. The CH2O.3 compound with the -CH2O- linking bridge connected with a longer methylene spacer possesses the chiral smectic phase with antiferroelectric properties (SmCA* phase), while the COO.6 liquid crystal with the -COO- linking bridge connected with a shorter alkyl chain forms the chiral smectic phase with ferroelectric properties (SmC* phase). Both compounds crystallize upon slow cooling, while fast cooling causes the vitrification of the conformationally disordered crystal phase. Dielectric measurements reveal the complex relaxation dynamics in the identified thermodynamic states. DFT calculations allow us to estimate the nature of relaxation processes.

Vitrification of the smectic CA* phase and kinetics of cold crystallization investigated for a fluorinated compound with a chiral centre based on (S)-(+)-3-octanol.

The formation of glass of the anticlinic high-tilted smectic CA* phase even at low cooling rates (≥2 K min-1) is reported for (S)-4'-(1-ethylhexyloxycarbonyl)biphenyl-4-yl 4-[5-(2,2,3,3,4,4,4-heptafluorobutoxy)pentyl-1-oxy]benzoate. The kinetics of crystallization is investigated via differential scanning calorimetry, polarizing optical microscopy and broadband dielectric spectroscopy. The temperature region of the largest crystallization rate, the activation energy of cold crystallization and the energy barrier of nucleation are determined. The coupling of the characteristic crystallization time with the α-relaxation time is studied. A high fragility index equal to 139 is obtained for this glassformer. Comparison with a very similar glassforming compound, with the chiral centre based on (S)-(+)-2-octanol instead of (S)-(+)-3-octanol, is presented.

Investigation of Chiral Smectic Phases and Conformationally Disordered Crystal Phases of the Liquid Crystalline 3F5FPhH6 Compound Partially Fluorinated at the Terminal Chain and Rigid Core.

Complementary methods are applied to investigate the phase transitions and crystallization kinetics of the liquid crystalline compound denoted as 3F5FPhH6. Two crystal phases are confirmed, and one of them is the conformationally disordered (CONDIS) phase. Complexity of the melt crystallization process is revealed by the analysis with Friedman's isoconversional method. The melt crystallization of 3F5FPhH6 shows different mechanisms depending on temperature, which is explained by the relation between the thermodynamic driving force and the thermal energy of translational degrees of freedom. The studied compound crystallizes even during fast cooling (30 K/min), unlike similar compounds with different fluorosubstitutions of the benzene ring, which form the smectic glass for moderate cooling rates. The tendency to vitrification of the smectic phase decreases apparently with the decreasing stability width of the SmCA* phase and the increasing relaxation time of the collective relaxation process in this phase, at least for homologues differing from 3F5FPhH6 only by the type of fluorosubstitution.

Comparative study of electrooptic, dielectric, and structural properties of two glassforming antiferroelectric mixtures with a high tilt angle.

Vitrification of the antiferroelectric smectic-C_{A}^{*} phase is reported for the orthoconic mixture W-1000 and its new derivative W-356. The crystallization is not observed even upon slow cooling and the cold crystallization on subsequent heating is also absent. Molecular dynamics in the smectic phases of both mixtures is investigated down to 173 K and the fragility parameters are determined from the temperature behavior of the α-process. X-ray diffraction is applied to compare the structural parameters of W-356 and W-1000 as well as to study the structural changes during the glass transition of the Sm-C_{A}^{*} phase. The evolution of the smectic layer order within the Sm-C_{A}^{*} glass is reported, while the correlation length of the short-range order in the smectic layers is shown to be almost constant below the glass transition temperature. Electrooptic properties of W-356: spontaneous polarization, tilt angle and switching time are determined and compared with these of W-1000. The observed differences between the properties of W-356 and W-1000 might be explained by the dimer formation of components with the -C≡N terminal group, present only in the W-356 mixture, and by the different structure of the aromatic molecular core in one of the W-356 components.

On relaxation and vibrational dynamics in the thermodynamic states of a chiral smectogenic glass-former.

