Properties Of Polymer Films Research Articles

Fabrication of amorphous lamellar freestanding poly(N‐dodecyl acrylamide) films and their mechanical properties

AbstractAn amorphous lamellar freestanding film composed of poly(N‐dodecyl acrylamide) (pDDA) was prepared by annealing a micrometer‐thick film under humid conditions (humid‐annealing). pDDA was blade‐coated onto a glass substrate, and its lamellar formation was studied by XRD and polarized optical microscopy (POM). The XRD pattern indicates that pDDA formed a highly oriented lamellar structure by humid‐annealing at 80 °C for 6 h. Moreover, the POM image of the cross‐section of the film indicates that lamellar formation started at the polymer–substrate interface, and the amorphous lamella covered the entire film area without randomly oriented regions. In contrast, the open Nicol microscopic image exhibited large cracks in the highly oriented film owing to shrinkage of the film. A crack‐free film was prepared using water‐saturated chloroform as the solvent for blade coating. Water is thought to adsorb to an amide moiety to induce a ‘pre‐lamellar’ structure in the solution. The formation of pre‐lamellae and the decrease in the humid‐annealing temperature reduced the shrinkage of the film by lamellar formation to form a crack‐free film. The mechanical properties of the crack‐free, freestanding pDDA films were studied using a simple tensile test. The film became increasingly stronger with the formation of an amorphous lamellar structure. These results indicate that the mechanical properties of polymer films can be improved without crystallization. © 2024 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Modulating the doping level of conductive polymers for all polymer-based triboelectric self-powered sensors

Triboelectric self-powered sensors, utilizing flexible conductive polymers in place of traditional metal electrodes, provide improved flexibility and reduced weight, making them highly promising for next-generation Internet of Things sensing applications. Here we demonstrate that ionic liquid (IL) additives notably enhance the mechanical and electrical properties of conductive polymer (PEDOT:PSS) films, optimizing their triboelectric performance. Results show that IL as molecular dopant induces structural change in PEDOT, thereby enhancing charge delocalization and doping levels. These IL-doped PEDOT:PSS films achieved high conductivity, significantly elevated surface potential, and a fourfold increase in output triboelectric voltage compared to the neat film. Additionally, flexible all-polymer tactile sensors with high sensitivity (3.6 V/kPa) were fabricated, demonstrating potential for diverse applications such as activity signal detection and human–machine interfaces.

Investigating the role of solvents in modulating glass transition and dynamic mechanical characteristics of polystyrene film

This study investigates how different solvents impact the glass transition and dynamic mechanical properties of polystyrene (PS) films. Using FTIR spectroscopy, it analyzes solvent-induced variations in molecular vibrations, particularly in the phenyl ring region. Results show solvent-specific effects on the 750 cm-1 peak, associated with the "meta-substituted aromatic ring," influencing phenyl ring vibrations. DSC analysis highlights solvent effects on the glass transition temperature (Tg), revealing complexities in PS films prepared with chloroform, tetrahydrofuran (THF), and toluene. Varied Tg behavior suggests solvent-driven structural modifications and gradual solvent removal. Dynamic Mechanical Analysis (DMA) demonstrates solvent-dependent changes in storage modulus, loss modulus, and tan δ, indicating solvent polarity role in polymer chain dynamics. Toluene-induced plasticization reduces Tg and increases creep compliance, revealing PS film sensitivity to solvents. These findings stress solvent selection importance in tailoring thermal and mechanical properties of polymer films for specific applications.

