Effects of liquid crystalline and shear alignment on the optical properties of cellulose nanocrystal films

Rheo-optics, microspectrophotometry, and optical contrast measurements were used to gain new insights into the interrelated effects of liquid crystalline phase behavior, flow alignment, and microstructural relaxation on cellulose nanocrystal (CNC) films’ alignment and optical properties. Optical contrast measurements were found to be an effective and facile way of determining changes in anisotropy directly from cross-polarized microscopy images. This method was used to continuously measure microstructural relaxation after the cessation of shear as well as the anisotropy of dried CNC films. Aqueous liquid crystalline CNC dispersions showed greater alignment after shear than isotropic or biphasic dispersions. However, CNC gels exhibited lower alignment at equivalent shear rates. The combination of greater initial alignment and slower relaxation of sheared liquid crystalline dispersions resulted in the most optically anisotropic films. Depending on their thickness, the CNC films were optically transparent in the visible regime or exhibited tunable interference colors. The results of this work highlight the tunability of CNC dispersion processing for producing color filters and other optical materials with controlled properties.     

Segmental size of poly(ethylene terephthalate) determined by optical birefringence and ESR spin-probe method

The segmental size in amorphous poly(ethylene terephthalate) (PET) was determined by two methods: a) from deformational behavior of amorphous samples in the elastic state by optical birefringence measurement, and b) from dynamic behavior of a small spin probe by ESR measurement of correlation times. The use of the network model for orientation of segments in amorphous polymer and of the generalized free-volume model for re-orientation of the probe in the amorphous phase gave comparable values ofn=2.3 and 2.1 structural units/segment. We conclude that trans gauche conformational transitions of rather small macromolecular segments are the basic motion mechanism in _a-segmental mobility in PET.     

Dielectrophoresis of cellulose nanocrystals and alignment in ultrathin films by electric field-assisted shear assembly

Ultrathin films of cellulose nanocrystals (CNCs) are obtained by using a convective assembly setup coupled with a low-strength external AC electric field. The orientation and degree of alignment of the rod-like nanoparticles are controlled by the applied field strength and frequency used during film formation. Calculated dipole moments and Clausius-Mossotti factors allowed the determination of the critical frequencies, the peak dielectrophoresis as well as the principal orientation of the CNCs in the ultrathin films. As a result of the combination of shear forces and low electric field highly ultrathin films with controlled, unprecedented CNC alignment are achieved.     

Measurements of HOMO-LUMO levels of poly(3-hexylthiophene) thin films by a simple electrochemical method

Journal of Solid State Electrochemistry - Though poly(3-hexylthiophene) (P3HT) is one of the most commonly used polymers in organic solar cells, a broad range of values, derived from cyclic...     

Modification of orientation birefringence of cellulose ester by addition of poly(lactic acid)

Effect of the addition of poly(lactic acid) (PLA) to cellulose acetate propionate (CAP) on the optical anisotropy is studied considering the morphology and molecular orientation. It is found that PLA is miscible with CAP when the amount of PLA is less than 3 wt.%. The dissolution of PLA chains having large intrinsic birefringence into CAP phase enhances the orientation birefringence of a stretched film, although the viscosity and thus the relaxation time of PLA is significantly shorter than those of CAP. The high level of orientation of PLA chains without relaxation is attained by the cooperative alignment with CAP chains. As a result, a retardation film having appropriate birefringence can be designed by polymer blends composed of biomass-based materials. When the amount of PLA is more than 3 wt.%, however, phase separation occurs. In the case of the blends with phase-separated morphology, the orientation birefringence is not greatly enhanced by blending PLA, because the molecular orientation of PLA in PLA phase relaxes immediately as compared with that of CAP.     

A simple method for preparing a diamino cellulose disk from a dialdehyde cellulose disk by reductive amination using 2-picoline-borane

Cellulose - A method for the preparation of dialdehyde cellulose disks (DACD) and subsequent diamino cellulose disks (DAmCD) was developed. DACD was prepared by oxidizing filter paper with sodium...     

