Hydrophilic Film Research Articles

Copper Polypropylene Metal Plastic Composite Copper Foil: Future-Proof Anode Current Collector Solution for Lithium-Ion Batteries with High Energy Density.

Composite copper foil is considered to be the future-proof anode current collector solution for lithium-ion batteries (LIBs) with high energy density, for its light weight and low cost. Polypropylene (PP) film is widely used as the support layer of composite copper foil current collectors (CCs) due to its excellent mechanical properties and chemical stability. However, the interface adhesion between the PP layer and the copper layer is weak, due to the significant difference in surface energy. In this study, we prepared a hydrophilic PP film by air plasma treatment. After magnetron sputtering and electroplating, the composite copper foil (PP@Cu-1) with strong adhesion was then successfully prepared. In the T-peel test, for PP@Cu-1, the pull required to separate PP from the copper layer is approximately 7 times that of PP@Cu-0. The PP@Cu-1 composite copper foil exhibits excellent electrochemical properties when applied to LIBs. As an anode CC material, it could be a favorable competitor to conventional commercial Bare Cu and holds broad prospects for application in high-energy-density LIBs.

Surface modification and patterning of polymer thin films by plasma and adsorption behavior of proteins

The surface wettability property of hydrophobic polystyrene (PS) and hydrophilic polyethylene glycol (PEG) thin films subjected to modification by direct current plasma glow discharge is studied. The polymer films exhibited change of surface wettability on exposure to air, nitrogen, oxygen or argon plasmas. In PS films a swift modification to hydrophilic surface and subsequent steady recovery following first order kinetics are observed. The rate of modification and recovery are adjustable by adjusting the plasma ambient and parameters and additional wet-chemical treatment using ionic solutions. In PEG films the hydrophobic wettability evolve with ageing following the first order kinetics, and is stable for long period on exposure to air ambient. Moreover, a vapor deposition like process is possible using the PEG films as source to deposit self-assembled molecular layers with hydrophobic wettability on other surfaces. Using these surface modification or molecular deposition processes, the fabrication of wettability patterns in the surface of PS and PEG films and on other surfaces by vapor transport using PEG films, and also the possibility to produce gradient wettability patterns are demonstrated. Moreover, the adsorption behavior of immuno-specific system of proteins on surface modified hydrophilic PS films is studied.

Small-Molecule Mixed Ionic-Electronic Conductors for Efficient N-Type Electrochemical Transistors: Structure-Function Correlations.

The fundamental challenge in electron-transporting organic mixed ionic-electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6-type/U-shaped non-fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol (OEG; g) sidechains from 1g to 3g, affording OMIECs 1gY, 2gY, and 3gY, respectively. The crystal structure of 1gY preserves key structural features of the Yn series: a U-shaped/planar core, close π-π molecular stacking, and interlocked acceptor groups. Versus inactive Y6 and Y11, all of the new glycolated compounds exhibit mixed ion-electron transport in both conventional organic electrochemical transistor (cOECT) and vertical OECT (vOECT) architectures. Notably, 3gY with the highest OEG density achieves a high normalized transconductance of 25.29 S cm-1, an on/off current ratio of ~106, and a turn-on/off response time of 94.7/5.7 ms in vOECTs. Systematic optoelectronic, electrochemical, architectural, and crystallographic analysis explains the superior 3gY-based OECT performance in terms of denser ngY OEG content, increased crystallite dimensions with decreased long-range crystalline order, and enhanced film hydrophilicity which facilitates ion transport and efficient redox processes. Finally, we demonstrate an efficient small-molecule-based complementary inverter using 3gY vOECTs, showcasing the bioelectronic applicability of these new small-molecule OMIECs.

