Cellulose Triacetate Films Research Articles

Preparation and Characterization of Cellulose Nanocrystal‐Doped Cellulose Triacetate Optical Films by Sol‐Gel Process

AbstractA bio‐based nanocomposite optical film was obtained through a simple sol‐gel process and solution casting. The dispersion effect of cellulose nanocrystals (CNCs) gel and the optical properties, mechanical performance and thermal stability of CNC‐doped cellulose triacetate (TAC) films (TAC−X) were systematically evaluated. The results show that CNCs can be well dispersed in hydrophobic organic solvents and TAC matrices through the sol‐gel process. TAC−X film has excellent optical properties, its light transmittance is above 92 %, its haze value and birefringence are low, ranging from 0.21±0.01 % to 0.38±0.02 %, and (1.64±0.26)×10−6 to (2.49±0.50)×10−6 respectively. When doped with 2 wt % CNCs, the tensile strength and Young's modulus of the TAC‐2 film were 33.0 % and 30.1 % higher than those of the pure TAC film, separately. At the same time, the TAC−X film also maintains good thermal stability, with its glass transition temperature and maximum decomposition temperature falling between 215–216 °C and 366–368 °C respectively. The simple sol‐gel process provides a convenient and efficient way to use CNCs doping to enhance the physical and mechanical properties of TAC optical films.

Tuning 3D refractive indices via constrained uniaxial stretch in cellulose triacetate films plasticized with triethyl citrate

Tuning 3D refractive indices of polymers is urgently needed for optical films, but it is quite challenging. Here, we proposed a simple constrained uniaxial stretch method that successfully tuned the 3D refractive indices in cellulose triacetate (TAC) films plasticized with triethyl citrate (TEC). Our results suggest that, under constrained uniaxial stretch, the main chains and side groups prefer to orientate in the stretch direction and the constrained direction, respectively. Such a unique chain arrangement differentiates the refractive indices in three directions of the film. The branched small molecule TEC is also crucial for tuning refractive indices, which promotes chain activity and enhances the chain orientation under stretching, leading to a considerable change in refractive indices before samples fracture. The polymer film we fabricated possesses a direction-dependent optical performance, where the refractive index in the film thickness direction is between that of the stretch direction and constrained direction. This work provides a fundamental understanding on the chain structure and optical performance of polymer films. The constrained uniaxial stretch method, in general, should also be applicable to tuning other 3D physical properties through tuning the direction-dependent orientation of polymers.

The degradation behaviors of optical cellulose triacetate films in alkali/acid solutions

Abstract In this research, the degradation behaviors of ramie-based cellulose triacetate (CTA) films in alkali or acid solutions at room temperature were assessed. Moreover, the attenuated total reflection infrared (ATR-IR), physicochemical properties testing, scanning electron microscope (SEM), and thermogravimetric analysis/differential scanning calorimeter (TG/DSC) were employed to evaluate the detailed degradation process of the CTA films, which were treated by alkali or acidic aqueous solutions. The research results demonstrated that the dominant reaction of CTA films in NaOH solution with various concentrations is deacetylation. Intriguingly, the degradation behaviors of CTA films in HCl depend on the concentration of acid. The CTA films were almost immune to HCl with the concentration less than 1 mol L−1. However, films were degraded directly when the concentration of acid was higher than 1 mol L−1. This study provides a theoretical basis and further understanding for the treatment of dumped CTA films at room temperature.

Influence of Disinfection Methods on Cinematographic Film.

Microbiological contamination of cinematographic films can cause damage and loss of image information. A large part of the films is made with the base of cellulose triacetate, which has been used from the 1940s until today. Cellulose triacetate is relatively resistant to common organic solvents, but some types of microorganisms can contribute to its faster degradation. In this work, we tested four types of disinfectants suitable for mass disinfection and sufficiently effective against various types of microorganisms. Butanol vapours, a commercial mixture of alcohols (Bacillol® AF), Septonex® (an aqueous solution of [1-(ethoxycarbonyl)pentadecyl] trimethylammonium bromide) and ethylene oxide applied as a gas mixed with carbon dioxide were tested. Samples of a commercial film made of cellulose triacetate were disinfected. The samples were aged for 56 days at 70 °C and 55% RH. Changes in optical, mechanical and chemical properties were studied. None of the disinfectants affected the change in the degree of substitution. For samples disinfected with Bacillol® AF (alcohol mixture), part of the plasticiser (triphenyl phosphate) was extracted and the intrinsic viscosity of the cellulose triacetate solution was reduced after ageing. A slight decrease in intrinsic viscosity also occurred after disinfection with ethylene oxide. Compared to the non-disinfected samples, butanol vapours and Septonex® appear to be the most gentle disinfectants for the cellulose triacetate film base, within the studied parameters.

