Surface Properties Of Polymers Research Articles

Functionalised Fibres as a Coupling Reinforcement Agent in Recycled Polymer Composites.

This study addresses the structure-property relationship within the green concept of wood fibres with cellulose nanofibre functionalised composites (nW-PPr) containing recycled plastic polyolefins, in particular, polypropylene (PP-r). It focuses especially on the challenges posed by nanoscience in relation to wood fibres (WF) and explores possible changes in the thermal properties, crystallinity, morphology, and mechanical properties. In a two-step methodology, wood fibres (50% wt%) were first functionalised with nanocellulose (nC; 1-9 wt%) and then, secondly, processed into composites using an extrusion process. The surface modification of nC improves its compatibility with the polymer matrix, resulting in improved adhesion, mechanical properties, and inherent biodegradability. The effects of the functionalised WF on the recycled polymer composites were investigated systematically and included analyses of the structure, crystallisation, morphology, and surface properties, as well as thermal and mechanical properties. Using a comprehensive range of techniques, including X-ray diffraction (XRD), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), zeta potential measurements, and dynamic mechanical analysis (DMA), this study aims to unravel the intricate interplay of factors affecting the performance and properties of the developed nanocellulose-functionalised wood fibre-polymer composites. The interfacial adhesion of the nW-PPr polymer composites, crystallisation process, and surface properties was improved due to the formation of an H-bond between the nW coupling agent and neat PP-r. In addition, the role of nW (1.0 wt%) as a nucleating agent resulted in increased crystallinity, or, on the other hand, promoted the interfacial interaction with the highest amount (3.0% wt%, 9.0% wt%) of nW in the PP-r preferentially between the nW and neat PP-r, and also postponed the crystallisation temperature. The changes in the isoelectric point of the nW-PPr polymer composites compared to the neat PP-r polymer indicate the acid content of the polymer composite and, consequently, the final surface morphology. Finally, the higher storage modulus of the composites compared to neat r-PP shows a dependence on improved crystallinity, morphology, and adhesion. It was clear that the results of this study contribute to a better understanding of sustainable materials and can drive the development of environmentally friendly composites applied in packaging.

New Surface Modification of Hydrophilic Polyvinyl Alcohol via Predrying and Electrospinning of Hydrophobic Polycaprolactone Nanofibers.

Despite the excellent oxygen barrier and biodegradability of polyvinyl alcohol (PVA), its poor physical properties owing to its inherent hydrophilicity limit its application. In this paper, we report a novel surface modification technique for PVA films, involving the control of the predrying conditions (i.e., amount of residual solvent) of the coated PVA film and adjusting the electrospinning process of hydrophobic polycaprolactone (PCL) nanofibers onto the PVA films. The residual solvent of the coated PVA film was varied by changing the predrying time. A shorter predrying time increased the residual solvent content significantly (p < 0.05) and the flexibility of the coated PVA film. Moreover, scanning electron microscopy depicted the improved physical binding of hydrophobic PCL nanofibers to the hydrophilic PVA surface with increased penetration depth to the PVA film with shorter drying times. The PVA/PCL composite films with different predrying times and electrospun PCL nanofibers exhibited an apparent increase in the contact angle from 8.3° to 95.1°. The tensile strength of the pure PVA film increased significantly (p < 0.05) from 7.5 MPa to 77.4 MPa and its oxygen permeability decreased from 5.5 to 1.9 cc/m2·day. Therefore, our newly developed technique is cost-effective for modifying the surface and physical properties of hydrophilic polymers, broadening their industrial applications.

Surface Modification of Polymers by Plasma Treatment for Appropriate Adhesion of Coatings.

In this study, recent advances in tailoring the surface properties of polymers for the optimization of the adhesion of various coatings by non-equilibrium gaseous plasma are reviewed, and important findings are stressed. Different authors have used various experimental setups and reported results that scatter significantly and are sometimes contradictory. The correlations between the processing parameters and the adhesion are drawn, and discrepancies are explained. Many authors have explained improved adhesion with the adjustment of the surface free energy or wettability of the polymer substrate and the surface tension of liquids used for the deposition of thin films. The adhesion force between the polymer substrate and the coating does not always follow the evolution of the surface wettability, which is explained by several effects, including the aging effects due to the hydrophobic recovery and the formation of an interlayer rich in loosely bonded low molecular weight fragments.

