Final Film Research Articles

Laponite vs. Montmorillonite as Eugenol Nanocarriers for Low Density Polyethylene Active Packaging Films

Although a lot of recent research revealed advantages of novel biopolymers’ implementation as active food packaging polymers, there is not an equivalent effort from industry to use such films, probably because of the required cost to change the supply chain and the equipment. This study investigates the use of two natural abundant nanoclays, laponite (Lap) and montmorillonite (Mt), as eugenol slow-release carriers for enhancing the functionality of low-density polyethylene (LDPE) active packaging films. The target is to combine the spirit of the circular economy with the existent technology and the broadly used materials to develop a novel attractive product for active food packaging applications. Utilizing a vacuum-assisted adsorption method, eugenol was successfully intercalated into Lap and Mt nanoclays, forming EG@Lap and EG@Mt nanohybrids. Testing results confirmed effective integration and dispersion of the nanohybrids within the LDPE matrix. The most promising final film seems to be the LDPE with 15% w/w EG@Lap nanohybrid which exhibited a higher release rate (k2 = 5.29 × 10−4 s−1) for temperatures ≤70 °C, similar mechanical properties, a significantly improved water barrier (Dwv = 11.7 × 10−5 cm2·s−1), and a slightly improved oxygen barrier (PeO2 = 2.03 × 10−8 cm2·s−1) compared with neat LDPE. Antimicrobial and sensory tests on fresh minced pork showed two days’ shelf-life extension compared to pure LDPE and one more day compared to LDPE with 15% w/w EG@Mt nanohybrid.

Brownian dynamics simulation of the structural evolution in monodisperse hard-sphere suspensions during drying and sedimentation processes.

The drying behavior of monodisperse colloidal films, with a focus on the influence of process variables on film microstructures, is explored via Brownian dynamics (BD) simulations. In our model, hard-sphere colloidal particles are dispersed in a Newtonian liquid with an initial particle volume fraction of 0.1. The effects of the drying rate and sedimentation on the evolving microstructures are systematically investigated using two dimensionless numbers: the Péclet number (Pe), which represents the competition between evaporation and diffusion, and the sedimentation number (Ns), which reflects the relative influence of sedimentation on evaporation. First, we analyze the local particle volume fraction and film structure at various Pe and Ns. As Pe increases, particle accumulation occurs near the liquid-gas interface, whereas a high Ns promotes dense packing near the substrate owing to sedimentation. The BD simulation results, viz. the local volume fraction profiles and drying regime maps, are in good agreement with those of the continuum model proposed by Wang and Brady. Structural analysis of the dried films reveals that at a low Pe (Pe = 0.1), a face-centered cubic (FCC) structure dominates, primarily independent of the sedimentation effects. In contrast, a high Pe leads to hexagonal close-packed or amorphous structure formation. Notably, at intermediate drying rates (Pe = 10), an increase in Ns promotes additional FCC ordering in the final film structure. Our study provides new insights into the hitherto underexplored role of sedimentation in the structural evolution of drying colloidal films, revealing the mechanisms of drying-induced assembly in colloidal systems.

Exceptional Electrical Detection of Trace NO2 via Mixed Metal MOF-on-MOF Film-Based Sensors.

