RESUMO
Unique and random wrinkle features are desired for applications, especially in anticounterfeiting. Multifunctional wrinkled materials as well as simple wrinkling methods are desired for more applications. In this study, free-standing wrinkle-patterned porous polymer films were prepared using a modified supercritical CO2 foaming strategy. Spontaneous wrinkling was generated by applying moderate normal stress to the polymer films while foaming in situ. The wrinkle characteristics (wavelength and amplitude) were shown to be governed by the film thickness and the magnitude of the applied stress. Excessive (>5000 N) or no stress produced no obvious wrinkling or foaming whatsoever. Moreover, different morphologies of the wrinkles such as brain coral and herringbone patterns were achieved depending upon the shape of the mold used to apply the stress. Thus, the patterns show unique features for each batch process. Notwithstanding, geometric shape of the foamed wrinkle area is customizable. The reported wrinkling strategy offers the complementary advantage of patterning a foam in a polymer film and templating a PDMS stamp for different applications such as "mask-less" soft lithography, anticounterfeiting, pattern transfer, flexographic printing, and displays.
RESUMO
HYPOTHESIS: The application of an external electric Field (E-Field) to control layer-by-layer (LBL) growth of polyelectrolyte multilayers (PEM) typically involves hydrolysis of the water at the electrodes. We hypothesize that by isolating the electrodes from contact with the water, high E-Fields could be used to control the conformation of the polyelectrolytes in the solution phase and thus, enable non-chemical control of the LBL growth. EXPERIMENTAL: Attenuated total reflectance infrared spectroscopy was used to monitor the bound fraction and adsorbed amount as a function of time for the sequential addition of polyacrylic acid and polydiallyldimethylammonium chloride adsorbed on a TiO2 film under the applied E-Field. FINDINGS: The direction of the E-Field relative to the TiO2 film controlled the PEM growth, resulting in non-linear growth or decay. In the case of non-linear LBL decay, there was a decrease in adsorbate mass in successive layers to a point of no growth.
RESUMO
Attenuated total reflectance infrared spectroscopy (ATR-IR) was used to study the dynamic layer-by-layer (LBL) growth of a sodium polyacrylate (NaPA)/poly(diallydimethylammonium) chloride (PDADMAC) multilayer on TiO2 particles. Molecular weights (Mw) used were 30 and 60 kDa for NaPA and 8.5 and 150 kDa for PDADMAC. IR spectra were recorded in situ as a function of time and were used to obtain the dynamic mass adsorbed and bound fraction of the polymers during each deposition step. For 30 kDa NaPA layers, the dynamics of adsorption show an initial rapid rise in mass followed by a slow increase toward a plateau value upon LBL with 150 kDa PDADMAC. In contrast, the 60 kDa NaPA layers achieve a plateau quickly and do not show a slow increase toward a plateau. In the case of LBL with 150 kDa PDADMAC, the dynamics of the bound fraction of polymer per layer suggest that polymer diffusion and conformational rearrangement occur for the layers of 30 kDa NaPA but not for the 60 kDa NaPA layers. Furthermore, PDADMAC adsorption profiles show that there is no diffusion of the PDADMAC layers and that PDADMAC flattens onto the underlying layer. A linear growth in the mass adsorbed per layer was observed for 150 kDa PDADMAC with both molecular weights of NaPA. In the case of 8.5 kDa PDADMAC, smaller growth increments and the desorption of underlying layers were observed. This work demonstrates the use of ATR-IR in obtaining the dynamics of LBL multilayer formation. Furthermore, it provides an example in which polymer diffusion during LBL film formation does not lead to exponential growth.