Surface modification strategies for improved hemocompatibility of polymeric materials: a comprehensive review.

Polymeric biomaterials are a widely used class of materials due to their versatile properties. However, as with all other types of materials used for biomaterials, polymers also have to interact with blood. When blood comes into contact with any foreign body, it initiates a cascade which leads to platelet activation and blood coagulation. The implant surface also has to encounter a thromboinflammatory response which makes the implant integrity vulnerable, this leads to blood coagulation on the implant and obstructs it from performing its function. Hence, the surface plays a pivotal role in the design and application of biomaterials. In particular, the surface properties of biomaterials are responsible for biocompatibility with biological systems and hemocompatibility. This review provides a report on recent advances in the field of surface modification approaches for improved hemocompatibility. We focus on the surface properties of polysaccharides, proteins, and synthetic polymers. The blood coagulation cascade has been discussed and blood - material surface interactions have also been explained. The interactions of blood proteins and cells with polymeric material surfaces have been discussed. Moreover, the benefits as well as drawbacks of blood coagulation on the implant surface for wound healing purposes have also been studied. Surface modifications implemented by other researchers to enhance as well as prevent blood coagulation have also been analyzed.

Evolution of surface functional groups and aromatic ring degradation upon treatment of polystyrene with hydroxyl radicals

The surface properties of hydrocarbon polymers are inadequate for numerous applications. Hence, they require alteration via functionalisation with desired functional groups. Hydroxyl groups are often preferred, since they enable appropriate polarity for the irreversible grafting of desired molecules. In this study, the surface kinetics resulting from the treatment of polystyrene with hydroxyl (OH) radicals from the gas phase was fundamentally investigated through a precisely-designed experiment. Polystyrene samples were exposed to various known fluences of OH radicals, and the evolution of surface functional groups versus the OH fluence was monitored using high-resolution X-ray photoelectron spectroscopy (XPS). The fluences of OH radicals varied between 1 × 1018 and 4 × 1023 m−2 in the process of finding a threshold fluence for the formation of specific groups. The surface concentration of carbonyl (C=O) groups could be measured using XPS at a fluence of approximately 5 × 1020 m−2. The C=O groups became measurable at a fluence of approximately 1.5 × 1021 m−2, and carboxyl (COOH)/ester groups at approximately 4 × 1021 m−2. As deduced from the XPS, a concentration of C=O groups at approximately 5 % occurred before the degradation of the aromatic ring. The formation of other oxygen-functional groups required opening of the aromatic ring. The results have been explained using a two-step process, considering available theories vis-a-vis initial stages in the functionalisation of PS with polar functional groups.

Deep learning algorithm to predict friction coefficient of matching pairs at different temperature domains based on friction sound

The tribological properties of matching pairs at different temperature domain is predicted through friction sound. Two deep learning algorithms respectively by virtue of the Nonlinear Auto-Regressive models with Exogenous Inputs and long short-term memory neural network are adopted to analyze the acoustic features of friction sound to predict tribological properties of polymer surface at five temperatures within a large temperature domain under different working conditions. The deep learning algorithm precisely fits the friction coefficient in accordance with the performance analysis.

Surface modification of polymers by ion irradiation: Reactivity principle and application

Modifying polymers through ion irradiation is an advantageous method for controlling polymer with desirable properties. The surface modification mechanism and application of polymers by ion irradiation are under exploration. This review systematically analyzes the recent progress on the surface modification of common polymers by ion irradiation. The fundamentals of irradiation principle and chemical interaction, the irradiation effect of microstructure, macroproperties, and related characterization methods are introduced for the innovated applications. The effect of ion beam conditions (heavy or light ions, high or low energy/fluences) on different polymers is systematically analyzed for the different irradiation effect to achieve surface modification, in which the coupling mechanism between nuclear and electronic stopping power is provided. To meet the requirement of various application, the relationship between micro representation and macro performance is thoroughly discussed and established combined with the concerns regarding ion irradiation induced regulation mechanism. For the practical/potential application prospects, the frontier research on membrane separation, electrical, and biomedical applications are discussed. This review offers valuable insights into the modified microstructures versus the necessary surface properties of polymer by ion irradiation.