CREATION OF LONG-ACTING DISINFECTANT EMULSIONS BASED ON POLYACRYLAMIDE POLYMERS AND FUNCTIONAL ADDITIVES

The principles of creating a water-organic disinfectant emulsion (WODE) are described. The emulsion can be applied to various types of surfaces and form a film with a prolonged bacteriostatic/bactericidal effect. When applied to the surface under treatment in a dropwise manner, the composition based on polyacrylamide and special additives will form a durable film, which, in turn, will promote the provision for high sanitary and anti-epidemic measures. The film formed on the surface can be removed by wetting with water and subsequent wiping, which will not lead to the disruption of the general disinfection regime. The water-organic disinfectant emulsion is a composition based on polyacrylamide, a surfactant, polyalcohol (glycerol) and zinc/copper sulphate. The factors responsible for the uniformity of WODE film formation were studied. The criteria for improving rheological and technological properties (wettability, spreadability, moisture absorption) under environmental conditions have been determined. It has been established that higher spreadability and improved strength properties of water-soluble polymer films are achieved by adding surfactants (especially nonionic ones) and a polyalcohol to the composition. By modelling the abrasion process, the mechanical parameters of water-soluble polymer biocidal films were studied. The disinfectant effect of the developed aqueous-organic film-forming composition was studied with respect to the strains of microorganisms: Klebsiella pneumoniae, Pseudomonas aeruginosa, Staphylococcus aureus and Escherichia coli. It is proven that the provision of bacteriostatic and bactericidal properties is explained not only by the introduction of copper sulphate or zinc sulphate into the biocide composition, but also by the inhibitory properties of polyacrylamides of various brands themselves. It has been established that polyacrylamide, despite the presence of carbon and nitrogen in its composition, is not an accessible source of nutrition for the cells of pathogenic microorganisms.

Process dependent properties of glassy polymer films revealed by molecular dynamics simulations

A molecular dynamics (MD) framework has been proposed to systematically simulate process (but not cooling rate) dependent properties of glassy polymer films. With the coarse-grained (CG) polylactide (PLA) of low molecular weight (MW), the simulated thermal properties of glassy films are confirmed to be surely decided by the routes to prepare them. While the glassy films initially prepared from the melt bulk are stable, the glassy film initially constructed from the glassy bulk appears to be unstable, featuring highest potential energy among those films and different averaged heat capacity from the bulk counterparts. Inspired by physical vapour deposition (PVD), a surface formation process is further applied to the unstable film to generate stable glassy polymer films. Similar to the PVD, an optimal temperature at which the film is most stable can be identified with lower potential energy than the conventional films, for which free surface and enhanced order of the middle layer are responsible. This work paves a way for obtaining simulated models of stable glassy films and experimentally preparing advanced glassy films for high MW polymers, which otherwise are hard to be realized by the PVD process.

Unlocking the Potential of Liquid Plasma Polymer Films: Characterizing Aging Effects and Their Impact on the Wrinkling Phenomenon.

Here, we present the study of the intricate dynamics between the physicochemical properties of liquid propanethiol plasma polymer films (PPFs) and the formation of wrinkles in PPF/Al bilayers. The study investigates the effect of liquid PPF aging in the air before top Al layer deposition by magnetron sputtering on the wrinkling phenomenon for 4 days. Thanks to atomic force microscopy, the wrinkle dimensions were found to decrease by approximately 55% in amplitude and 66% in wavelength, correlated with an increase in the viscosity of the PPF over the aging duration (i.e., from less than 107 to 1010 Pa·s). This behavior is not linked to alterations in cross-linking degree as evidenced by time-of-flight secondary ion mass spectrometry experiments but rather to network densification driven by the inherent molecular chain mobility due to the viscous state of the PPF. X-ray photoelectron spectroscopy measurements emphasizing the absence of oxidation of the PPF over the aging duration support this, revealing a unique aging mechanism distinct from other plasma polymer families. Overall, this study offers valuable insights into the design and application of mechanically responsive PPFs involved in bilayer systems, paving the way for advancements in nanotechnology and related fields.

The Effect of Macromonomer Surfactant Microstructure on Aqueous Polymer Dispersion and Derived Polymer Film Properties.

Water-borne coatings were prepared from poly(methyl methacrylate-co-butyl acrylate) latexes using different methacrylic acid containing macromonomers as stabilizers, and their physical properties were determined. The amphiphilic methacrylic acid macromonomers containing methyl, butyl, or lauryl methacrylate as hydrophobic comonomers were synthesized via catalytic chain transfer polymerization to give stabilizers with varying architecture, composition, and molar mass. A range of latexes of virtually the same composition was prepared by keeping the content of methacrylic acid groups during the emulsion polymerization constant and by only varying the microstructure of the macromonomers. These latexes displayed a range of rheological behaviors: from highly viscous and shear thinning to low viscous and Newtonian. The contact angles of the resulting coatings ranged from very hydrophilic (<10°) to almost hydrophobic (88°), and differences in hardness, roughness, and water vapor sorption and permeability were found.