The tunability of metal-organic frameworks (MOFs) makes them exceptional materials for the development of highly selective, low-power sensors for toxic gas detection. Herein, we demonstrate enhanced detection of NO2 gas by a MOF-based electrical impedance sensor made using a unique mixed metal MOF-on-MOF synthesis. A combined experimental and computational study was performed using the exemplar NixMg1-x-MOF-74 to understand the fundamental structure-property relationships behind metal mixing and MOF film synthesis methods on sensor performance. Density functional theory results indicated that the presence of Ni in Mg-MOF-74 increased framework stability and increased the electron density of states at lower energies near the HOMO, as well as enhanced the NO2-Mg adsorption interaction. Impedance data of the NixMg1-x-MOF-74 films with larger Ni contents showed greater impedance change after exposure to 1 ppm of NO2 gas. Furthermore, when synthesized through either a drop-cast or direct solvothermal film growth approach, the monometallic Ni-based sensors had the best performance. However, the mixed metal NixMg1-x-MOF-74 sensors synthesized through a MOF-on-MOF approach resulted in the highest impedance change, outperforming all monometallic Ni-based sensors. In particular, the mixed metal Ni-on-Mg-MOF-74 film was the best-performing sensor with an impedance change of 309 upon trace NO2 exposure. Change in impedance response after NO2 exposure was improved by 52% compared to the best monometallic Ni-on-Ni-MOF-74 sensor. Structural analysis of the Ni-on-Mg film showed that the first Mg-MOF-74 layer acts as a structural template controlling the structural features of the final film after metal exchange with Ni. This led to improved film quality, evidenced by the greater crystallinity and larger MOF grain sizes, and resulted in enhanced sensor performance which was not achievable through other metal mixing methods. Altogether, this study identifies structure-property relationships and synthetic templating methods that inform MOF-based sensor design, allowing for improved detection of toxic compounds.

Ground tests for a future space experiment: Evaporation rates through a centimetric square chimney by vapor interferometry and simulation

In this paper, results of preparatory tests for a space experiment “Marangoni in Films” on board International Space Station are reported. The setup is thermalized at a setpoint temperature so that (thermal) Marangoni convection is exclusively a result of evaporative cooling of the film, here composed of a Hydrofluoroether (HFE)-7100, evaporating into nitrogen at a given setpoint pressure. The present paper is entirely devoted to the evaporation rates, whereas the Marangoni convection itself will be analyzed in future studies. Apart from the temperature and nitrogen pressure, various setpoints for the initial relative saturation in HFE-7100 vapor are explored. A special design of the test cell with a square chimney surrounding a square opening of the liquid layer permits to largely stabilize the evaporation rates during a longest-lasting middle stage (beyond the initial transients and the final film dry-out). In addition, it facilitates the use of vapor (digital-holographic) interferometry for measuring the evaporation rates, the results of which are compared with independent measurements by means of the pressure evolution within our sealed cell of a fixed volume. An excellent agreement is found before the final dry-out stage for all setpoint parameter combinations tested. The study is accompanied by numerical finite-element simulations in an axisymmetrized geometry, neglecting a possible influence of the Marangoni convection and verifying certain premises used in interferometric post-processing. Even if the simulation results might somewhat over-/underpredict in each particular case, the overall dependence of the evaporation rate on the setpoint parameters is well reproduced and the role of the buoyancy convection is thereby explored.

Crystallization Control to Prepare Uniform CsPbI2Br Thin Films for High-Efficiency Perovskite Solar Cells.

All-inorganic perovskite solar cells (PSCs) face challenges related to film inhomogeneity, which arises from nonideal crystallization. This issue significantly impedes the advancement of all-inorganic PSCs. In this study, we observed that during the crystallization process of CsPbI2Br, the Br-rich intermediate phase is often preferentially deposited, leading to an uneven distribution in the out-of-plane direction of the perovskite film. To address this issue, crown ether molecules (dibenzo-18-crown-6) were introduced into the perovskite precursor solution. The complexation of crown ether with Cs cations and Br anions optimizes the crystallization sequence of the perovskite, ensuring that the intermediate phase closely conforms to the standard stoichiometric ratio. This adjustment significantly mitigates the problem of uneven halogen ion distribution along the out-of-plane direction. Furthermore, the crown ether thermally decomposes during the high-temperature annealing process, thereby not affecting the composition of the final perovskite film. Following crown ether treatment, the efficiency of the PSCs reached 14.08%, and the unpackaged devices maintained 80% of their initial efficiency after 1000 h of exposure to light in an atmospheric environment.