Surface and Mechanical Properties of 3D-Printed Biocompatible ABS Polymers

Surface and Mechanical Properties of 3D-Printed Biocompatible ABS Polymers

Advanced method for efficient functionalization of polymers by intermediate free-radical formation with vacuum-ultraviolet radiation and producing superhydrophilic surfaces

An efficient approach for tailoring surface properties of polymers is presented, which enables rapid modification leading to superhydrophilic properties. The approach is based on vacuum-ultraviolet radiation (VUV) pretreatment of the surface to create reactive dangling bonds. This step is followed by a second treatment using neutral oxygen atoms that react with the dangling bonds and form functional groups. The beneficial effect of VUV pretreatment for enhanced functionalization was clearly demonstrated by comparing VUV pretreatment in plasmas created in different gases, i.e., hydrogen, nitrogen, and oxygen, which differ in the intensity of VUV/UV radiation. The emission intensity of VUV radiation for all gases was measured by vacuum ultraviolet spectroscopy. It was shown that VUV has a strong influence on the treatment time and final surface wettability. A superhydrophilic surface was obtained only if using VUV pretreatment. Furthermore, the treatment time was significantly reduced to only a second of treatment. These findings show that such an approach may be used to enhance the surface reaction efficiency for further grafting of chemical groups.

Design of Soft Material Surfaces with Rationally Tuned Water Diffusivity.

Water structure and dynamics can be key modulators of adsorption, separations, and reactions at soft material interfaces, but systematically tuning water environments in an aqueous, accessible, and functionalizable material platform has been elusive. This work leverages variations in excluded volume to control and measure water diffusivity as a function of position within polymeric micelles using Overhauser dynamic nuclear polarization spectroscopy. Specifically, a versatile materials platform consisting of sequence-defined polypeptoids simultaneously offers a route to controlling the functional group position and a unique opportunity to generate a water diffusivity gradient extending away from the polymer micelle core. These results demonstrate an avenue not only to rationally design the chemical and structural properties of polymer surfaces but also to design and tune the local water dynamics that, in turn, can adjust the local activity for solutes.

Surface electric charge decay behavior of Polypropylene (PP) films treated by atmospheric air dielectric barrier discharge

Atmospheric air dielectric barrier discharge (DBD) is one of the most effective physical techniques for the cold plasma source. It is a promising technique used to modify the surface properties of polymers. This modification leads to improving wetting and adhesion properties, a change in surface roughness and other significant technological features. In recent studies, researchers have showed that DBD plasma exposure can modify the electric properties of insulating materials. In this study, we focused our attention on the influence of DBD plasma treatment on the surface electric charge behavior in polypropylene (PP) thin films. The effect of DBD plasma has been studied as a function of treatment time for two values of applied discharge voltages; 7 and 12 kV. After being exposed to DBD plasma, the samples were charged for 5 seconds in ambient air using a negative triode corona electrode system. The influence of DBD plasma treatment on the surface electric charge behaviour in PP thin films was investigated. The surface characterization of the untreated and treated PP films is performed using surface electric charge decay measurements, for identical charging conditions.

Recent Advances in Transition Metal-Based Catalysts for Ethylene Copolymerization with Polar Comonomer.

The synthesis of polar functionalized polyolefin (PFP) offers improvement in mixing properties, polymer surface, and rheological properties with the potential of upgraded polyolefins for modern and ingenious applications. The synthesis of PFP from metal-based catalyzed olefin (non-polar in nature) copolymerization with polar comonomers embodies energy-efficient, atom-efficient, and apparently an upfront methodology. Despite their outstanding success during conventional polymerization of olefin, 3rd and 4th group (early transition metal)-based catalysts, owing to their electrophilic nature, face challenges mainly due to Lewis basic sites of the polar monomers. On the contrary, late transition metal-based catalysts have also made progress, in recent years, for PFP synthesis. The recent past has also witnessed several advancements in the development of dominating palladium-based catalysts while their lower resistance towards ligand functional groups has limited the practical application of abundant and cheaper nickel-based catalysts. However, the relentless efforts of the scientific community, during the past half-decade, have indicated rigorous progress in the development of nickel-based catalysts for PFP synthesis. In this review, we have abridged the recent research trends in both early as well as late transition metal-based catalyst development. Furthermore, we have highlighted the role of transition metal-based catalysts in influencing the polymer properties.

Plasma Surface Engineering of Natural and Sustainable Polymeric Derivatives and Their Potential Applications.