Small‐Molecule Mixed Ionic‐Electronic Conductors for Efficient N‐Type Electrochemical Transistors: Structure‐Function Correlations

The fundamental challenge in electron‐transporting organic mixed ionic‐electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6‐type/U‐shaped non‐fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol (OEG; g) sidechains from 1g to 3g, affording OMIECs 1gY, 2gY, and 3gY, respectively. The crystal structure of 1gY preserves key structural features of the Yn series: a U‐shaped/planar core, close π‐π molecular stacking, and interlocked acceptor groups. Versus inactive Y6 and Y11, all of the new glycolated compounds exhibit mixed ion‐electron transport in both conventional organic electrochemical transistor (cOECT) and vertical OECT (vOECT) architectures. Notably, 3gY with the highest OEG density achieves a high normalized transconductance of 25.29 S cm‐1, an on/off current ratio of ~106, and a turn‐on/off response time of 94.7/5.7 ms in vOECTs. Systematic optoelectronic, electrochemical, architectural, and crystallographic analysis explains the superior 3gY‐based OECT performance in terms of denser ngY OEG content, increased crystallite dimensions with decreased long‐range crystalline order, and enhanced film hydrophilicity which facilitates ion transport and efficient redox processes. Finally, we demonstrate an efficient small‐molecule‐based complementary inverter using 3gY vOECTs, showcasing the bioelectronic applicability of these new small‐molecule OMIECs.

Using a Carbon Quantum Dot Suspension as a New Solvent for Clear Hydrophobic Surface Coating on Hydrophilic PVA Films.

Polyvinyl alcohol (PVA) is a popular material used in the packaging industry. However, it is vulnerable to moisture, which can affect its performance and durability. Introducing hydrophobic substances, such as tetraethyl orthosilicate (TEOS) and hexadecyltrimethoxysilane (HDTMS), on the top layer of PVA can help maintain the excellent properties of PVA under high-humidity conditions. The low compatibility of hydrophobic materials with the hydrophilic layers allows them to aggregate more easily. To overcome these issues, we focused on the effects of particle size when increasing the coating suspension's dispersibility. A carbon quantum dot (CQD) suspension is an appropriate novel solvent for hydrophobic TEOS/HDTMS coating suspensions because its particles are small and light and exhibit good dispersibility. The CQD suspension formed a smooth hydrophobic coating on the TEOS/HDTMS materials. Furthermore, the uniformly coated PVA with the CQD suspension exhibited a water contact angle of 110°. The water droplets remained intact without being absorbed, confirming the effectiveness of the surface coating facilitated by CQDs. These results suggested that CQDs improved the dispersibility and enhanced the coating quality of TEOS/HDTMS on PVA. Enhancing the hydrophobicity of PVA is ideal for applications in packaging and other fields.

Octadecylamine modified gelatin-based biodegradable packaging film with good water repellency and improved moisture service reliability

Industrial gelatin is a good candidate for fabricating biodegradable packaging film, but the strong hydrophilicity of gelatin-based film lowers its moisture service reliability. Herein, we demonstrated a low surface energy water repellency surface design combined with covalent cross-linking for decreasing the water absorption and improving the moisture service reliability. Biodegradable octadecylamine (ODA) was chosen as the low surface energy providing material to fabricate the water repellency surface through a dehydration condensation reaction between the amine groups of ODA and gelatin chains via tetra-hydroxymethyl phosphonium chloride (THPC) in an aqueous phase. THPC also was employed as the cross-linking agent to form covalent bonding between the gelatin chains. The results determined that ODA modification and covalent cross-linking endowed the gelatin-based film with good water repellency and improved moisture service reliability. But high dose of ODA would result in phase separation and mechanical strength loss of the fabricated film. Additionally, ODA modification did not change the biodegradability of gelatin-based film, all the modified films were completely biodegradable in natural soil. Considering the sustainable modification process and abundant raw materials, the proposed strategy facilitates the effective utilization of low value industrial gelatin and provides a facile way for gelatin-based film as biodegradable packaging film.