An effective cellulose triacetate interlayer to construct a dendrite-free zinc anode for advanced aqueous zinc-ion batteries

For Zn anodes of aqueous rechargeable zinc-ion batteries, the poor electrochemical performance caused by undesirable zinc dendritic formation and side reactions limit their practical application. Herein, a Zn2+ redistributor is created to reduce dendrites growth by inserting a cellulose triacetate (CTA) film as an interlayer between the zinc anode and the separator. The zinc dendritic formation and side reactions can be suppressed by the CTA interlayer. Consequently, the Zn anode covered by CTA interlayer exhibits highly reversible plating/stripping behavior with lifetime exceeding 2500 h and 600 h at current densities of 1 and 5 mA cm−2, respectively. In particular, the electrochemical performance of the full cells is investigated by using VO2 as the cathode and the CTA as interlayer. The Zn + CTA||VO2 full cells exhibit superior performance including high reversible capacity (490.2 mAh g−1 at 0.2 A g−1), excellent cycle performance (60.2% and 71.5% capacity retention after 5000 cycles at 5 A g−1 and 10 A g−1) and superior rate performance. This work demonstrates that designing a CTA interlayer is considered a cost-effective strategy to light up the practical application of aqueous zinc-ion batteries.

Factors to control the alignment of surface-treated titanium dioxide powders to maximize performance of sunscreens.

Titanium dioxide powders are contained in a large class of colour cosmetics and sunscreen formulas. When they are used, the formation of a uniform functional powder layer on the skin is an important factor to show their functionality, such as aesthetic and UV protection. Attempts were made to extract the factors that affect the UV shielding ability of the deposited powder layer. Seven kinds of surface treatments were conducted on nano-sized titanium dioxide powder to modify the surface characteristics. Dispersion samples were prepared by mixing these powders with liquids, such as mixed solutions of cyclopentasiloxane, isododecane, coconuts alkane and dimethicone using a disperser and a bead mill. The dispersions were applied using an applicator on cellulose triacetate film, polycarbonate film and polymethyl pentene film. Laser microscope observation and micro-gloss glossmeter analysis were carried out to assess the flatness of the deposited powder layers, and the UV shielding ability was evaluated using SPF analyser. Factors whose influences on the structure and UV shielding ability of the deposited powder layer being analysed were pseudo-HLB of the powders, liquids for preparing the dispersions and material of the substrates. Higher UV shielding ability was attained when powders having pseudo-HLB at around 6 were employed independent from the kinds of liquids and substrates. Flatness of the deposited layer was found to enhance the UV shielding ability of the UV-B region, while that of the UV-A region was scarcely influenced by the flatness. Employing lower surface tension liquids for preparing the dispersions and materials exhibiting lower polar components of surface free energy as substrates tended to enhance the UV shielding ability. Surface treatments conducted on the powders in this study were found to change UV shielding ability, especially UV-B shielding ability, and the relation between pseudo-HLB and UV shielding ability was scarcely influenced by the kinds of liquids. Both surface tension of liquids and the polar component of surface free energy of substrates affected the UV shielding ability. It was suggested that pseudo-HLB calculated based on chemical structure becomes useful information to choose optimum surface treatment to make uniform powder alignment independent from the surrounding environment.

Regulation of orientation birefringence for cellulose acetate film: The role of crystallization and orientation

Cellulose acetate (CA) based films are widely used in liquid crystal displays due to their outstanding transparency, and a certain orientation birefringence of CA films is required when they are used as retardation films. The regulation of orientation birefringence is usually from the perspective of stretch-induced orientation, while the effects of crystallization behaviors of CA films remain obscure. In this study, the roles of crystallization and orientation on the orientation birefringence of CA films were elucidated. For cellulose diacetate films, the orientation birefringence is dominated by the orientation degree. In comparison, apart from the orientation degree, crystallinity is another key variable to regulate the orientation birefringence of cellulose triacetate and plasticized cellulose triacetate films, originating from the birefringence heterogeneity of the crystalline and amorphous phases. These results provide valuable guidelines for the production of CA-based optical films with excellent optical performance.