Impact of molecular architecture and draw ratio on enhancement of targeted mechanical properties of machine direction oriented polyethylene films produced after blown film extrusion

Conventional multi-material multi-layer flexible packaging offers excellent properties. However, it has recycling challenges, necessitating a shift to mono-material multi-layer flexible packaging for example all-polyethylene (PE) packaging which can be tailored through various synthesis and processing methods for different layers. In this work, we study how the key molecular properties (number-average molecular weight ( Mn), weight-average molecular weight ( M w), molecular weight distribution (MWD), comonomer content (short chain branching)) and machine direction orientation (MDO) process draw ratio (MDX) influence the final morphology and mechanical properties of MDO-PE films which are intended as the outer layer of mono-material all-polyethylene multi-layer flexible packaging. Five PE grades and various blends were extruded and blown into films. Selected blown films were machine direction oriented to obtain the final MDO-PE films. Furthermore, one selected PE blown film was processed at different MDO process draw ratios while keeping other process parameters constant. From the molecular properties point of view, the higher molecular weight fractions provide a higher possibility for uniform stretching whereas lower molecular weight fractions provide a higher natural draw ratio and therefore higher modulus and stiffness enhancement. Further, the results show that increasing MDO process draw ratio leads to more fibrillation and increased crystallinity. Consequently, the tensile modulus and stiffness at the higher draw ratios increase as well and are comparable to conventionally used polymers in outer layers of multilayer flexible packaging. Thus, this work demonstrates that MDO-PE films with enhanced modulus can provide sufficient stiffness for the design of outer layer of mono-material multi-layer all-PE packaging which presents higher potential for mechanical recyclability.

Step‐Directed Epitaxy of Unidirectional Hexagonal Boron Nitride on Vicinal Ge(110)

Insulating hexagonal boron nitride (hBN) films with precisely controlled thickness are ideal dielectric components to modulate various interfaces in electronic devices. To achieve this, high‐quality hBN with controlled atomic configurations must be able to form pristine interfaces with various materials in devices. However, previously reported large‐scale hBN films with uniform thickness either are polycrystalline or are not suitable for atomically clean assembly via mechanical exfoliation, limiting their applications in device technology. Herein, the large‐scale growth of monolayer (ML) single crystalline hBN films on Ge(110) substrates by using chemical vapor deposition is reported. Vicinal Ge(110) substrates are used for the step‐directed epitaxial growth of hBN, where Ge atomic steps act as the hBN nucleation sites, guiding the unidirectional alignments of multiple hBN domains. Density functional theory calculations reveal that the optimum hydrogen passivations on both hBN edges and Ge surfaces enable the epitaxial coupling between hBN and the Ge step edges and the single crystallinity of the final hBN films. Using epitaxially grown ML hBN films, a few hBN films with controlled stacking orders and pristine interfaces through a layer‐by‐layer assembly process are fabricated. These films function as high‐quality dielectrics to enhance carrier transport in graphene and MoS2 channels.

The Role of Formulations in the Ageing Process of Vinyl Acetate Based Emulsion Films: A Multivariate Approach

Vinyl acetate (VAc)-based emulsions represent one of the main media used by modern and contemporary artists. Their long-term behaviour is still not completely understood, especially due to the scarce knowledge on the influence of other compounds in the formulation, which may impact ageing over time. Besides the polymer backbone based on vinyl acetate, other co-monomers and additives can be added to the emulsion to alter the final film’s physical, chemical, and optical properties. By extension, the formulation will also impact the long-term stability of artworks and objects on which it has been applied, as well as possible current and future conservation interventions such as cleaning. For those reasons, studies shedding light on the correlation between composition and long-term stability are largely necessary. In this study, different emulsions, including homopolymers, copolymers, plasticised, and un-plasticised compositions, were gathered and artificially aged. A multivariate analyses approach based on the application of principal component analyses (PCA) and hierarchical cluster analyses (HCA) was employed for the first time on the combination of data obtained by pH, contact angle (CA), colour measurements, Fourier transform infrared spectroscopy in attenuated total reflection (FTIR-ATR), and size exclusion chromatography (SEC). This approach helped to highlight the changes that occurred during ageing and find correlations with the formulation compositions. The results further sustain the thesis that not all vinyl acetate-based emulsions are chemically the same and that their formulation deeply impacts their long-term behaviour.

