Highly transparent nancomposite films based on polybutylmethacrylate and functionalized cellulose nanocrystals

Efficient surface functionalization of cellulose nanocrystals (CNC) with hydroxyl butyl acrylate monomer (HBA) was carried on under mild condition using N,N′-carbonyldiimidazole as an activator. The grafting of the acrylic monomer was shown to bring about the high yield grafting of polymer chains on the functionalized CNC during in situ polymerization process. Surface functionalization of CNC with HBA and the polymer grafting on the modified CNC were confirmed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Nanocomposite film prepared from in situ polybutylmethacrylate polymerization process using HBA functionalized nanocrystals exhibited high transparency degree here assigned to improved dispersion. DMA analysis proved that the best mechanical/rheological performance is obtained for HBA–CNC contents of 4 %.     

Highly transparent and flexible field emission devices based on single-walled carbon nanotube films

Single-walled carbon nanotubes (SWNTs) have been used successfully to fabricate highly transparent and flexible field emission displays (FEDs). Field emission measurements indicated that SWNTs films have great potential to work as building blocks for next generation transparent and flexible FEDs.     

Bio and soft-imprinting lithography on bacterial cellulose films

Bacterial cellulose (BC) is a biocompatible polysaccharide produced by bacteria currently used in packaging, cosmetics, or health care. A highly attractive feature of BC is the possibility of patterning the BC pellicle during its biosynthesis, a concept coined as bio-lithography. BC-patterned films have demonstrated improved properties for cellular-guided growth, implant protection, or wound dressing. However, aspects such as the diversity and size of the features patterned, how those features withstand postprocessing steps, or if large areas can be patterned remain unanswered. Gathering knowledge on these characteristics could extend the use of patterned cellulose-based materials in emerging fields such as transient devices, nanogenerators, or microfluidics. Here, we show that bio-lithographed BC films present good-quality micropatterned features for various motifs (wells, pillars, and channels) in a wide range of sizes (from 200 to 5 μm) and areas as large as 70 cm². Besides, we have studied the fidelity of the motifs and the fiber organization for wet, supercritical, and oven-dried films. When wells and pillars were patterned, the x and y dimensions were faithfully replicated in the wet and dried samples, but only wet and supercritically dried films afforded mold accuracy in the z-direction. In addition, x/z ratio should be carefully considered for obtaining self-standing pillars. Finally, we compared bio-lithography and soft-imprint lithography. In the latter case, fiber alignment was not observed and the depth of the resulting features dramatically decreased; however, this technique allowed us to produce submicron features that remain after the rewetting of the BC films.     

Glucomannan composite films with cellulose nanowhiskers

Spruce galactoglucomannans (GGM) and konjac glucomannan (KGM) were mixed with cellulose nanowhiskers (CNW) to form composite films. Remarkable effects of CNW on the appearance of the films were detected when viewed with regular and polarizing optical microscopes and with a scanning electron microscope. Addition of CNW to KGM-based films induced the formation of fiberlike structures with lengths of several millimeters. In GGM-based films, rodlike structures with lengths of several tens of micrometers were formed. The degree of crystallinity of mannan in the plasticized KGM-based films increased slightly when CNW were added, from 25 to 30%. The tensile strength of the KGM-based films not containing glycerol increased with increasing CNW content from 57 to 74 MPa, but that of glycerol-plasticized KGM and GGM films was not affected. Interestingly, the notable differences in the film structure did not appear to be related to the thermal properties of the films.     