Pattern Formation in Evaporating Polymer Solutions-Interplay between Dewetting and Decomposition.

Pattern formation during solution evaporation is common in several industrial settings and involves a complex interplay of multiple processes, including wetting/dewetting, diffusion, and rheological characteristics of the solution. Monitoring the emergence of patterns during evaporation under controlled conditions may allow deconvolution of different processes and, in turn, improve our understanding of this common yet complex phenomenon. Here, we probe the importance of initial conditions, defined by the solution concentration c 0, on the pattern formation in evaporating polymer solutions on the air-water interface. Intriguingly, the initial decrease in the lateral length scale (ξ), characterizing the patterns, takes an upturn at higher concentrations, revealing reentrant behavior. We employ a gradient dynamics model consisting of coupled evolution equations for the film height and the polymer fraction in the solution. Our simulations capture two different length scales revealing the reasons underlying the re-entrant behavior of ξ(c 0). While the long-range destabilizing interactions between suspension and water result in the dewetting of thin film solutions, the phase separation between the polymer and solvent occurs at shorter length scales. Our results demonstrate the importance of initial concentration on pattern formation and, thereby, on the resultant properties of thin polymer films.

Resistive Memristors Using Robust Electropolymerized Porous Organic Polymer Films as Switchable Materials.

Porous organic polymers (POPs) with inherent porosity, tunable pore environment, and semiconductive property are ideally suitable for application in various advanced semiconductor-related devices. However, owing to the lack of processability, POPs are usually prepared in powder forms, which limits their application in advanced devices. Herein, we demonstrate an example of information storage application of POPs with film form prepared by an electrochemical method. The growth process of the electropolymerized films in accordance with the Volmer-Weber model was proposed by observation of atomic force microscopy. Given the mechanism of the electron transfer system, we verified and mainly emphasized the importance of porosity and interfacial properties of porous polymer films for memristor. As expected, the as-fabricated memristors exhibit good performance on low turn-on voltage (0.65 ± 0.10 V), reliable data storage, and high on/off current ratio (104). This work offers inspiration for applying POPs in the form of electropolymerized films in various advanced semiconductor-related devices.

Bioinspired All‐Polyester Diblock Copolymers Made from Poly(Pentadecalactone) and Poly(3,4‐Ethylene Furanoate): Synthesis and Polymer Film Properties

AbstractBio‐based, fully degradable aliphatic‐aromatic block copolymers are synthesized from ω‐pentadecalatone and cyclic oligo(3,4‐ethylene furanoate). In the first approach, the ring‐opening polymerization of the cyclic oligo(3,4‐ethylene furanoate) is initiated by a poly(pentadecalactone) macroinitiator with a terminal hydroxy group. The reaction temperatures of the melt polymerization are 210–230 °C due to the high melting points of the oligo(3,4‐ethylene furanoate). Under these conditions, transesterification is observed. The blockiness of the reaction products depends on the reaction temperature and on the ratio of pentadecalactone to 3,4‐ethylene furanoate repeat units, which is 50:50, 80:20, and 90:10. At lower temperatures and more pentadecalactone content, the blockiness is larger. The number average molar mass of the block copolymers remains smaller than 20 000 g mol−1. In the second approach, poly(pentadecalactone) is functionalized with an alkyne group, and the OH group of the oligo(3,4‐ethylene furanoate) (molar mass 1900 g mol−1) is converted into an azide group. Connecting the two polymers in a copper‐catalyzed 1,3‐dipolar addition reaction (“click reaction”) yields block copolymers with a number average molar mass of 12 400 g mol−1. The mechanical properties of the polymer films are intermediate between those of the parent homopolymers.