The evolution of morphology and structure of spin-coated Zinc Acetate thin films and their impact on ZnO film morphology

The deposition of ZnO thin films using sol-gel technology is a straight forward and widely used method for fabricating ZnO films with diverse morphologies and tunable electrical and optical properties. Notably, the preparation of ZnO compact layers from a zinc acetate and monoethanolamine (ZA:MEA) solution via spin-coating has gained popularity due to its simplicity. The pretreatment of spin-coated ZA:MEA films significantly impacts the morphology and structure of the resulting ZnO films. While the effects of preheating and its rate on ZnO precursor films have been extensively studied, the morphological and structural evolution of ZA:MEA films immediately after spin-coating and its subsequent impact on the final ZnO film have not been previously explored. In this study, we present the topography and phase composition of as-grown ZA:MEA films using atomic force microscopy (AFM). We conduct an in-situ investigation of the morphological evolution of ZA:MEA films. Our results reveal that as-grown ZA:MEA films possess an inhomogeneous structure. AFM phase image shows two distinct domains in the ZA:MEA films. Over time, we observe the growth of crystals in both vertical and perpendicular directions. ZA:MEA film aged for at least 20 h develops arrays of vertically oriented crystals throughout the film covered with sheet-like crystals forming on the film surface. This temporal evolution in the morphology and structure of ZA:MEA films significantly influences the morphology of the final ZnO film.

High-Performance Broadband Photodetectors Combining Perovskite and Organic Bulk Heterojunction Bifunctional Layers

Perovskite can be used to prepare high-performance photodetectors due to its excellent optical properties. However, the detection range of perovskite photodetectors is mostly limited to the visible light range, restricting their further development and application. In recent years, combining perovskite with organic bulk heterojunctions to prepare photodetectors with broadband detection capability has proven to be an effective strategy. Through this approach, the response spectrum of the photodetector can be flexibly regulated, and organic compounds can improve the perovskite film quality by passivating defects and inhibit the penetration of water molecules in the air, thereby improving the device performance and stability. In this work, we propose and demonstrate the feasibility of combining MAPbI3 perovskite with PTB7-Th:COTIC-4F to prepare high-performance photodetectors with wide spectral response characteristics. With the assistance of an organic bulk heterojunction, the defects of perovskite crystals are effectively passivated, and the detection spectrum of the device is successfully extended to about 1100 nm. As a result, the responsivity achieved is 0.58 A/W, 1.19 A/W, and 1.41 A/W under laser illumination of 532 nm, 808 nm, and 980 nm, with the power density of 5 μW/cm2 at the bias voltage of −0.5 V, respectively, which is one of the best performances among vertical device structures of this type. Moreover, the stability of the final hybrid film has been greatly improved. This work provides a new approach to the preparation of high-performance and broadband perovskite photodetectors.

High-strength and toughness CNT films from microwaving-promoted purification and structural reconstruction

Carbon nanotube (CNT) films can now be prepared by catalytic floating chemical vapor deposition (CVD) with low cost and high yield. However, their performance deteriorates drastically due to the presence of impurities and structural defects all over the films. In this study, we report a simple and fast heating and quenching approach to tackle this issue by using a household microwave oven. Experimental results show that the strong interaction between CNTs and low-power microwaves within 10 s not only triggered the diffusion of Fe particles from the interior to the surface of the film for easy purification but also improved the graphitic structure of CNTs and their inter-tube binding for mechanical strengthening and electrical conduction. After a sequential treatment of microwaving-acid washing-microwaving, followed by additional rolling, the final CNT film exhibited a tensile strength of 7.45 GPa, an elongation at break of 11.33 %, and an electrical conductivity of 1.85 × 106 S m−1. The combination of such mechanical and electrical properties is superior to previous fibers and films reported in open literature. Considering its efficient and environment-friendly features, the present approach is suitable for the large-scale production of high-performance CNT films, thereby meeting the requirements for practical applications in many fields.