Nanofibrillated cellulose/nanographite composite films

Though research into nanofibrillated cellulose (NFC) has recently increased, few studies have considered co-utilising NFC and nanographite (NG) in composite films, and, it has, however been a challenge to use high-yield pulp fibres (mechanical pulps) to produce this nanofibrillar material. It is worth noting that there is a significant difference between chemical pulp fibres and high-yield pulp fibres, as the former is composed mainly of cellulose and has a yield of approximately 50 % while the latter is consist of cellulose, hemicellulose and lignin, and has a yield of approximately 90 %. NFC was produced by combining TEMPO (2,2,6,6-tetramethypiperidine-1-oxyl)-mediated oxidation with the mechanical shearing of chemi-thermomechanical pulp (CTMP) and sulphite pulp (SP); the NG was produced by mechanically exfoliating graphite. The different NaClO dosages in the TEMPO system differently oxidised the fibres, altering their fibrillation efficiency. NFC–NG films were produced by casting in a Petri dish. We examine the effect of NG on the sheet-resistance and mechanical properties of NFC films. Addition of 10 wt% NG to 90 wt% NFC of sample CC2 (5 mmol NaClO CTMP-NFC homogenised for 60 min) improved the sheet resistance, i.e. from that of an insulating pure NFC film to 180 Ω/sq. Further addition of 20 (CC3) and 25 wt% (CC4) of NG to 80 and 75 wt% respectively, lowered the sheet resistance to 17 and 9 Ω/sq, respectively. For the mechanical properties, we found that adding 10 wt% NG to 90 wt% NFC of sample HH2 (5 mmol NaClO SP-NFC homogenised for 60 min) improved the tensile index by 28 %, tensile stiffness index by 20 %, and peak load by 28 %. The film’s surface morphology was visualised using scanning electron microscopy, revealing the fibrillated structure of NFC and NG. This methodology yields NFC–NG films that are mechanically stable, bendable, and flexible.     

Highly transparent memory states in polymer dispersed liquid crystal films

Electro-optical properties of polymer dispersed liquid crystal (PDLC) films which have reversed morphology are investigated. Highly transparent memory states, for which transmittances exceed more than 80 per cent, are observed in these PDLC films. The saturation voltage V₉₀ can be decreased by a PTF (a phase transition with a field) operation and becomes 10 times lower than that without PTF operation. A contrast ratio of more than 600 is obtained in the memory state of a thick PDLC film.     

Highly transparent memory states in polymer dispersed liquid crystal films

Abstract

Electro-optical properties of polymer dispersed liquid crystal (PDLC) films which have reversed morphology are investigated. Highly transparent memory states, for which transmittances exceed more than 80 per cent, are observed in these PDLC films. The saturation voltage V ₉₀ can be decreased by a PTF (a phase transition with a field) operation and becomes 10 times lower than that without PTF operation. A contrast ratio of more than 600 is obtained in the memory state of a thick PDLC film.     

Ag/DNQ-novolac-based nanocomposite films for controllable UV lithography morphological patterning

In this study, the detailed characterisation of silver (Ag) nanoparticles/polymer nanocomposite chemical structure and morphology of grating has been carried out. Scanning electron microscopy measurements show spherical shape of Ag nanoparticles (40–80 nm in diameter) prepared in chloroform by reduction of silver nitrate. In the positive photoresist based on 2-diazo-2H-naphthalen-1-one (DNQ)–novolac, Ag nanoparticles were deposited from organic colloidal solution. The content of nanoparticles in the polymer matrix was varied by increasing the concentration of Ag colloidal solution. Grating was formed by contact lithography. The quantification of Ag nanoparticles and chemical analysis of Ag/DNQ-novolac-based nanocomposite was performed by means of energy dispersive X-ray analyzer and SEM/EDS. In order to study the effect of Ag nanoparticles on the DNQ-novolac-based nanocomposite structure, investigations with Fourier transform infrared spectroscopy were conducted. Ag nanoparticles cause changes associated with substituent-sensitive out-of-plane C–H bending vibrations of aromatic ring. Ag/DNQ-novolac-based nanocomposite film surface morphology and grating topography imaging were performed using atomic force microscopy. Added Ag nanoparticles change the geometrical parameters of the gratings. The split of corrugations was achieved in Ag/DNQ-novolac-patterned films. Their morphology can be tailored by altering the content of Ag nanoparticles.     