Microencapsulation of nisin in alginate-cellulose nanocrystal (CNC) microbeads for prolonged efficacy against Listeria monocytogenes

The present study was undertaken to develop edible nisin-microencapsulated beads in order to inhibit growth of Listeria monocytogenes in ready-to-eat (RTE) ham. Different concentrations of nisin (16, 31, and 63 μg/ml) were microencapsulated into alginate-cellulose nanocrystal beads. Microencapsulation kept the available nisin (63 μg/ml) content 20 times greater compared with free nisin (63 μg/ml) during 28 days of storage at 4 °C. Results showed that 63 μg/ml microencapsulated nisin exhibited 31.26 μg/ml available nisin content after 28 days of storage at 4 °C, whereas there was no available nisin content left for free nisin. Cooked ham slices were then coated by the microencapsulated nisin beads, inoculated with L. monocytogenes [~3 log colony-forming units (CFU)/g], and stored at 4 °C under vacuum packaging for 28 days. The beads containing 16, 31, and 63 μg/ml nisin significantly (P ≤ 0.05) reduced the L. monocytogenes counts by 2.65, 1.50, and 3.04 log CFU/g after 28 days of storage compared with free nisin. Furthermore, microencapsulated nisin beads did not change the physicochemical properties (pH and color) of RTE ham during storage.     

Fluorimetric determination of iron(III) by a kinetic method

A sensitive and relatively interference-free method for the kinetic determination of iron(III) is described. The method is based on the catalytic action of this ion on the autoxidation process of 4,8-diamino-1,5-dihydroxyanthraquinone-2,6-disulfonate (disodium salt), to produce a strong pink fluorescence that increases with time. The reaction is monitored at 585 nm, when excited at 525 nm, and the initial rate method is applied to perform the analytical procedure. The influence of reaction variables and the effect of foreign ions are discussed. Iron(III) contents between 0.1 and 1 μg ml^?1 can be determined with R.S.D. of ± 3.7%.     

Lead zirconate titanate (PZT) films deposited by a hydrothermal method

We present a hydrothermal method to deposit PZT films. It uses a single-step hydrothermal process and user-friendly precursors. Pb(Zr_0.52,Ti_0.48)O₃ polycrystalline films, 5–10 μm thick, were produced in an aqueous basic solution (4M KOH) on a titanium substrate in a closed autoclave at 180 °C. A time-depending study to see the evolution of the films' formation is described. Some actuation testing is also presented.     

X-ray spectrometric method for the determination of uranium in solution by a cellulose disc technique

An X-ray fluorescence spectrometric method is described for the determination of uranium in liquid samples by absorbing drops of solution on cellulose discs. Internal standards thorium, strontium or yttrium are added in the uranium solution to follow the non-uniform absorption of the liquid on the disc. A precision of better than ±0.5% is obtained for uranium determination with all the three internal standards. The method was also employed to determine uranium in the presence of plutonium and americium without any interference effects.     

Comparison of cellulose nanocrystal (CNC) filler on chemical,mechanical, and corrosion properties of epoxy-Zn protective coatings for mild steel in 3.5% NaCl solution

Cellulose - This present work evaluated the influence of oil palm frond cellulose nanocrystal (OPF-CNC) as a nanofiller to improve the barrier protection of the epoxy-Zn coating to lessen the...     

Mechanical,thermal and barrier properties of pectin/cellulose nanocrystal nanocomposite films and their effect on the storability of strawberries (Fragaria ananassa)

In this work, two formulations of pectin/cellulose nanocrystals/glycerol nanocomposites were employed as packaging to extend storage life of strawberries. The effects of incorporating cellulose nanocrystals extracted from bleached Kraft wood pulp on the mechanical, thermal, and barrier properties of pectin‐based nanocomposites were evaluated. Nanocomposite films with different filler levels of cellulose nanocrystals (1, 2, 4 and 8% w/w) were prepared by casting. Compared with the neat film of pectin, improvements in the mechanical properties of the nanocomposites were observed, but these films became fragile. To improve the film flexibility, glycerol was added as a plasticizer and then new variations in the mechanical, thermal, and barrier properties of these nanocomposites were evaluated. The effects of nanocomposite films on storability of strawberries were compared with Poly vinyl chloride packaging films. The Poly vinyl chloride film and the nanocomposites showed similar behavior regarding weight loss by the strawberries, especially in the initial days of storage. The results show that pectin/cellulose nanocrystals/glycerol nanocomposites could be considered as a viable packaging alternative for replaced the Poly vinyl cloride film. Copyright © 2015 John Wiley & Sons, Ltd.     