Introduction of Ionic Liquids as Highly Efficient Plasticizers and Flame Retardants of Cellulose Triacetate Films

Introduction of Ionic Liquids as Highly Efficient Plasticizers and Flame Retardants of Cellulose Triacetate Films

Structural transition in cellulose triacetate films

Electron microscopy data are used to comparative analysis of the topological structure of the surface of two samples of cellulose triacetate (CTA) films. The samples were obtained from CTA solutions without use (sample N 1) and with the use of a small sodium fluoride additive that lowers the viscosity of the solution (sample N2). It is shown that in sample N 1, the nodes of the physical network of macromolecules are periodically alternating regions of local orientation order --- microdomains of average size d~18 nm. In sample N 2, due to repackaging of microdomains on the scale R>d, a uniformly disordered fractal cluster of the mesophase CTA is formed. The fractalization of the surface and the growth of structural anisotropy are consistent with the decrease in the viscosity of the solution and explain the change in the deformation properties of sample N 2 compared to N 1. Keywords: polymer films, electron microscopy, microdomains, mesophase, structural transition, fractal clusters.

Структурный переход в пленках триацетата целлюлозы

Electron microscopy data are used to comparative analysis of the topological structure of the surface of two samples of cellulose triacetate (СTA) films. The samples were obtained from CTA solutions without use (sample №1) and with the use of a small sodium fluoride additive that lowers the viscosity of the solution (sample №2). It is shown that in sample №1, the nodes of the physical network of macromolecules are periodically alternating regions of local orientation order - microdomains of average size d~18 nm. In sample №2, due to repackaging of microdomains on the scale R >d, a uniformly disordered fractal cluster of the mesophase CTA is formed. The fractalization of the surface and the growth of structural anisotropy are consistent with the decrease in the viscosity of the solution and explain the change in the deformation properties of sample №2 compared to №1.

Liver dysfunctions in workers with methylene chloride and methanol in connection with sanitary and hygienic examination of their working conditions

During the production of the base of the triacetate (non-combustible) film, vapors of methylene chloride, methanol, acetone are in the working room. In connection with the examination of the workers of this production, the state of the air environment in all the main departments of the workshop was also studied. The influence of individual operations on air pollution was revealed.

Radiation hardened H-diamond MOSFET (RADDFET) operating after 1 MGy irradiation

Although the surface conductivity of a hydrogen-terminated diamond (H-diamond) enables production of high-performance field effect transistors (FETs), the total ionizing dose effect is yet to be clarified for H-diamond FETs. We fabricated a RADiation hardened H-terminated Diamond metal–oxide–semiconductor FET (RADDFET) using an oxide gate dielectric deposited at high temperatures. This paper describes its stable operation after 1 MGy irradiation. H-diamond films were prepared using microwave plasma assisted chemical vapor deposition with a p+ layer for reduction of contact resistance. The Al2O3 passivation layer was deposited by atomic layer deposition at 450 °C to achieve operation in high-temperature environment; then a RADDFET was fabricated on them using a Ru electrode. Several current–voltage characteristics were compared before irradiation and after certain dose levels up to 1 MGy. Before they were irradiated in air, the dose rate was measured using a cellulose triacetate film dosimeter. Even after an irradiation level of 1 MGy, the off-current at gate bias voltage (VG) of 3 V was more than six orders of magnitude lower than the on-current at VG of −6 V. Variation of the drain current density (JDS) in the measurements was less than 2%. The threshold voltage shifted approximately 1.7 V with 3 kGy of x ray irradiation, but no marked degradation was confirmed at higher levels. The subthreshold swings were 238, 215, and 264 mV/decade, respectively, after irradiation of 100 kGy, 300 kGy, and 1 MGy. These results indicate that the RADDFET was very stable at higher doses after initial stabilization.

Gamma and electron beam irradiation effects for conservation treatment of cellulose triacetate photographic and cinematographic films

Photographic and cinematographic films of cellulose triacetate safeguarded in historical and cultural institutions are often contaminated by fungi when stored in inadequate conditions of humidity and temperature. The presence of fungi affects the image contained in the films, accelerates the process of biodeterioration and represents a risk to the health of people working with contaminated materials. In addition, another common physicochemical degradation affecting cellulose triacetate films causing deacetylation of polymer chain is called “vinegar syndrome”. Considering the dose interval established for the disinfection of cultural heritage materials, in this work the effects of irradiation with gamma rays and electron beam on photographic and cinematographic films of cellulose triacetate were evaluated. Additionally, the thermal stability behavior of the films and the feasibility of crosslinking of CTA films were investigated. Film samples were selected and characterized by FTIR-ATR spectroscopy. Irradiated samples by gamma rays and electron beam with radiation absorbed doses between 6 kGy and 200 kGy were examined by FEGSEM microscopy, UV–Vis spectrophotometry and differential scanning calorimetry (DSC). The results showed that disinfection by gamma and electron beam irradiation, in the dose range of 6 kGy–10 kGy, does not change or modification of main properties of the constitutive materials of photographic and cinematographic films. The applied dose of 50 kGy, both gamma rays and electron beam, indicated a crosslinking effect on the films and can be considered a possibility for the treatment of films affected by the “vinegar syndrome”.