可制备透明紫外阻隔膜的可聚合木质素的研究

作为制浆造纸业的副产物,由于溶解性太差,工业木质素在大规模、增值利用方面一直面临巨大挑战。本文中,通过10-十一碳烯酰氯（11ene）与脱碱木质素（DAL）的羟基进行酯化反应,合成了三种具有不同取代度的可聚合物木质素（DAL-11ene-1、DAL-11ene-2和DAL-11ene-3）。通过1H NMR、FTIR和UV-vis吸收光谱对其结构进行了表征。通过31P NMR测定了羟基取代度。研究发现,引入取代基后三种目标产物在商用丙烯酸酯单体HDDA中的溶解性均获得不同程度的改善,其中取代度最高的DAL-11ene-3在HDDA中的添加量可以达到10 wt%。将DAL-11ene-3以1–5 wt%的比例掺入预聚物配方中,经光固化制备了五种聚合物薄膜（DLE1–DLE5）,对其紫外阻隔性能、光稳定性、热稳定性、表明形貌进行了研究。结果表明,五种薄膜均表现出优异的紫外阻隔性能,能阻挡所有UVC和UVB光以及大部分UVA光,其中掺入量最高的DLE5膜的紫外阻隔效果最好,可以阻挡超过95%的UVA光并且具有较好的光稳定性。此外,五种薄膜在可见光区具有很高的透过率。进一步地,将预聚物键合到烷基化的玻璃基底上,制备了五种相应的玻璃涂层（DLE1-DALE5）,并对其表面润湿性和机械性能进行了评价。玻璃基底上的聚合物涂层表现出更高的硬度和模量以及更疏水的性能。这项工作提出了一种可行的方案来实现木质素的增值利用并有望应用于生活中的各类防紫外薄膜或涂层。     

Preparation of flexible and transparent polylactic acids films by crystallization manipulation

Highly flexible and transparent polylactic acids (PLAs) films were successfully prepared by manipulating their crystallization. The semicrystalline poly(L ‐lactic acid) (L) was blended with a noncrystalline poly(DL ‐lactic acid) (DL) together with diglycerol tetraacetate (DGTA). Optimal DGTA content to plasticize PLAs was about 17%. Addition of DL hindered the crystallization of the films. Tensile strengths of the films having DL content more than 5% were about 10 MPa while the elongations at break were boosted as DL content increased. Films having L/DL ratio of 50/50 showed elongations at break of 270%. Stretch ability and clarity of films containing 15–50% DL were fair although they were subjected to annealing at 60 °C for 1 h. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6489–6495, 2008     

Novel approaches to flexible visible transparent hybrid films for ultraviolet protection

Herein, we present an overview of the most recent achievements and innovations regarding the development of flexible visible transparent films for selective ultraviolet (UV) shielding, with focus on those based on hybrid inorganic–organic materials. The main synthetic paths used nowadays to ensure a high degree of protection are reviewed. Polymers containing organic UV absorbing molecules, hybrid mixtures of polymers and nanoparticles, and the recently introduced series of structures displaying structural color, are identified as the three main types of materials used for this purpose. The use of biocompatible and flexible films to achieve spectrally selective UV protection can find applications in a wide diversity of fields such as photo‐treatment of skin diseases, food and beverage packing, and storage of cosmetics. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

UV cured transparent films including non‐aqueous conductive microgels

UV cured transparent films containing non‐aqueous conductive microgels coated with poly(aniline)/dodecyl benzenesulfonic acid(DBSA) were obtained. The conductive microgels were prepared by interface polymerization of aniline/DBSA in the presence of non‐aqueous polymeric microgels. The electrical conductivity and the particle size of the prepared conductive microgel were 0.5 S/cm and 58 nm, respectively. The prepared conductive microgels were easily blended with a UV curable coating formulation, and then were cured to make highly optically transparent films. For the UV cured film containing about 35 wt% of the conductive microgels, a surface resistance in the range of 10⁷ to 10⁸ Ω/square was obtained. In a polar cosolvent, such as NMP and m‐cresol, the critical volume was shifted to the lower range, with a value of 10 wt%. The UV cured films containing the conductive microgels exhibited good electrical stability against the thermal aging and humidity. Copyright © 2002 John Wiley & Sons, Ltd.     