Eliminating performance loss from perovskite films to solar cells.

Preoptimizing perovskite films may generally improve the performance of the final perovskite solar cells (PSCs). However, the research on whether the film optimization fully contributes to the enhancement of the final PSCs has been long neglected. We demonstrated that the preparation of metal electrodes by high-vacuum thermal evaporation, an unavoidable step in almost all device fabrication processes, will damage the surface of perovskite films, resulting in component escape, defect density rebound, carrier extraction barrier, and film stability deterioration. Therefore, the prepared perovskite film and the final film actually working in devices are not exactly the same, and the contribution of film optimization to the device improvement was weakened. We designed a bilayer structure composed of graphene oxide and graphite flakes to eliminate the unwanted film inconsistencies and thus save the film optimization loss. Therefore, the efficient PSCs with power conversion efficiency of 25.55% were obtained, which demonstrated negligible photovoltaic performance loss after operating for 2000 hours.

Physical Crosslinking of Aqueous Polymer Dispersions: A Perspective

AbstractColloidal polymers, and in particular aqueous polymer dispersions, are widely used in commercial applications such as coatings and adhesives. Historically, the solvent resistance and mechanical properties of these systems have been improved by covalently crosslinking the polymer chains after drying. More recently, work has been directed toward replacing this covalent crosslinking, which typically involves highly reactive functional groups, by physical crosslinking through the use of supramolecular interactions. While conceptually similar to the use of covalent crosslinking, physical crosslinking has a unique influence on the rheology of the polymer, which leads to substantial differences in the development of mechanical strength during drying, as well as the mechanical properties of the final polymer film. In this perspective, the advantages and challenges of this approach are outlined, and an outlook for future research in this direction is provided.

Columnar Macrocyclic Molecule Tailored Grain Cage to Stabilize Inorganic Perovskite Solar Cells with Suppressed Halide Segregation

AbstractSolidifying the soft lattice of all‐inorganic mixed‐halide perovskites is of great importance to restrain the notorious halide segregation under persistent light illumination. Herein, a multifunctional columnar macrocyclic molecule additive, namely cucurbituril into perovskite precursor to enhance the crystallization and reduce the defect density in the final perovskite film is introduced. Based on the theoretical calculation and simulation, the cucurbituril molecule with a strong double‐ended negatively‐charged cavity surrounded by terminated oxygen atoms not only coordinates with dangling Pb2+ ions to form host‐guest complexation but also induces an electric dipole field at perovskite grain boundary to effectively repel the iodide ion migration from the inside grain to the defective boundary, significantly suppressing the halide segregation and improving the device performance. As a result, the carbon‐based, all‐inorganic CsPbI2Br solar cell achieves an enhanced efficiency of 15.59% with great tolerance to environmental stresses. These findings provide new insights into the development of a novel passivation strategy with macrocyclic molecules for making high‐efficiency and stable perovskite solar cells.

Cd‐Free High‐Bandgap Cu2ZnSnS4 Solar Cell with 10.7% Certified Efficiency Enabled by Engineering Sn‐Related Defects

AbstractCd‐free high‐bandgap Cu2ZnSnS4 (CZTS) solar cells are expected to offer green and low‐cost solutions to single‐junction and tandem photovoltaic markets. Despite attracting considerable attention in past years, reported certified efficiency has yet to exceed the 10% threshold. Sn‐related defects, especially those originating from Sn2+ oxidation states, lead to severe recombination loss and limit device performance. Here, the formation of these detrimental defects is suppressed by creating a more benign chemical environment during sulfurization annealing. With dominant Sn4+ states in the source material and the precursor, the oxidation state of Sn remains primarily in its native Sn4+ state during annealing and in the final film. Engineering the Sn‐related defects leads to shallower tail states in bulk CZTS and fewer interfacial defects. As a result, both radiative and non‐radiative recombination losses are alleviated, contributing to a certified 10.7% efficiency of the Cd‐free high‐bandgap CZTS solar cell. This strategy may advance various kesterite materials and other technologies with multivalent constituents.