Boosting photocatalytic stability: hydrophilic Sr-doped ZnO thin films prepared via the SILAR method for enhanced performance over multiple cycles

This study deals with the synthesis and characterization of Sr-doped ZnO thin films with different concentrations (1, 3, 5, and 7 wt%) using the SILAR method (Successive Ionic Layer Adsorption and Reaction). The main objective is to evaluate the effectiveness of the films as photocatalysts for the degradation of methylene blue under natural sunlight conditions. X-ray diffraction analysis confirms the polycrystalline nature of the films, with the crystallite size increasing with increasing Sr doping along the (100) plane. Morphological changes on the film surfaces are revealed by scanning electron microscopy and correlate with the increasing Sr content. Energy dispersive x-ray spectroscopy (EDX) confirms that there are no impurities in all films. 3D surface topography shows that higher Sr doping leads to an increase in average roughness and root mean square (Rq) values. Measurements of the water droplet contact angle (WDCA) indicate the hydrophilicity of the surface. Optical analysis shows that the absorption capacity of the films increases with Sr doping and shifts slightly towards longer wavelengths. Additionally, the band gap energy (Eg) shows a linear increment with higher Sr dopant concentrations. The unique contribution of this work lies in the careful investigation of the photocatalytic degradation of methylene blue using Sr-doped ZnO films as photocatalysts under natural sunlight. In particular, the films doped with 5 wt% Sr show exceptional performance, achieving degradation rates of 94.82%, 94.61%, and 93.48% for the first, second, and third cycles, respectively. The novelty of these results lies in the successful synthesis of Sr-doped ZnO thin films by SILAR, the comprehensive characterization of their properties and the remarkable photocatalytic efficiency observed under real sunlight conditions. This work provides valuable insights into the potential application of these unique films for the efficient degradation of methylene blue, thus contributing to the further development of environmentally friendly photocatalytic materials.

Fish-Mimicking Hydrophilic and Hygroscopic Transparent Films with Long-Lasting Anti-Oil Adhesion and Its Application to PET Bottles

With the recent ban on the production and use of long-chain perfluorinated compounds, the development of alternative approaches to prepare liquid-repellent surfaces that avoids the use of such compounds has become an urgent issue. We have succeeded in the development of fish-mimicking hydrophilic transparent hydrogel-based films with long-lasting anti-oil adhesion properties. Such films could be prepared by simply mixing poly(vinylpyrrolidone) (PVP), nanoclay particles (NCPs), and a waterborne aminosilane (AOS) using an integral blend (IB) method. When submerged in water, these films displayed underwater superoleophobicity (advancing and receding contact angles (CAs) of diiodomethane were ~171°/~163°) with low CA hysteresis (less than 8°), because the hydrophilic nature of the films promoted the formation of a thin layer of adsorbed water on the topmost film surfaces, similar to fish scales. Furthermore, when our films were coated onto the inside of poly(ethylene terephthalate) (PET) bottles and pre-wetted using 80 °C hot water vapors, these film surfaces could effectively repel various oils and were able to maintain their oil-repellent properties for more than 5 weeks. These water-driven, non-perfluorinated transparent hydrogel-based films are expected to increase recycling of PET bottles for oils that are generally incinerated or landfilled.

Thermodynamic water adsorption analysis of biodegradable films based on corn starch-chitosan added with triblock copolymers

Adding triblock copolymers to hydrophilic films is an option to improve the functional properties and water resistance under high equilibrium relative humidity (RHeq) environments. Sorption isotherms of corn starch-chitosan based films added with triblock copolymers (L64 and P123) measured at 4, 20, and 36 °C were fitted using the Guggenheim-Anderson-De Boer equation. Thermodynamic analysis allowed allocating the minimum integral entropy value between 0.09 and 0.50 of water activity. The compensation enthalpy-entropy showed that the entropy driven the process at low water activities (0.10–∼0.33) and the enthalpy driven the water sorption at high water activities (∼0.33–∼0.90).