This article shows the full characteristics (i.e., the phase situation as well as the relaxation and vibrational dynamics) of the (S)-4'-(1-methyloctyloxycarbonyl)biphenyl-4-yl 4-[5-(2,2,3,3,4,4,4-heptafluorobutoxy)pentyl-1-oxy]-benzoate chiral liquid crystal. Besides two enantiotropic chiral smectic phases (SmC* and ), the compound under study also forms the hexatic smectic phase and two crystal phases (Cr1 and Cr2). The XRD patterns imply a similar structure of both crystal phases. The sample crystallizes upon slow cooling, while the phase undergoes a glass transition during fast cooling. Upon subsequent heating, cold crystallization is observed. Our research reveals the complex relaxation dynamics in the identified thermodynamic states, e.g., two relaxations up to the beginning of cold crystallization, three modes in the crystal phases and seven processes in all smectic phases. The results from the scaling of the dielectric response indicate that the origin of the dynamics and behavior of the dielectric permittivity is the same for all phases, regardless of the change in temperature and/or external biasing field. The high value of the fragility index (mf ≈ 146) indicates that the compound under study is a fragile glass-forming system. The region of the -COO- and -COC- group stretching vibrations is primarily sensitive to the structural changes occurring during phase transitions.

Investigation of crystallization kinetics and its relationship with molecular dynamics for chiral fluorinated glassforming smectogen 3F5HPhH6.

The phase transitions, crystallization kinetics and molecular dynamics of (S)-4'-(1-methylheptylcarbonyl)biphenyl-4-yl 4-[5-(2,2,3,3,4,4,4-heptafluorobutoxy)pent-1-oxy] benzoate (3F5HPhH6) are investigated by differential scanning calorimetry, polarizing optical microscopy and broadband dielectric spectroscopy. The vitrification of the antiferroelectric hexatic phase is observed for cooling rates ≥5 K min-1 and the fragility index determined from dielectric data is mf ≈ 90. Two regimes of non-isothermal cold crystallization are distinguished using the Kissinger and Augis-Bennett methods in the heating rate ranges of 1-5 K min-1 (larger activation energy) and 8-20 K min-1 (lower activation energy). The correlation between the time of non-isothermal cold crystallization (using isothermal approximation) and relaxation time of the α-process is determined. The obtained coupling coefficient ξ ≈ 0.7 and temperature dependence of the crystallization rate Z from the Ozawa model imply a mainly diffusion-controlled cold crystallization below 275 K. The Avrami exponents n and Ozawa exponents nO determined for isothermal melt crystallization and non-isothermal cold crystallization, respectively, weigh in favour of two- rather than three-dimensional crystal growth. The transition between crystal phases is observed on heating, with a lower activation energy for 1-3 K min-1 than for 5-20 K min-1 rates.

Effect of high pressure on relaxation dynamics and crystallization kinetics of chiral liquid crystal in its smectic phase.

The impact of high pressure on molecular dynamics and the crystallization process in the smectic phase with antiferroelectric properties of partially fluorinated liquid crystal (S)-4'-(1-methyloctyloxycarbonyl)biphenyl-4-yl-4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy)heptyl-1-oxy]-benzoate (3F7HPhH7) was studied by broadband dielectric spectroscopy (BDS). By analyzing dielectric spectra measured under isobaric and isothermal conditions, the changes of the activation volume vs. temperature and the activation enthalpy vs. pressure have been determined to better understand the molecular system's behaviour in terms of its thermodynamic properties. The isothermal and isobar crystallization was studied by a BDS method along the trajectory of constant relaxation time τ on the (T, p) plane. The kinetics of this process was compared to that at ambient pressure, derived from the results of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The melt crystallization depends primarily on the formation of nuclei with the activation energy of approx. 50 kJ mol-1. This energy corresponds with the intramolecular movements of the carbonyl group in the rigid core. The behaviour of the apparent activation energies suggests that this process becomes easier with the progressive crystallized volume fractions. The obtained values of the Avrami exponent nA suggest that the crystal growth is three-dimensional. Additionally, we successfully used the scaling of dielectric response for experimental data. The scaling of the dielectric relaxation processes indicates that the dynamics and the behaviour of dielectric permittivity have the same origin for all phases regardless of the change in temperature and/or pressure.

On the relaxation dynamics of a double glass-forming antiferroelectric liquid crystal.