A radioanalytical method for the determination of Pb(II) with the use of a chelating cellulose filter

A functionalized cellulose filter, with iminodiacetate chelating units, has been characterized for the uptake of ultratrace Pb(II) (1 to 10^–6 mg · ^–1) with the use of²¹⁰Pb. The different behaviour in batch and in flow-through experiments has been observed both in the rate of metal uptake, as well as in the relative yield of metal recovery. Flow-through uptake appeared to be a faster process and to occur with higher % yield in the entire range investigated. A radioanalytical method for the determination of Pb(II) in liquid samples (10 to 10^–2 mg · ^–1) has been developed, based on the measurement of the²¹⁰Pb activity exchanged between a iminodiacetic acid filter loaded with²¹⁰Pb and the solution under analysis. Results and interferences are considered and discussed.     

Uniaxial alignment of the columnar super-structure of a hexa (alkyl) hexa-peri-hexabenzocoronene on untreated glass by simple solution processing

Uniaxially aligned, thin films of a discotic columnar thermotropic liquid crystalline material can be prepared by a simple solution zone-casting method, without the need for modified surfaces or traditional alignment techniques. Atomic force microscopy together with X-ray diffraction reveals single-crystalline-like order over several square centimeters, far exceeding the requirements for application of such films in organic molecular electronic devices such as field-effect transistors.     

Greener analytical method for the determination of copper(II) in wastewater by micro flow system with optical sensor

Greener analytical method using micro flow system for the determination of Cu(II) in wastewater samples was designed and investigated. The micro flow system consisted of a planar glass chip with poly(dimethylsiloxane) (PDMS) top plate and fixed with fiber optic probe as optical sensor for monitoring of Cu(II) that reacted with 2-carboxy-2′-hydroxy-5′-sulfoformazyl benzene (zincon) on the chip at 605 nm. This design gave a satisfied sensitivity with a linear calibration graph over the range of 0.1-3.0 μg mL⁻¹ of Cu(II) and correlation coefficient 0.9991. The percentage relative standard deviation was 2.5 for 10-replicate measurements and the limit of detection (LOD) was 0.1 μg mL⁻¹. This system has been successfully applied to the determination of Cu(II) in wastewaters from electroplating industry with less reagents and samples consumption and diminutive waste generation.     

Preparing the reinforced wood via embedding cellulose nanocrystals (CNC) into delignified fast-growing wood followed by densification

Cellulose - Delignified wood (DW) was prepared from fast-growing poplar wood by delignification with a formic acid–water azeotropic system. Compressed wood (CW) was then obtained through a...     

Improved signals ratio resolution method by optimization of resolution function--simultaneous determination of Cu(II) and Cd(II) in water samples.

From an ecological and economical point of view, it is important to design analytical procedures for monitoring heavy metals in the environment and industrial processes in a way to minimize the use of hazardous reagents and reduce the analysis time. In this paper, a well-known dithizonate extraction-based method for the determination of many metal ions was improved by using chemometrical selectivity of the strongly overlapped spectra of copper and cadmium dithizonates in CCl4 for their simultaneous determination from a single extraction at pH 10. The individual absorption spectra, having absorption maxima difference of only 20 nm, were separated, and the metal ions were quantified by using an improved procedure for optimizing the resolving function in a recently proposed signals ratio method. The procedure consists of using many different resolving functions and plotting the difference of the mean of absolute and nonabsolute mean values of pseudosignals [PDMMV (PS)] against analyte concentrations obtained with each of the resolving functions, thus obtaining 2 straight lines having intersections that give a unique and reliable value of the unknown concentration of the individual analyte in mixture giving strongly overlapped spectra. In this way, the main drawback of the signals ratio resolution method, that is, the visual estimation of optimal resolving function, is eliminated. The proposed parameter, PDMMV (PS), was tested by using both simulated and experimental spectra. Copper was determined in the mixture with ca 20-fold excess of cadmium, and cadmium was determined in ca 10-fold excess of copper at submicromolar concentration levels.     

Spectrophotometric determination of Zineb (a dithiocarbamate fungicide) by the methylene blue method

Summary A spectrophotometric method has been developed for the determination of Zineb in water and vegetables. The method is based on the liberation of hydrogen sulphide from Zineb, which is trapped in an absorbing solution of triethanolamine, sodium hydroxide and ethylenediamine tetraacetic acid. The absorbing solution is treated with N-N-dimethyl-p-phenylene diamine sulphonate and ferric chloride to form methylene blue. Beer's law is obeyed over the concentration range of 3–32 ppm. The method is simple and can be used for the determination of Zineb in the presence of other dithiocarbamates.