How to Control Powder Alignment to Maximize Functionality and Performance of Color Cosmetics and Sunscreen

Control of powder alignment is essential for maximizing the functionality of color cosmetics and sunscreens. Various surface treatments were applied to nanosized titanium dioxide to modify their surface characteristics. Such modifications can be used to control the behavior of dispersions in cosmetics, enabling them to align uniformly. The powders were mixed with solvents and applied to a cellulose triacetate film. The features of powder alignment on the film were evaluated using several approaches. When the type of surface treatment changed by varying the weight ratio, there was no significant correlation between its alignment and treatment. However, when we focused on the pseudo-HLB each treated pigment, their alignments were correlated. It was confirmed that the powders subjected to the appropriate surface treatment combinations from the pseudo-HLB standpoint made it possible to align uniformly and create a smooth coating film. As a result, it has a high UV-shielding ability. The surface-treated powders in this study were found to change the UV shielding ability and surface roughness of the layer formed when they were formed by spreading the sample powder dispersion and drying of the film. It was suggested that the pseudoHLB, which is calculated based on the chemical structure after the surface treatment process, is useful for choosing the optimum surface treatment to create a uniformly aligned pigment layer.

Transparent and high barrier plasma functionalized acrylic coated cellulose triacetate films

Transparent and high moisture barrier acrylic coatings were obtained by deposition of acrylic resin containing crosslinking agents onto cellulose ester films, followed by exposure to atmospheric plasma. The effects of monomers, crosslinking agents, and polymerization methods were studied. The surface chemical composition, morphology, water vapor transmission rate (WVTR), light transmittance, and adhesion performance of the coated cellulose triacetate (CTA) films were characterized for the acrylic coated films and for different plasma treatments. Coated films showed a significant reduction in water vapor permeability while maintaining excellent transparency when compared with uncoated films. Furthermore, adhesion of the coating to the CTA film was also improved due to plasma treatment. It was also found that plasma curing on the coated oligomers can induce morphological changes and significantly increase surface roughness and hydrophilicity. The roughness texture observed via SEM analysis indicated that the types of plasma polymerization and the amount of crosslinking agents control the texture types for acrylic coating. Plasma-assisted acrylic coated CTA films can be used in electronic displays, medical, and packaging applications.

Sustainable atmospheric-pressure plasma treatment of cellulose triacetate (CTA) films for electronics

Surface treatments of cellulose triacetate (CTA) films via atmospheric pressure plasmas containing helium and either O2 or C3F6 as plasma reactive gas were performed to study their effects on moisture barrier, transmittance, thermal, surface chemistry, and morphological properties. Plasma treated CTA films were characterized using X-ray photoelectron spectroscopy (XPS), attenuated total reflectance-Fourier transform infrared spectroscopy, time-of-flight secondary ion mass spectrometry (ToF-SIMS), differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy analytical techniques. Both surface chemical and morphological changes were correlated with water vapor transmission rates (WVTRs) and contact angle measurements. XPS spectra showed that the relative chemical composition of the C 1s spectra after O2 plasma treatments exhibits an increase in the relative amount of C—C bonds, which may be due to a change in surface cross-linking. ToF-SIMS spectra showed the depth of treatment of atmospheric plasma treatment of CTA films at about 100 nm. The WVTR of the CTA film was reduced up to 20% after sustainable atmospheric O2/helium plasma, while no significant changes were observed in light transmittance. Thus, the use of sustainable atmospheric plasmas to enhance moisture barrier while maintaining other critical properties such as light transmittance, thermal stability, and morphology of a CTA film could provide significant benefits to the electronics industry.

Quantification of sorption, diffusion, and plasticization properties of cellulose triacetate films under mixed-gas CO2/CH4 environment