Design and Characterization of Printed Flexible Humidity Sensor

The development of humidity sensors is essential for applications in the environmental, agriculture, medical and semiconductor industries [1-2]. The basic mechanism of humidity sensors is explained by a Grotthuss chain reaction, which is usually simplified as a proton-hopping process [3]. This refers to a dynamic charge transfer process at a certain relative humidity (RH). The humidity sensors can be of different types such as capacitive type, resistive, colorimetric and surface acoustic wave [4-7]. Capacitive type sensors are linear, require less complex circuitry and can operate for a wide range of humidity [8]. A typical capacitive type humidity sensor uses hydrophilic films as sensing layers which are stable at higher humidity levels [9]. Polymers that are being used for the fabrication of capacitive type humidity sensors include poly (2-hydroxyethyl methacrylate) (pHEMA) [9], cellulose acetate butyrate (CAB) [10], polyimide [11] and polymethyl methacrylate (PMMA) [12]. In this work, a humidity sensor has been fabricated on glass and flexible substrates.The design of humidity sensor consists of printed pattern of a conductor such as silver and a spin coated dielectric such as polymer poly (2-hydroxyethyl methacrylate) (p-HEMA) and polyimide. The printing of conductor was done in an interdigitated pattern as shown in figure 1. The thickness of sensitive materials was controlled by varying the spin time from 10 to 30 seconds. A thick solution of sensitive materials was prepared by adding a 3 gm of polymer in 50 mL ethanol in the case of p-HEMA. Currently we are preparing one more set of samples using polyimide and we will present a comparison of two humidity sensors- one with p-HEMA and another with polyimide. A humidity sensor that employs interdigitated capacitors (IDC) printed with silver on a glass and flexible substrate was successfully fabricated using p-HEMA and polyimide at spin speed of 2000 rpm for 20 seconds. Our goal is to integrate the humidity sensor into a robotic arm to perform real-time object characterization in agricultural applications via comprehensive understanding of the operations of harvesting robots in various crop types and environmental conditions.

Investigation of the effect of mass percentage concentration of polystyrene–toluene solution on the surface properties of the plasma‐treated polystyrene thin films

AbstractPolystyrene (PS) finds diverse applications across various fields, often necessitating a hydrophilic PS surface. In this study, the PS films were prepared using PS–toluene solutions of 15, 20, and 25 mass percentage concentrations (% w/v). Here, the main focus is on the influence of concentration on the hydrophilization of the prepared PS thin films under atmospheric pressure air dielectric barrier discharge plasma treatment. The contact angle, surface energy measurements, atomic force microscopy, and Fourier‐transform infrared spectroscopy analysis were conducted to evaluate the PS surface properties. Our results demonstrate, for the first time, the significant role of concentration in altering surface properties; the lower concentration of PS films leads to the most hydrophilic surface. Fourier‐transform infrared spectroscopy analysis confirms an increase in the OH functional group on the PS surface. atomic force microscopy analysis reveals needle‐shaped surface morphology, increased roughness and an expanded effective surface area. Surface energy analysis confirms an increase in the polar sector of surface energy. Overall, the findings from this research underscore the increase in film hydrophilicity with a decrease in PS–toluene concentration.Highlights Polystyrene (PS)–toluene solutions with different concentrations were prepared. PS–toluene films were spin‐coated and were been treated with dielectric barrier discharge plasma. The contact angle, surface energy measurements, atomic force microscopy, and Fourier‐transform infrared spectroscopy analysis were conducted. PS films with lower concentration have more impact from plasma treatment. Concentration, impact the hydrophilicity and roughness of treated PS films.

High-Performance Humidity Sensor Capable for Monitoring Low-Moisture Levels in Energy Industries