Double layer bacterial nanocellulose - poly(hydroxyoctanoate) film activated by prodigiosin as sustainable, transparent, UV-blocking material

Synthetic materials alternatives are crucial for reaching sustainable development goals and waste reduction. Biomaterials and biomolecules obtained through bacterial fermentation offer a viable solution. Double-layer active UV-blocking material composed of bacterial nanocellulose as an inner layer and poly(hydroxyoctanoic acid) containing prodigiosin as an active compound was produced by layer-by-layer deposition. This study referred the new material consisted of the three components produced in sustainable manner, by bacterial activity: bacterial bio-pigment prodigiosin, bacterial nanocellulose and poly(hydroytoctanoate) - biopolymer obtained by microbial fermentations. Prior the final double layer film was produced, PHO films containing different PG concentrations as a layer in charge of the bioactivity (0.2, 0.5 and 1 wt%) was casted and systematically characterized (FTIR, DSC, XRD, wettability, SEM, transparency, mechanical tests) to optimize their properties. The formulation with the best UV-blocking properties and less toxicity effect tested using MRC5 cells was chosen as an outer layer in double-layer films production. Water contact angle measurements confirmed that hydrophilic – hydrophobic double layer film was obtained with the improved mechanical properties in comparison to the native BNC. Migration test indicated release of PG in all tested media as a consequence of bilayer formulation, while the PG release from PHO in 10 % ethanol was not detected. All findings from the study suggested this activated, UV-blocking material as a candidate with excellent potential in packaging industry.

A cellulose-based light-management film incorporated with benzoxazine resin/tannic acid exhibiting UV/blue light double blocking and enhanced mechanical property

Cellulose, as a biomass resource, has attracted increasingly attention and extensive research by virtue of its widely sources, ideal degradability, good mechanical properties and easy modification due to its rich hydroxyl groups. Nevertheless, it is still a challenge to attain high performance cellulose-based composite film materials with diverse functional combinations. In this work, we developed a multifunctional cellulose-based film via a facile impregnation-curing strategy. Here, benzoxazine resin (BR) is used as an optically functional component to endow the microfibrillated cellulose (MFC) film with powerful light management capabilities including UV and blue light double shielding, high transmittance, and high haze. Meanwhile, the introduction of tannic acid (TA) substantially enhanced the mechanical properties of the film, including tensile strength and toughness, by constructing energy-sacrificial bonds. An effective self-healing of the film was achieved by controlling the degree of BR curing. The final films exhibited 98.24 % UV shielding and 89.98 % blue light blocking, good mechanical properties including a tensile strength of 202.21 MPa and tensile strain of 7.1 %, as well as desirable thermal healing properties supported by incompletely cured BR. This work may provide new insights into the high-value utilization of biomass resources.

Hybrid Molecular Layer Deposition of Molybdenum-Aminates as Hydrogen Evolution Reaction Electrocatalysts