The relaxation dynamics in the thermodynamic states of the glass-forming antiferroelectric liquid crystal (S)-4'-(1-methyloctyloxycarbonyl) biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]-benzoate (3F7HPhH7) was studied by broadband dielectric spectroscopy (BDS). Two glass transitions were found at Tg,1 = 259 K and Tg,2 = 239 K, which were associated with the freezing of anti-phase motions and reorientation around the long molecular axis in the antiferroelectric SmCA* phase, respectively. The low temperature α2-relaxation process shows a Vogel-Fulcher-Tammann (VFT)-type temperature dependence of its structural relaxation time τ(T). The two secondary ß- and γ-relaxation modes ascribed to the intramolecular motions observed in the glassy state show Arrhenius behaviour of τ(T). Analysing the band shifts and the oscillator strengths of specific IR absorption bands and their temperature dependencies enables comparing them with the dielectrically determined relaxation dynamics. The kinetics of the isothermal cold crystallization in the temperature range between Tg,1 and Tg,2 was studied in detail using the Avrami and Avrami-Avramow models. This process depends primarily on the diffusion rate and the activation energy is equal to 132 kJ mol-1. The obtained values of the Avrami exponent nA suggest that the crystal growth is three-dimensional.

Designing the disorder: the kinetics of nonisothermal crystallization of the orientationally disordered crystalline phase in a nematic mesogen.

This article presents the molecular dynamics and solidification behavior of a 2,3-difluoro-4-propylphenyl 2,3-difluoro-4-(4-pentylcyclohexyl)benzoate nematic liquid crystal (5C4FPB3) observed by broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC). Polarized optical microscopy (POM) is also performed to confirm the phase transition temperatures. Our investigation reveals rare crystallization of the orientationally disordered crystal (ODIC) phase from the nematic phase and a glass transition of the crystal at cooling rates higher than 1 K min-1. The deconvolution of the dielectric spectra with derivative techniques is necessary because of the complex molecular dynamics in the crystalline phase. The BDS method enables us to capture the relaxation processes reflecting pre-crystallization molecular movements. The kinetics of nonisothermal crystallization is studied using the Ozawa, Mo, and isoconversional methods. The present studies suggest that the dominant factor of the crystal growth mechanism depends on the cooling rate. Two types of crystallization mechanisms are identified at cooling rates lower and higher than 5 K min-1. We design a diagram with crystallization and glass transition borders against the cooling rates. Estimations show that crystallization of the present compound can be bypassed at cooling rates higher than 78 kK min-1, at which a glass transition of the nematic phase occurs. We show various scenarios of the molecular order and the crystallization mechanism designed based on the process rate.

Relaxation dynamics and crystallization study of glass-forming chiral-nematic liquid crystal S,S-2,7-bis(4-pentylphenyl)-9,9-dimethylbutyl 9H-fluorene (5P-Am*FLAm*-P5).

The chiral nematic S,S-2,7-bis(4-pentylphenyl)-9,9-dimethylbutyl9H-fluorene (5P-Am*FLAm*-P5) liquid crystal shows a complex phase diagram strongly dependent on thermal treatment as identified by Polarizing Optical Microscopy (POM) and differential scanning calorimeter (DSC). The molecular dynamics in various thermodynamics states was studied by means of broadband dielectric spectroscopy (BDS). The vitrification of a chiral nematic phase (N*) is manifested by a Vogel-Fulcher-Tammann (VFT)-type temperature dependence of structural relaxation time ([Formula: see text]). Three dielectric relaxation processes exhibiting Arrhenius-like thermal activation were found in conformationally disordered (condis) Cr1 and Cr2 structures. The isothermal cold crystallization process of Cr2 occurs in the metastable N* phase; however, in the non-isothermal experiments, the Cr2 phase is formed in the isotropic phase obtained on heating the metastable N* phase. The findings for the isothermal process were compared with those regarding non-isothermal crystallization.

Interplay between Crystallization and Glass Transition in Nematic Liquid Crystal 2,7-Bis(4-pentylphenyl)-9,9-diethyl-9 H-fluorene.

This article presents the crystallization behavior and molecular dynamics of the supercooled nematic state of the newly synthesized liquid crystal 2,7-bis(4-pentylphenyl)-9,9-diethyl-9 H-fluorene (5P-EtFLEt-P5) studied by means of broadband dielectric spectroscopy (BDS). 5P-EtFLEt-P5 is a fragile glass-forming system with a high fragility parameter ( mf ≈ 121). The study compares the isothermal melt- and cold-crystallization processes at several selected temperatures Tc in the vicinity of the glass-transition temperature Tg (1.07 Tg ≤ T ≤ 1.17 Tg). Our findings reveal that at low temperatures, the crystallization of the Cr1 phase from the nematic melt state occurs more quickly than the cold crystallization. The dimensionality of the growing crystallites ( n) was found to be slightly higher for the cold- than for the melt-crystallization process, varying from n ∼ 5 to n ∼ 3 with increasing temperature. Our experimental results are discussed in terms of dynamic and thermodynamic properties of the material. The study also uses polarized optical microscopy to investigate the isothermal secondary cold crystallization (the formation of Cr2 from Cr1 upon heating), which is inaccessible by BDS measurements because of its very fast crystallization rates.