Humidity sensors are extensively used in industrial processing and environmental control. There are two categories of humidity sensors: High-humidity (relative humidity) measurement and Low-humidity (moisture) measurement. The proper units for low-humidity measurement are dew point and parts per million in volume (ppmv) or parts per billion in volume (ppbv). It is very important to monitor moisture levels in natural gas during processing and transportation in pipelines. It is of critical importance to monitor moisture levels in lithium-ion battery manufacturing. In these cases, the moisture levels are limited to be less than -50°C dew point or 40 ppmv. The conventional relative humidity sensors cannot be used because of their low sensitivity. The dew point sensors on the market are polymer-based and gamma-phase-alumina based. The polymer-based sensors have low sensitivity, which can only accurately detect moisture levels of -60°C dew point and higher. The gamma-phase alumina sensors suffer from long-term drift due to phase change.We present novel high-performance humidity sensors based on porous alpha-phase alumina and silicon dioxide nanostructures, which are capable of detecting moisture levels as low as -100°C dew point or 13 ppbv with excellent long-term stability. The porous alpha-phase alumina films were produced by anodic-spark-deposition on aluminum substrates in which electric sparks were produced due to high-voltage anodization (>120V). Local high-temperature (about 2200°C) at the points of sparks converted the amorphous alumina into alpha-phase alumina (Sapphire). It provides an extremely stable structure for humidity sensors. Hydrophilic silicon dioxide films deposited by atomic layer deposition was used as sensing materials. The sensors’ sensitivity, temperature coefficient, response speed, and long-term stability were studied in details. The sensors have great promise for monitoring moisture levels in natural gas industry and lithium-ion battery manufacturing.

Surface modification of polylactide films and their hydrolytic degradation performances in artificial seawater

AbstractBenzophenone (BP) and N‐vinylpyrrolidone (NVP) were used to modify the surface of polylactide (PLA) films by UV grafting method. The effects of light distance, temperature, reaction time, and modifier concentration on the structure and properties of PLA films were investigated by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy (XPS), nuclear magnetic resonance spectroscopy, differential scanning calorimetry (DSC), and universal testing machine (UTM). With BP and NVP UV grafting, the hydrophilicity of PLA films is improved, but their thermal and mechanical properties are reduced under different surface modification condition. Base on the principle of good surface hydrophilicity, better mechanical and thermal properties, the hydrolytic degradation performance of modified PLA films in artificial seawater at 70°C was studied by scanning electron microscopy, XPS and DSC. The research results show that the degradation of modified PLA films mainly occurs in the amorphous region, and the degradation process conforms to surface hydrolysis mechanism. The grafting modification of NVP is better than BP to accelerate the degradation process of PLA films in artificial seawater. The degradation of modified PLA undergoes water molecule erosion and autocatalytic degradation reaction. The degradation of BP‐PLA obeys the first‐order kinetics in part, while the degradation of NVP‐PLA is more complex. Therefore, surface hydrophilicity modification is an effective technique for improving the degradability of PLA.

Study of the structure, composition and wettability of the DLC:N films

Encoders are widely used for measurements of very small displacements, position and movement speed in metrology instruments, motion systems, and high-precision machining tools, ranging from digital calipers to coordinate measuring machines. Optical scales are the most accurate encoders. Their effectiveness at a near-dew point is limited, thus hydrophilic coatings are being developed for proper instrument functioning at these conditions. Here, we study wetting and structural properties of nitrogen-doped DLC (DLC:N) films, produced with reactive magnetron sputtering (RMS) and inductively coupled plasma (ICP) beam-assisted magnetron sputtering as potential coatings for optical scale technologies. The slope parameter of the DLC:N films increases as the nitrogen content increases. The toughness of DLC:N coatings changes between methods used and is higher for samples when the RMS growth method is used. The DLC:N wetting varies from 33° to 58.8° for different nitrogen content in the DLC films. The increase in atomic nitrogen concentration increases the number of nitrogen-based functional groups and should lessen the hydrophobic influence of the CH group on the contact angle. Furthermore, CO and OH functional groups' promote even higher contact angle decline, hence it seems that introducing oxygen-based groups, encourages hydrophilicity of DLC films.