Recently, natural as well as synthetic polymers have been receiving significant attention as candidates to replace non-renewable materials. With the exponential developments in the world each day, the collateral damage to the environment is incessant. Increased demands for reducing pollution and energy consumption are the driving force behind the research related to surface-modified natural fibers (NFs), polymers, and various derivatives of them such as natural-fiber-reinforced polymer composites. Natural fibers have received special attention for industrial applications due to their favorable characteristics, such as low cost, abundance, light weight, and biodegradable nature. Even though NFs offer many potential applications, they still face some challenges in terms of durability, strength, and processing. Many of these have been addressed by various surface modification methodologies and compositing with polymers. Among different surface treatment strategies, low-temperature plasma (LTP) surface treatment has recently received special attention for tailoring surface properties of different materials, including NFs and synthetic polymers, without affecting any of the bulk properties of these materials. Hence, it is very important to get an overview of the latest developments in this field. The present article attempts to give an overview of different materials such as NFs, synthetic polymers, and composites. Special attention was placed on the low-temperature plasma-based surface engineering of these materials for diverse applications, which include but are not limited to environmental remediation, packaging, biomedical devices, and sensor development.

The efficient adsorption of tetracycline from aqueous solutions onto polymers with different N-vinylpyrrolidone contents: equilibrium, kinetic and dynamic adsorption.

Extensive use of antibiotics in the world will cause potential risks to human health and ecosystems. The removal of these antibiotics has attracted much attention. Composite materials are growing attention for diverse pollutants separation and removal based on their specific functionality and surface area. In this study, a series of N-vinylpyrrolidone-divinylbenzene polymers (NVPD) with different N-vinylpyrrolidone (NVP) contents were facilely prepared for the adsorption of tetracycline (TC). The effect of polymer surface properties and aqueous solution chemistry (pH, ionic strength, humic acid) on TC adsorption was further studied. The dynamic adsorption and regeneration experiments were also assessed. The results showed that only 25% of NVP was involved in the reaction. When NVP dosage (%) was 75%, polymer (NVPD-g) owned the largest BET surface area (613.23 m2/g) and obtained the maximum TC adsorption capacities (258.76mg/g). In the kinetic, the adsorption between TC and polymers with NVP was controlled by chemical adsorption and intra-particle diffusion. The TC adsorption process of NVPD-g depended on the contribution of the hydrophobic effect, electrostatic interactions, H-bonding, π-πelectron donor-acceptor(EDA) interactions, and cation-π bonding. Moreover, the removal efficiency of TC by NVPD-g was enhanced in the presence of humic acid (HA) in the dynamic adsorption and 1197 BV (2394mL) of TC simulated wastewater can be treated. These findings suggest that NVPD-g has a potential application inthe purification of TC.

Physiochemically Distinct Surface Properties of SU-8 Polymer Modulate Bacterial Cell-Surface Holdfast and Colonization.

SU-8 polymer is an excellent platform for diverse applications due to its high aspect ratio of micro/nanostructure fabrication and exceptional physicochemical and biocompatible properties. Although SU-8 polymer has often been investigated for various biological applications, how its surface properties influence the interaction of bacterial cells with the substrate and its colonization is poorly understood. In this work, we tailor SU-8 nanoscale surface properties to investigate single-cell motility, adhesion, and successive colonization of phytopathogenic bacteria, Xylella fastidiosa. Different surface properties of SU-8 thin films have been prepared using photolithography processing and oxygen plasma treatment. A more significant density of carboxyl groups in hydrophilic plasma-treated SU-8 surfaces promotes faster cell motility in the earlier growth stage. The hydrophobic nature of pristine SU-8 surfaces shows no trackable bacterial motility and 5-10 times more single cells adhered to the surface than its plasma-treated counterpart. In addition, plasma-treated SU-8 samples suppressed bacterial adhesion, with surfaces showing less than 5% coverage. These results not only showcase that SU-8 surface properties can impact the spatiotemporal bacterial behavior but also provide insights into pathogens' prominent ability to evolve and adapt to different surface properties.