The development of high-performance hydrogen evolution reaction (HER) electrocatalysts from noble metal-free materials is critical to achieving cost-effective water splitting and ultimately realizing affordable hydrogen based on renewable energy. Compounds based on earth-abundant transition metals have been the subject of great research interest for this purpose, with metal nitrides gaining recent attention due to their high conductivity and corrosion resistance. Molybdenum nitride-based electrocatalysts have shown particular promise, with many of the best reported activities occurring in composite systems wherein crystalline MoNx domains are embedded in an amorphous N-doped carbon matrix. The present work demonstrates the formation of such uniquely active morphologies in films deposited by organic-inorganic hybrid molecular layer deposition (MLD).Hybrid MLD is a hybridization of other well-established layer-by-layer deposition techniques – namely atomic layer deposition (used to deposit inorganic films) and purely organic MLD. This family of techniques involves the cyclical exposure of a growth surface to alternating vapor-phase chemical precursors which react in a self-limiting fashion to saturate available surface sites, offering atomic- and molecular-level control over the resulting films. This presentation will introduce the successful development of hybrid MLD deposition procedures for new Mo-aminate materials using Mo(CO)6 as a Mo precursor and various amine precursors, including ethylenediamine, p-phenylenediamine, and tris(2-aminoethyl)amine.We will describe how the molecular level of control offered by this technique enables tunable variations in film composition and structure, lending unique insights into how the local bonding environment of Mo active sites affects their catalytic properties towards HER. Increased nitrogen loading in the MLD films was shown to decrease the overpotentials required to drive HER in acidic media (0.5 M H2SO4) and improve film stability. Catalysts with N/Mo ratios above 2 demonstrated the best performance, with overpotentials lower than 400 mV at -10 mA/cm2. By incorporating organic components in the MLD films, it was possible to induce desirable morphological changes in the catalytic material – notably including the development of increased active site density – simply through initial exposure to HER testing conditions. The choice of organic precursor affected the rate and extent of these changes through structural effects like crosslinking and crystallinity, which led to more stable catalysts, slowed the rate of morphological changes, and impacted final film structure.

Effects of Lithium bis(trifluoromethanesulfonyl)imide loading on thermal, mechanical and ion conducting properties of specialty interlayer films derived from scrap Polyvinyl butyral

This work investigates the feasibility of using scrap poly(vinyl butyral) (PVB) film derived from laminated glass factories as an ion-conductive interlayer film for producing electrochromic glass. The process uses PVB films made from masterbatches containing 10 to 60 wt% lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). The investigation focused on how LiTFSI loading affected both the PVB masterbatches and the final PVB films. Higher LiTFSI loading correlated with increased ionic conductivity. The best electrochromic devices are obtained when the PVB films are directly prepared from the masterbatch without additional PVB flakes dilution during extrusion. The highest ionic conductivity 2.72 × 10−4 S/cm, is achieved from a masterbatch containing neat PVB and scrap PVB flakes with 60 wt% LiTFSI. Additionally, LiTFSI acted as a plasticizer for PVB, lowering the glass transition temperature and increasing the PVB film percent elongation.

The dual action of N2 on morphology regulation and mass-transfer acceleration of CO2 hydrate film

The morphology characteristics of CH4, CO2 and CO2+N2 hydrate film forming on the suspending gas bubbles are studied using microscopic visual method at supercooling conditions from 1.0 to 3.0 K. The hydrate film vertical growth rate and thickness along the planar gas-water interface are measured to study the hydrate formation kinetics and mass transfer process. Adding N2 in the gas mixture plays the same role as lowering the supercooling conditions, both retarding the crystal nucleation and growth rates, which results in larger single crystal size and rough hydrate morphology. N2 in the gas mixture helps to delay the secondary nucleation on the hydrate film, which is beneficial to maintain the pore-throat structure and enhance the mass transfer. The vertical growth rate of hydrate film mainly depends on the supercooling conditions and gas compositions but has weak dependence with the experimental temperature and pressure. Under the same gas composition condition, the final film thickness shows a linear relationship with the supercooling conditions. The mass transfer coefficient of CH4 molecules in hydrates ranges from 4.54 to 7.54×10–8 mol·cm–2·s–1·MPa–1. The maximum mass transfer coefficient for CO2+N2 hydrate occurs at the composition of 60% CO2+40% N2, which is 3.98×10–8 mol·cm–2·s–1·MPa–1.