Ana R. Brás

Molecular mobility of nematic E7 confined to molecular sieves with a low filling degree

The nematic liquid crystalline mixture E7 was confined with similar filling degrees to molecular sieves with constant composition but different pore diameters (from 2.8 to 6.8 nm). Fourier transform infrared analysis proved that the E7 molecules interact via the cyanogroup with the pore walls of the molecular sieves. The molecular dynamics of the system was investigated by broadband dielectric spectroscopy (10(-2)-10(9) Hz) covering a wide temperature range of approximately 200 K from temperatures well above the isotropic-nematic transition down to the glass transition of bulk E7. A variety of relaxation processes is observed including two modes that are located close to the bulk behavior in its temperature dependence. For all confined samples, two relaxation processes, at frequencies lower than the processes observed for the bulk, were detected. At lower temperatures, their relaxation rates have different temperature dependencies whereas at higher temperatures, they seem to collapse into one chart. The temperature dependence of the slowest process (S-process) obeys the Vogel-Fulcher-Tammann law indicating a glassy dynamics of the E7 molecules anchored to the pore surface. The pore size dependence of both the Vogel temperature and fragility revealed a steplike transition around 4 nm pore size, which indicates a transition from a strong to a fragile behavior. The process with a relaxation rate in between the bulklike and the S-process (I-process) shows no dependence on the pore size. The agreement of the I-process with the behavior of a 5CB surface layer adsorbed on nonporous silica leads to the assignment of E7 molecules anchored at the outer surface of the microcrystals of the molecular sieves.

Characterization of a nematic mixture by reversed‐phase HPLC and UV spectroscopy: an application to phase behaviour studies in liquid crystal–CO2 systems

In the present work a simple but selective reversed‐phase high performance liquid chromatographic method (HPLC) was developed for the analysis of the nematic liquid crystal mixture E7 to determine precisely the composition of the liquid crystal mixture used in PDLC film preparation. Ultraviolet absorption spectrophotometry experiments were carried out to determine the HPLC detection wavelength and to characterize the absorptivity constants of E7 constituents. The technique developed is applied in the case of equilibrium solubility studies for E7 in supercritical carbon dioxide (scCO2). The results indicate unambiguously that scCO2 can fractionate the mixture towards the E7 components. The four single component peaks of the E7 mixture were distinctively separated by this method, which enabled the determination of the solubility of E7 constituents in the scCO2.

Dielectric relaxation studies and electro‐optical measurements in poly(triethylene glycol dimethacrylate)/nematic E7 composites exhibiting an anchoring breaking transition

Electric field driven anchoring breakage in poly(triethylene glycol dimethacrylate)/nematic E7 composites was studied using dielectric spectroscopy and transmittance measurements. The transmittance hysteresis observed on increasing and decreasing an applied electric field, associated with different alignment states of the liquid crystal (LC), was monitored through dielectric loss. Essential changes are felt mainly in the δ‐peak, i.e. the dielectric response of the nematic when the director lies parallel to the applied electric field. An irreversible effect persists after the field had exceeded a critical value, which was manifest in a higher transmittance and a higher dielectric strength of the δ‐peak in the OFF state. The initial scattering/opaque state of the sample can only be recovered by heating to the clearing temperature of the nematic LC. The effect referred, commonly called memory effect, is rationalized in terms of anchoring breakage of the LC at the polymer–LC interfaces. The electro‐optical response was tested for different poly(triethylene glycol dimethacrylate)/nematic E7 composites in different composition ratios prepared by polymerisation‐induced phase separation. The lowest threshold field was observed for the 30:70 composite.

Molecular Motions in Amorphous Pharmaceuticals

Dielectric Relaxation Spectroscopy (10−1 Hz to 106 Hz) was used in order to get relevant information regarding the different modes of motion, from supercooled liquid down to the glassy state, present in the glass‐forming Ibuprofen. This pharmaceutical drug easily avoids crystallization on cooling from the melt, forming a glass below the dielectric Tg(100 s) = 226 K, and undergoes cold crystallization upon further heating. In the supercooled state, attained from above, a dominating relaxation process associated with the glass transition was detected. The relaxation time temperature dependence of this α process presents the usual VFT type curvature found in non‐pharmaceutical glass formers, which steepness gave a fragility index of m = 93 allowing to classify ibuprofen as a fragile glass‐former. In the glassy state, two secondary relaxation processes were found, β and γ, in decreasing temperature location. Analysis of the spectra using the Coupling Model confirms that the β process is the genuine Johari‐Gol...