Bio-based modification of polyhydroxyalkanoates (PHA) towards increased antimicrobial activities and reduced cytotoxicity

With the increased occurrence of bacteria resistance to conventional antibiotics, the development of novel antimicrobials is urgently needed. Traditional biomaterials used for delivering these agents often struggle to achieve sustained release while maintaining non-cytotoxic properties. In this study, we present an innovative approach using bacterial polyhydroxyalkanoates (PHA) as a carrier for antimicrobial delivery, specifically designed for wound healing applications. Octenidine dihydrochloride (OCT), a widely used antimicrobial agent, served as our model drug. To achieve the desired balance of OCT release and low cytotoxicity, we introduced a novel bio-derived additive, 3-hydroxy-pentadecanoic acid (3OHC15), extracted from bacteria. This additive significantly improved the hydrophilicity of PHA films, resulting in enhanced and sustained release of OCT. Importantly, the additive did not adversely affect the material's tensile strength or thermal properties. The increased OCT release led to improved antibacterial activity against both Gram-negative and -positive strains. Most notably, the incorporation of 3OHC15 in PHA mitigated the cytotoxic effects of the released drug on human fibroblasts, ensuring biocompatibility. This work represents a novel strategy in the design of biomaterials for the delivery of bioactive compounds, achieving a critical balance between efficacy and cytocompatibility, and marks a significant advancement in the field of antimicrobial delivery systems.

Dual-mode electrochemical/colorimetric capillary-driven microfluidic device for simultaneous determination of Δ⁹-tetrahydrocannabinol and cannabidiol in cannabis flower

Cannabis flower is well-known for its high levels of cannabidiol (CBD). However, the medical-grade cannabis flowers must meet strict standards to guarantee high CBD content and minimal to no contamination of Δ⁹-tetrahydrocannabinol (Δ⁹-THC). Given their similar redox potentials as determined by electrochemical detection, a dual readout approach becomes essential for accurately measuring the individual concentrations of Δ⁹-THC. In this work, we developed a capillary-driven microfluidic device that integrated electrochemical and colorimetric detections. The device was made from low-cost, transparent hydrophilic PET film and double-sided adhesive film with a pump-free delivery function. Once the sample solution was loaded, analysis of total Δ⁹-THC and CBD was conducted using an electrochemical technique, with a limit of detection (LOD) of 0.26 μg/mL and linear ranges of 0 – 120 μg/mL for both total Δ⁹-THC and CBD. Simultaneously, the sample solution autonomously flowed to the colorimetric zone within the transparent hydrophilic PET film, with corresponding LOD and linear ranges of 0.44 μg/mL and 0–120 μg/mL specifically for CBD. The method involved subtracting the CBD concentration obtained by colorimetry from the total Δ⁹-THC and CBD concentration obtained by electrochemical detection. Therefore, the proposed device, with its excellent analytical performance and advantageous features of affordability, simplicity, and fully portable light-controlled box, offers a practical alternative for quality control in the assessment of Δ⁹-THC and CBD levels in cannabis flowers.

Enhancing polyvinyl alcohol surface properties through pre-drying treatment and modified electrospun polycaprolactone nanofibers

The application of polyvinyl alcohol (PVA) as a biodegradable polymer is restricted by its low water resistance, particularly for the packaging of moisture-sensitive products. In this paper, we report on a surface-modification approach for PVA films using electrospinning of beeswax-modified polycaprolactone (PCL) following a 10 min pre-drying process. The pre-drying process led to physical binding between the hydrophobic PCL/beeswax nanofibers and the hydrophilic PVA substrate while the addition of beeswax to PCL improved its physical properties, leading to larger surface roughness and lower wettability of the PVA film. In particular, by adding a proper amount of beeswax to PCL, a PVA/PCL/beeswax composite film showed high hydrophobicity with a water contact angle of 144.1°, demonstrating a significant improvement in the surface properties compared to the hydrophilic bare PVA film. Moreover, the oxygen permeability of the PVA film decreased from 5.5 to 2.2 cc.m−2.day−1 after electrospinning the PCL/beeswax, which was related to the rougher surface morphology generated by the electrospun nanofibers. Therefore, our cost-effective approach has the potential to modify the physical properties of hydrophilic polymers and to broaden their industrial applications.

KOH Activated Carbon Coated 3D Wood Solar Evaporator with Highest Water Transport Height and Evaporation Rate for Clean Water Production.