Experimental and theoretical investigation on surfactant segregation in imprint lithography

The effects of template surface composition on fluorinated surfactant segregation were investigated for imprint lithography with photopolymerizable vinyl ether formulations. Heptadecafluoro-1,1,2,2-tetrahydrodecyl vinyloxy-methyloxy dimethylsilane, containing a vinyl ether group, was employed as the surfactant, and blanket templates were pressed onto the liquid and illuminated with UV radiation from below. The extent of surfactant segregation to the vinyl ether-template interface before polymerization was characterized using contact angle measurements and angle-resolved X-ray photoelectron spectroscopy after removing the template from the cured vinyl ether polymer. Blanket surfaces consisting of bare quartz, high-density polyethylene, and quartz treated with tridecafluoro-1,1,2,2,-tetrahydrooctyltrichlorosilane afforded templates with different surface energy and polarity. The highest degree of surfactant segregation was found with tridecafluoro-1,1,2,2,-tetrahydrooctyltrichlorosilane-treated quartz, whereas little surfactant segregation was found for bare quartz. A thermodynamic model is developed to predict the surface segregation profiles.     

Mold design rules for residual layer-free patterning in thermal imprint lithography

We present the mold design rules for assuring residual layer-free patterning in thermal imprint processes. Using simple relations for mass balance, structural stability, and work of adhesion, we derive the conditions with respect to the given single or multigeometrical feature of the mold, which are compared with simple thermal imprint experiments using soft imprint molds. Our analysis could serve as a guideline for designing the optimum mold geometry and selecting mold material in residual layer-free thermal imprint processes.     

Highly transparent solution processed In-Ga-Zn oxide thin films and thin film transistors

Highly transparent In-Ga-Zn oxide (IGZO) thin films were fabricated by spin coating using acetate- and chlorate-based precursors, and thin film transistors (TFTs) were further fabricated employing these IGZO films as the active channel layer. The impact of the post-annealing temperature on the physical properties of IGZO films and performance of IGZO TFTs were investigated. Compared to the nitrate-based IGZO precursor, the chlorate-based precursor increases the phase change temperature of IGZO thin films. The IGZO films changed from amorphous to nanocrystalline phase in an annealing temperature range of 600–700 °C. The transparency is more than 90% in the visible region for IGZO films annealed with temperatures higher than 600 °C. With the increase of post-annealing temperature, the carrier concentration of IGZO film decreases, while the sheet resistance increases firstly and then saturates. The bottom-gate TFT with IGZO channel annealed at 600 °C in oxygen showed the best performance, which was operated in n-type enhancement mode with a field effect mobility of 1.30 cm²/V s, a threshold voltage of 10 V, and a drain current on/off ratio of 2.5 × 10⁴.     

Influence of high loading of cellulose nanocrystals in polyacrylonitrile composite films

Polyacrylonitrile-co-methacrylic acid (PAN-co-MAA) and cellulose nanocrystal (CNC) composite films were produced with up to 40 wt% CNC loading through the solution casting method. The rheological properties of the solution/suspensions and the structural, optical, thermal, and mechanical properties of the resulting films were investigated. The viscosity of the composite suspensions increased with higher CNC loadings and with longer aging times. PAN-co-MAA/CNC films maintained a similar level of optical transparency even with up to 40 wt% CNC loading. The glass transition temperature (Tg) increased from 92 to 118 °C, and the composites had higher thermal stability below 350 °C compared to both neat PAN-co-MAA and neat CNC. The mechanical properties also increased with higher CNC loadings, elastic modulus increased from 2.2 to 3.7 GPa, tensile strength increased from 75 to 132 MPa, and the storage modulus increased from 3.9 to 10.5 GPa. Using the Kelly and Tyson model the interfacial shear strength between the PAN-co-MAA and CNC was calculated to be 27 MPa.     

Recyclable and transparent bacterial cellulose/hemiaminal dynamic covalent network polymer nanocomposite films

Recyclable and transparent nanocomposite films based on bacterial cellulose (BC) and hemiaminal dynamic covalent network polymer (HDCN) have been synthesized by in situ polymerization of 4,4′-diaminodiphenyl ether (ODA) with paraformaldehyde. Transparency and structural and mechanical properties of such nanocomposite films are investigated. It was found that BC/HDCN nanocomposite films exhibits a high optical transparency (86 % at 550 nm). Scanning electron microscopy reveals excellent compatibility of the reinforcement of BC nanofibers and HDCN matrix, which leads to the improvement of 20 and 200 % in tensile strength and storage modulus, respectively, as compared to neat HDCN films. BC hydrogels are readily recoverable from nanocomposite films by the sulphuric acid treatment and ODA monomer is deposited and also recycled.