Membrane technology is employed in large-scale removal of acid gases from natural gas, and cellulose acetate is by far the most adopted material for this application. Because of its utmost industrial relevance, we analyzed the gas sorption behavior of CO2–CH4 mixtures in cellulose triacetate (CTA) at 35 °C. CO2 solubility in CTA was only slightly affected by the presence of methane, whereas competition effects sharply reduced CH4 uptake. Regardless of mixture concentration, CO2vs. CH4 solubility coefficients regressed linearly, which translated in solubility selectivities that increased as equilibrium pressures increased. Specifically, compared to other relevant glassy polymer membrane materials, CTA positioned very close to the solubility selectivity upper bound at infinite dilution and demonstrated the highest affinity to CO2 at all investigated pressures. The experimental solubility and permeability data were used in the framework of the solution-diffusion theory to determine pure- and mixed-gas concentration averaged diffusion coefficients of CTA. CO2 diffusion was essentially unaffected by mixture effects, whereas methane diffusivity was boosted by the CO2-induced plasticization of CTA. The ratio between the pure- and mixed-gas concentration averaged diffusion coefficients of methane was used to quantify the effect of plasticization on the mixed-gas performance of CTA and other relevant membrane materials previously analyzed in similar experimental studies. When we further extended this comparison in a mixed-gas diffusion analysis (at 10 atm partial pressure), we observed that CTA had lower diffusion selectivity due to an inferior size-sieving capability than a reference material, 6FDA-mPDA polyimide, but displayed superior solubility selectivity.

EFEITO DO TEOR DE GLICEROL NO TRANSPORTE DE VAPOR D’ÁGUA ATRAVÉS DE FILMES DE TRIACETATO DE CELULOSE PRODUZIDOS A PARTIR DO APROVEITAMENTO DA PALHA DE MILHO (ZEA MAYS L.)

EFFECT OF GLYCEROL CONTENT ON WATER VAPOR TRANSPORT THROUGH CELLULOSE TRIACETATE FILMS PRODUCED FROM THE USE OF CORN (Zea mays L.) STRAW. Glycerol is a plasticizer widely used due to its good plasticization efficiency, great availability, biocompatibility and low exudation. It is a renewable raw material that, when introduced in biodegradable films, promotes significant changes in its properties and, thus, guarantees a wide spectrum of application. In this work, corn straw was used to produce cellulose triacetate films from mixtures with glycerol (10%, 20% and 30%). The films were characterized by X-Ray Diffraction, Scanning Electron Microscopy, Thermogravimetric Analysis, Water Vapor Transport Rate and Water Vapor Permeation. The cellulose triacetate films produced with 20% glycerol have high barrier properties, when compared to films with concentrations 0, 10 and 30%.

Are we overestimating the permanence of cellulose triacetate cinematographic films? A mathematical model for the vinegar syndrome

Among the earliest signs of degradation in cellulose triacetate cinematographic films is the generation of acetic acid due to hydrolytic deacetylation of the polymer, marked by an increase in the acidity of the films and emissions of acetic acid leading to a characteristic vinegar odour. We propose a mathematical model for predicting the onset of the vinegar syndrome which accounts for the autocatalytic effect of acetic acid on the deacetylation reaction. Model parameters are estimated from previously published experimental data from other research groups. These show free acidity changes in cellulose triacetate films subjected to accelerated ageing at temperatures of 70–100 °C. The model is validated against a different set of previously published experimental data of cellulose triacetate films aged at 21 °C and 35 °C, at 20, 35 and 50% relative humidity. The model demonstrates good quantitative agreement with the published experimental data. Predictions of film permanence at lower temperatures, similar to those present in the archives in which the films are typically stored, are made and compared with the predictions of film conservation guidelines. The results indicate that film permanence may be overestimated by existing guidelines, which do not account for autocatalysis in their modelling of the deacetylation rate. Our results suggest that cold storage, a common film conservation strategy, may be less effective at inhibiting degradation than previously thought. As cold storage typically requires film to be kept in confined spaces with limited air movement, conditions which promote autocatalysis, the inclusion of autocatalysis in our model is highly applicable to simulating this environment.

Structural evolution of cellulose triacetate film during stretching deformation: An in-situ synchrotron radiation wide-angle X-Ray scattering study

Structural evolutions of cellulose triacetate (CTA) film during uniaxial stretching process at different temperatures were studied by in-situ synchrotron radiation wide-angle X-ray scattering (WAXS) combined with dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The results show that four temperature regions can be divided for the CTA film stretching, in which different structural evolutions and deformation mechanisms will be observed. The structural evolutions of CTA film at temperatures between 60 and 125 °C (region I) are seriously influenced by the absorbed moisture, resulting in a large variation of the crystallinity (χc). At temperatures around Tg (195 °C), stretch-induced orientations for crystal can be achieved more easily although χc and crystal size have no large change compared with the flexible-chain semi-crystalline polymers like polyethylene. Interestingly, the CTA film presents various deformation mechanisms including the elongation of amorphous and slipping, formation, destruction and recrystallization of crystals during stretching at different temperatures, which are often observed for the flexible-chain semi-crystalline polymers. These results can provide valuable guidance for the hot-stretching processing and application of CTA retardation film.