The water evaporation rate of 3D solar evaporator heavily relies on the water transport height of the evaporator. In this work, a 3D solar evaporator featuring a soil capillary-like structure is designed by surface coating native balsa wood using potassium hydroxide activated carbon (KAC). This KAC-coated wood evaporator can transport water up to 32cm, surpassing that of native wood by ≈8 times. Moreover, under 1kWm-2 solar radiation without wind, the KAC-coated wood evaporator exhibits a remarkable water evaporation rate of 25.3kgm-2h-1, ranking among the highest compared with other reported evaporators. The exceptional water transport capabilities of the KAC-coated wood should be attributed to the black and hydrophilic KAC film, which creates a porous network resembling a soil capillary structure to facilitate efficient water transport. In the porous network of coated KAC film, the small internal pores play a pivotal role in achieving rapid capillary condensation, while the larger interstitial channels store condensed water, further promoting water transport up more and micropore capillary condensation. Moreover, this innovative design demonstrates efficacy in retarding phenol from wastewater through absorption onto the coated KAC film, thus presenting a new avenue for high-efficiency clean water production.

Synthesis of palm oil-based bio-polyol by thiol-ene reaction: Preliminary study of its potential as cationic waterborne polyurethane for coating application

Thailand has the world's third-largest planting area for oil palm. Palm oil can be chemically modified to obtain bio-polyol instead of petroleum-based polyol. In this research, a new bio-polyol based on modified palm oil (MPO) was successfully synthesized by thiol-ene click reaction using Darocur1173 as a photoinitator. The molar ratios 2-Mercaptoethanol (ME) to carbon‑carbon double bonds for MPO synthesis was studied. The kinetics of the thiol-ene click reaction was investigated by monitoring with 1H NMR technique. The chemical structure of MPO was confirmed by 1HNMR and FTIR spectroscopy. In addition, the average molecular weight (Mn) of a series of MPO was determined by GPC. The influence of N-methyl diethanolamine (NMDEA) content as an internal emulsifier on cationic waterborne polyurethane (cWPU) was investigated. The resulting cWPU based on MPO showed well-dispersed particles with a shelf life of >6 months and the zeta potential increased with increasing NMDEA content ranging from 5.6 % to 9.6 %wt. Moreover, the plywood with cWPU coatings had a shiny gloss surface, with increasing NMDEA content. The cWPU coating with NMDEA content lower than 7.6 %wt protected the plywood surface against QUV accelerated weathering for 48 h without cracking the cWPU film. The cWPU showed a high gloss value, decreased contact angle, and increased water absorption behavior. The hydrophilicity of cWPU film increased with increasing NMDEA content. Also, increasing the NMDEA content led to a higher ratio of hard segment to soft segment in the PU chain which improved the tensile strength and thermal stability. These results demonstrated an efficient synthesis procedure which offers an opportunity to use palm oil as bio-polyol to develop green cWPU that can be used as a binder in coating applications.

Utilization of Pickering emulsion stabilized by chitin nanofibers for improving water and oxygen resistance of gelatin films

The hydrophilicity of gelatin films obviously limits their application. In this work, novel protonated chitin nanofiber was prepared with green methods, surficial deacetylation combined with acidic and mechanical treatment. Composite films with excellent water and oxygen barrier properties were successfully prepared by blending O/W Pickering emulsions stabilized by chitin nanofibers with gelatin substrates. The films were characterized by Fourier-transform infrared, X-ray diffraction, mechanical properties, water and oxygen permeability, moisture content, water solubility, water contact angle and optical properties. The results demonstrated that the amino groups of chitin nanofibers bound to the carboxyl groups of gelatin via electrostatic interactions, which contributing to the excellent mechanical and barrier properties of composite films. The elongation at break of composite film (the concentration of chitin nanofiber was 0.2 wt%) was 2.66 times of gelatin film. And the water vapor and oxygen permeability of composite films lowered to 65.9 % and 52.9 %, respectively. The introduction of O/W Pickering emulsion significantly enhanced the hydrophobicity of gelatin-based film and the chitin nanofibers played a positive role in stabilizing the gelatin chains to a certain extent. This study expands the application fields of gelatin-based films and provides valuable technical route for the preparation of barrier films.