Rewritable Film Research Articles

Stretchable photochromic hydrous TiO2‐embedded glycerol‐poly(dimethylsiloxane) film for rewritable information storage

AbstractPhotoreversible, color‐changing films have great potential in various optical applications. In this study, we developed a photochromic film by embedding droplets of metatitanic acid (hydrous TiO2) and glycerol in commercially available poly(dimethylsiloxane) (PDMS) silicone elastomers. Benefiting from the electron–hole pair scavenging abilities of glycerol, the resulting film exhibited rapid photoresponse, high photoreversible stability, excellent antiaging capability, and remarkable stretchability. The degree of color changes upon ultraviolet (UV) irradiation was effectively controlled by adjusting both the concentration of hydrous TiO2 (1–20 wt%) and UV irradiation time (5–30 min), thereby increasing total color‐changing ability (ΔE). High‐resolution patterns could be repetitively printed, erased, and rewritten (≥20 times) with no significant loss of clarity. After a 30‐day exposure to ambient air, there were no significant aging effects in the photochromic ability of the films, thus demonstrating promising potential as rewritable films for information storage.

PEDOT:PSS: Smart Infrared Rewritable Materials

AbstractThermal radiation spectrum regulation plays an important role in energy and information fields. Effectively hiding targets and rendering it invisible to infrared imaging detectors are great challenges in past decades. Herein, a smart infrared rewritable and emissivity tunable polymer film is proposed based on PEDOT:PSS. The adjustment ability for the thermal emission is attributed to the mobile polaronic of PEDOT that can be effectively regulated by redox agents, resulting in an infrared emission modulation > 30%. The conformation and molecular stacking order of PEDOT also present reversible property, accompanied with the transformation between dication state and neutral state. Finally, a technique for direct writing and erasing process in the infrared region is implemented, based on the simple redox treating process. This work aims to provide a simple strategy on fabricating rewritable films based on conducting polymer PEDOT:PSS, which can be potentially applied in infrared optics security printing.

Lanthanide Polyoxometalate Based Water-Jet Film with Reversible Luminescent Switching for Rewritable Security Printing.

Luminescent security printing is of particular importance in the information era. However, the use of conventional paper still carries a lot of economic and environmental issues. Therefore, developing new environmentally friendly security printing material with a low cost is imperative. To achieve the aforementioned goals, novel lanthanide polyoxometalate doped gelatin/glycerol films with high transparency, high strength, and good flexibility have been developed via a solution-casting method. The electrostatic interaction between zwitterionic gelatin and polyoxometalate was confirmed by attenuated total reflection Fourier transform infrared spectroscopy. Luminescent spectra and digital images indicated that the films exhibited reversible luminescent switching properties through association and dissociation of hydrogen bonds between glycerol and water molecules, allowing its potential application as water-jet rewritable paper for luminescent security printing. Furthermore, the printed information can be conveniently "erased" by heating, and the film can be reused for printing. The film exhibited excellent ability to be both rewritten and re-erased. A QR code pattern and hybrid printing were employed to improve the security of information. In addition, the rewritable films possessed excellent regeneration ability and low toxicity, as well as good stability against UV irradiation and organic solvents. The water-jet rewritable film based on lanthanide polyoxometalate for luminescent security printing, to the best of our knowledge, has not yet been reported up to date. This work provides an attractive alternative strategy on fabricating rewritable films for luminescent security printing in terms of cutting down the cost, simplifying the preparation process, and protecting the environment.

Effect of Dispersants on Photochromic Behavior of Tungsten Oxide Nanoparticles in Methylcellulose.

Tungsten oxide-based photochromic films that change reversibly in air between colorless-transparent in the dark and dark blue under UV irradiation were prepared by using methylcellulose as a film matrix and various dispersants. Alpha-hydroxyl acid such as glycolic acid (GA) or glyceric acid (GlyA) is the best dispersant because it can make the film transparent by adding a small quantity much less than that of 3-hydroxypropionic acid or ethylene glycol. Fourier-transform infrared spectra and Raman spectra indicate that a strong interaction exists between WO3 and GA or GlyA. The coloration and bleaching processes of the prepared films were investigated to clarify the effect of the dispersants and the moisture contents. The bleaching rate remarkably decreased in the films containing GA or GlyA but accelerated by increasing the contact with O2. Measurements of electron-spin resonance reveals that GA and GlyA as dispersants stabilize the W5+ state. This paper shows that the coloring rate and the period for keeping the blue-colored state are tunable by changing the dispersants. The photochromic films containing α-hydroxyl acid as the dispersant have the potential for application as rewritable film on which information displayed with blue-colored state can be clearly readable for longer times compared with other dispersants.

Self-Assembled Hierarchical Superstructures from the Benzene-1,3,5-Tricarboxamide Supramolecules for the Fabrication of Remote-Controllable Actuating and Rewritable Films.

The well-defined hierarchical superstructures constructed by the self-assembly of programmed supramolecules can be organized for the fabrication of remote-controllable actuating and rewritable films. To realize this concept, we newly designed and synthesized a benzene-1,3,5-tricarboxamide (BTA) derivative (abbreviated as BTA-3AZO) containing photoresponsive azobenzene (AZO) mesogens on the periphery of the BTA core. BTA-3AZO was first self-assembled to nanocolumns mainly driven by the intermolecular hydrogen-bonds between BTA cores, and these self-assembled nanocolumns were further self-organized laterally to form the low-ordered hexagonal columnar liquid crystal (LC) phase below the isotropization temperature. Upon cooling, a lamello-columnar crystal phase emerged at room temperature via a highly ordered lamello-columnar LC phase. The three-dimensional (3D) organogel networks consisted of fibrous and lamellar superstructures were fabricated in the BTA-3AZO cyclohexane-methanol solutions. By tuning the wavelength of light, the shape and color of the 3D networked thin films were remote-controlled by the conformational changes of azobenzene moieties in the BTA-3AZO. The demonstrations of remote-controllable 3D actuating and rewritable films with the self-assembled hierarchical BTA-3AZO thin films can be stepping stones for the advanced flexible optoelectronic devices.

Study on NIR Optical Rewritable Film Based on Dithienylethene and Upconversion Nanocrystals

Tm3+ and Yb3+ codoped NaYF4 upconversion (UC) nanoparticles (NPs) with intense ultraviolet (UV) fluorescence were synthesized using a solvothermal approach. NIR optical rewritable film incorporated with the UCNPs and dithienylethene (DTE) were performed for optical storage based on the photochromic reaction of DTE induced by the intense UV from themultiphoton UC fluorescence of NaYF4NPs. The photochromic DTE did not exhibit obvious fatigue after repetitious write/erase cycles using NIR/green irradiation.

Simple full-color rewritable film with photochromic fulgide derivatives

A trial full-color rewritable film has been prepared by mixing fulgide derivatives as three primary-coloring dyes in a polymer, giving practically colorless or black form upon irradiation with white light or UV light. A good color image was obtained by a simple, one-shot irradiation with white light above the positive-color mask attached on the black film. The image could be erased and rewritten with another positive mask though degraded after many erase–write cycles.