The synergistic effect of body modification and surface coating for the moisture barrier of hydrophilic PU film

Polyurethane (PU) films have established a distinctive position among various protective materials due to their outstanding chemical and physical properties. However, their limited moisture barrier performance hinders their broader applications. To solve this difficult problem, PU film is first modified by adding reactive fillers (MgO) and physical barrier fillers (Modified graphene oxide, M-GO), and then Si-DLC coating is deposited on the surface of the film by hollow cathode plasma immersion ion implantation (HCPIII) method at near room temperature. MgO can react with the water molecules diffused into the film, while the addition of M-GO extends the diffusion path of water molecules. It is revealed that the addition of 5% MgO and 0.5% M-GO, along with the deposition of a 2.56 μm Si-doped DLC coating, leads to a remarkable 14.67-fold reduction in the water vapor transmittance rate (WVTR). The result of molecular dynamics simulations shows that the reactive sheet filler captures the water molecules and reduces the WVTR. In addition, the combination method of PU body modification and surface coating is suitable for polyurethane foam (PUF) to reduce the WVTR as a double coating. It's amazing that the WVTR of PUF significantly reduces by 15.29 times after double-coating. The combination of body modification and surface coating provides an effective route for significantly improving the moisture barrier property of hydrophilic polymer film and polymer foam.

Carbon nanocone mechanical behavior and their use as AFM tips for the characterization of polymers in Peak Force mode

Compared to carbon nanotube-based Atomic Force Microscopy probes, carbon nanocone-based probes appear as promising candidates for investigating topography and mechanical properties thanks to the reduced number of artefacts. In this paper, we intend to investigate some of the mechanical features of carbon nanocone (CnC) tips and to evaluate their performances as probes for investigating the mechanical properties of polymer films and composites. Using their force distance curve, the cantilever/CnC spring constant of several CnC probes is determined and the related bending force for each cone is extracted. The results demonstrate CnC bending forces ranging from 100 nN up to 3 μN, which is up to 2 orders of magnitude higher than values reported in the literature for carbon nanotubes. Moreover, the bending phenomenon occurred only when the CnC axis was not strictly perpendicular to the substrate surface. Using Peak-Force Quantitative NanoMechanical (PF-QNM) mode, we demonstrate that CnC probes are suitable to accurately probe polymer mechanical properties, provided the same targeted deformation is used for both the calibration and PF-QNM measurements.

In-plane oxygen diffusion measurements in polymer films using time-resolved imaging of programmable luminescent tags

Oxygen diffusion properties in thin polymer films are key parameters in industrial applications from food packaging, over medical encapsulation to organic semiconductor devices and have been continuously investigated in recent decades. The established methods have in common that they require complex pressure-sensitive setups or vacuum technology and usually do not come without surface effects. In contrast, this work provides a low-cost, precise and reliable method to determine the oxygen diffusion coefficient D in bulk polymer films based on tracking the phosphorescent pattern of a programmable luminescent tag over time. Our method exploits two-dimensional image analysis of oxygen-quenched organic room-temperature phosphors in a host polymer with high spatial accuracy. It avoids interface effects and accounts for the photoconsumption of oxygen. As a role model, the diffusion coefficients of polystyrene glasses with molecular weights between 13k and 350k g/mol are determined to be in the range of (0.8–1.5) × 10–7 cm2/s, which is in good agreement with previously reported values. We finally demonstrate the reduction of the oxygen diffusion coefficient in polystyrene by one quarter upon annealing above its glass transition temperature.

Electrochemical synthesis and properties of multicolor electrochromic triphenylamine-based polymer films

Electrochemical synthesis and properties of multicolor electrochromic triphenylamine-based polymer films

Thickness-dependent thermoelectric properties of ultrathin polymer film on self-assembled monolayers

Conductive polymers have attracted attention for wearable and implantable thermoelectric devices due to their lightweight, flexibility, and solubility. With the development of microsystems, thermoelectric power generation devices are trending toward miniaturization, flexibility, high integration, and lightweight thin films. Therefore, the study of the thickness of thermoelectric materials has become increasingly important. In this study, we prepared ultrathin polymer thermoelectric (TE) films with different thicknesses (14–52 nm) by modifying the substrate with self-assembled monolayers (SAMs). The thickness-dependent thermoelectric performances on SAMs are investigated. It is found that SAMs regulate the carrier concentration in polymer ultrathin TE films, and a smoother surface contributes to the improvement of carrier mobility, thus optimizing the thermoelectric performance. The maximum modulation of thermoelectric performance is observed at a film thickness of approximately 35 nm, which contains nine molecular layers.

Investigation of optical properties of nanoparticle-dispersed polymer films

Composite films of polystyrene and polymethyl methacrylate with added ZnO and ZrO2 nanoparticles have been prepared. Effective medium approximations have been applied to calculate final refractive indices. Results are compared to the experimental values of films with different thickness. Transparency of neat polymer and nanocomposite layers is also studied.