Glassy dynamics of two poly(ethylene glycol) derivatives in the bulk and in nanometric confinement as reflected in its inter- and intra-molecular interactions.

The inter- and intra-molecular interactions as they evolve in the course of glassy solidification are studied by broadband dielectric-and Fourier-transform infrared-spectroscopy for oligomeric derivatives of poly(ethylene glycol) derivatives, namely, poly(ethylene glycol) phenyl ether acrylate and poly(ethylene glycol) dibenzoate in the bulk and under confinement in nanoporous silica having mean pore diameters 4, 6, and 8 nm, with native and silanized inner surfaces. Analyzing the spectral positions and the oscillator strengths of specific IR absorption bands and their temperature dependencies enables one to trace the changes in the intra-molecular potentials and to compare it with the dielectrically determined primarily inter-molecular dynamics. Special emphasis is given to the calorimetric glass transition temperature Tg and Tαß ≈ 1.25Tg, where characteristic changes in conformation appear, and the secondary ß-relaxation merges with the dynamic glass transition (α-relaxation). Furthermore, the impact of main chain conformations, inter- and intra-molecular hydrogen bonding, and nanometric confinement on the dynamic glass transition is unraveled.

ZnS coating for enhanced environmental stability and improved properties of ZnO thin films.

Low environmental stability of ZnO nanostructures in hydrophilic systems is a crucial factor limiting their practical applications. ZnO nanomaterials need surface passivation with different water-insoluble compounds. This study describes a one-step passivation process of polycrystalline ZnO films with ZnS as a facile method of ZnO surface coating. A simple sulfidation reaction was carried out in gas-phase H2S and it resulted in formation of a ZnS thin layer on the ZnO surface. The ZnS layer not only inhibited the ZnO dissolving process in water but additionally improved its mechanical and electrical properties. After the passivation process, ZnO/ZnS films remained stable in water for over seven days. The electrical conductivity of the ZnO films increased about 500-fold as a result of surface defect passivation and the removal of oxygen molecules which can trap free carriers. The nanohardness and Young's modulus of the samples increased about 64% and 14%, respectively after the ZnS coating formation. Nanowear tests performed using nanoindentation methods revealed reduced values of surface displacements for the ZnO/ZnS system. Moreover, both ZnO and ZnO/ZnS films showed antimicrobial properties against Escherichia coli.

Glass Transition Dynamics and Crystallization Kinetics in the Smectic Liquid Crystal 4-n-Butyloxybenzylidene-4'-n'-octylaniline (BBOA).

The molecular dynamics of 4-n-butyloxybenzylidene-4'-n'-octylaniline (BBOA, abbreviated also as 4O.8) was studied by broadband dielectric spectroscopy (BDS) for samples that were exposed to various thermal treatments. Phase transitions between liquid crystalline phases (N, SmA, SmBhex, and SmBCr) were evidenced by abrupt changes in the temperature dependence of the dielectric permittivity spectra and dielectric relaxation times. A particularly complex dynamic behavior was revealed for the highly ordered SmBCr phase that showed clear evidence for cooperative dynamics of a glass-forming liquid as manifested by a Vogel-Fulcher-Tammann (VFT)-type temperature dependence of its structural relaxation time τ(T). At low temperatures, dependence τ(T) again changes from VFT to Arrhenius behavior, a phenomenon commonly observed for supercooled liquids confined to nanometer length scales and occasionally discussed as strong-fragile transition on heating. In this context, our observation supports the idea of partial orientation disorder in a quenched SmBCr phase, where the length scale of cooperative motions is restricted to the nanometer size of glassy domains causing the deviation from "bulk" VFT-type behavior. Finally, the isothermal crystallization kinetics of the metastable SmBCr phase was studied in detail. On the basis of structural information about the SmBhex and SmBCr phases, determined by X-ray diffraction, the subtle relation between molecular order and relaxation behavior is discussed.