Temperature Coefficient of Electronic Polarizability in Thin Polymer Films Deposited on Si and SiO2 Substrates Determined via Spectroscopic Ellipsometry

Ellipsometry is widely used to determine the thermo-optical properties of thin polymer films. However, if the thermo-optic coefficient (TOC) and the linear thermal expansion coefficient (LTEC) are to be used to determine the temperature coefficient of electronic polarizability (TCEP) in thin polymer films, their values must be determined with the greatest possible accuracy, as both have the opposite effect. In this article, we analyze changes in ellipsometric parameters resulting from changes in the thin film temperature in order to develop a data analysis method for temperature-dependent spectroscopic ellipsometry that will facilitate the accurate determination of thermo-optical parameters, including the TCEP, in polymer thin films. As practical application examples, we identified optimal spectral windows to accurately determine the thermo-optical parameters of 50 to 150 nm-thick PMMA thin films deposited on Si and SiO2 substrates. The influence of thin-film thickness on the accuracy of TOC and LTEC determination is discussed.

Cellulose Nanofiber and Carrageenan Films Infused Eugenol for Food Preservation

This study explores the physicochemical and antioxidant properties of bio-based polymer films made from semi-refined carrageenan (SRC), plasticized with glycerol, and enhanced with eugenol to inhibit lipid degradation in meat patties. The active films were developed using 2% w/w SRC, 0.9% v/v glycerol, 10% v/v cellulose nanofiber (CNF) as a reinforcing agent, and 0.2% and 0.4% v/v eugenol (Eu). The wettability of the films was evaluated using contact angle analysis, while weight loss was assessed through soil burial degradation over a period of four weeks. Additional tests examined the films’ swelling and transparency properties. Lipid degradation in meat patties was measured using Thiobarbituric Acid Reactive Substances (TBARS). The CNG-0.4%Eu films showed a contact angle of 109.01º and a swelling rate of 93.44%. The antioxidant films successfully delayed lipid oxidation in meat patties, with final TBARS values of 0.768–0.844 mg malondialdehyde per kg of sample. Therefore, the CNG-0.4%Eu formulation demonstrates potential as an alternative food packaging material to extend shelf life.

Simulation study of the conformation and dynamics of substrate-supported ring and linear polymer films.

The effects of chain topology on the conformational and dynamic properties of substrate-supported ring and linear polymer films were investigated by molecular dynamics simulations. The study reveals that the adsorbed ring polymer chains exhibit stronger adsorbability but less deformation than the linear ones. This results in a slower desorption of ring chains in a short time. However, over a long time, the desorption rate of the ring chain is larger because of the faster diffusion of the ring chain in bulk. In addition, the non-adsorbed chains in the interface region also exhibit obvious deformation and suppressed diffusivity due to the interchain interaction between non-adsorbed chains and adsorbed ones. The suppression degree of diffusivity is approximately the same for both films. The possible underlying physics is that the interchain interaction between non-adsorbed chains and adsorbed ones in the linear polymer films is overall stronger, but each non-adsorbed ring chain experiences stronger interchain interactions with the adsorbed chains. The results show that tails in the linear polymer film and loops in the ring polymer film play an important role in the interchain interaction.

МОДИФИЦИРОВАННЫЕ В ПЛАЗМЕ СКОЛЬЗЯЩЕЙ ДУГИ ГИДРОИЗОЛЯЦИОННЫЕ ПОЛИМЕРНЫЕ ПЛЕНКИ

The article considers the use of polyethylene modified in sliding arc plasma as a waterproofing material. It assesses influence of plasma modification on physical and mechanical properties of polyethylene films by testing for relative elongation and maximum load. The study establishes increase in the size of supramolecular structures in crystalline parts, changing the strength properties of polymer film. It has been experimentally proven that application of 10-second plasma modification by sliding arc using the developed plasma installation results in formation of activated layer on the surface of polyethylene films, which increases the strength characteristics of the material. It has been determined that modifying the polyethylene within 10 seconds increases the strength of the polymer films. Due to increased mechanical strength and changed surface structure, modified polyethylene films are of interest as a base material for creating polymer-roll waterproofing materials.