Ultrasonication-induced and diluent-assisted suspension polymerization for size-controllable synthesis of polydimethylsiloxane droplets

Submicroscale polydimethylsiloxane (PDMS) spheres are emerging as a promising solution for a variety of engineering applications due to their unique material properties and size. It is, however, still considered as challenging to produce submicroscale PDMS droplets. This leads to the need for development of a deterministic method for producing size-controllable, monodisperse PDMS droplets and, by extension, comprehensive understanding of the physicochemical players and processes involved in the synthesis method. Here, we develop an ultrasonication-induced and diluent-assisted (UIDA) suspension polymerization process to achieve the scalable synthesis of monodisperse PDMS droplets. The UIDA suspension polymerization process is essentially the same as conventional suspension polymerization processes except ultrasonic agitation and organic diluent addition. The use of ultrasonication is intended to controllably reduce the size of PDMS droplets, while the addition of a diluent to PDMS is designed to enhance the monodispersity of PDMS droplets (major) and decrease their size (minor). First, we explore the dependence of PDMS droplet size and polydispersity on rudimentary factors such as stabilizer (i.e., polyvinyl alcohol (PVA)), magnetic stirring, ultrasonication, diluent (i.e., benzene), and synthesis vessel. Next, a time-variant change in the size and size distribution of PDMS droplets under UIDA suspension polymerization process are investigated by deconvoluting the droplet dispersity in size into two components, each of which is described using an envelope of the log-normal distribution. The main cause of a bimodal distribution is also identified. Finally, we demonstrate the applicability of PDMS droplets in altering the hydrodynamic properties of polymer surfaces by fabricating a set of rose petal-inspired substrates through evaporation coating of PDMS droplets on flat PDMS surfaces. The findings of this study will lead to better understanding of suspension polymerization for synthesizing monodisperse submicroscale droplets made of thermosetting polymers.

Sodium hypochlorite as an oxidizing agent for removal of soil organic matter before microplastics analyses.

The omnipresence of microplastics (MPs) across Earth's surface has raised concerns about their environmental impact and created an urgent need for methods to identify them in complex soil and sedimentary matrices. However, detecting MPs in the O horizons of soils is difficult because plastic polymers share many physical and chemical properties with natural soil organic matter (SOM). In this study, we assessed whether sodium hypochlorite (NaOCl), a reagent that can oxidize SOM and simultaneously preserve mineral constituents, can be used for MP analysis and characterization in soil environments. In addition, we scrutinized how factors such as MP size, polymer type, extraction methods, and soil matrix affect the recovery of microplastic particles. We used both hydrophobic and density-dependent separation methods to assess the effects of our oxidation treatment on the recovery of MP. We observed that NaOCl effectively removed SOM without greatly altering the surface properties of resistant MP polymers (polypropylene, polylactic acid, low-density polyethylene, and polyethylene terephthalate), which were characterized using scanning electron microscopy and Fourier-transform infrared spectroscopy after SOM removal. The NaOCl treatment caused some chlorination and formation of additional C-OH bonds on polymer surfaces, which likely contributed to the reduced efficiency of the hydrophobic-based (oil) extraction. We conclude that NaOCl treatment can improve detection of MPs in SOM-rich soil and that recovery of MPs from soils is influenced by MP size, polymer type, extraction method, and soil type, which makes it challenging to develop a universal analytical method.

Effect of crystallinity and related surface properties on gene expression of primary fibroblasts.

The biomaterial-cells interface is one of the most fundamental issues in tissue regeneration. Despite many years of scientific work, there is no clear answer to what determines the desired adhesion of cells and the synthesis of ECM proteins. Crystallinity is a characteristic of the structure that influences the surface and bulk properties of semicrystalline polymers used in medicine. The crystallinity of polycaprolactone (PCL) was varied by changing the molecular weight of the polymer and the annealing procedure. Measurements of surface free energy showed differences related to substrate crystallinity. Additionally, the water contact angle was determined to characterise surface wettability which was crucial in the analysis of protein absorption. X-ray photoelectron spectroscopy was used to indicate oxygen bonds amount on the surface. Finally, the impact of the crystallinity, and related properties were demonstrated on dermal fibroblasts' response. Cellular proliferation and expression of selected genes: α-SMA, collagen I, TIMP, integrin were analysed.

Non-Equilibrium Plasma Methods for Tailoring Surface Properties of Polyvinylidene Fluoride: Review and Challenges.

Modification and functionalization of polymer surface properties is desired in numerous applications, and a standard technique is a treatment with non-equilibrium gaseous plasma. Fluorinated polymers exhibit specific properties and are regarded as difficult to functionalize with polar functional groups. Plasma methods for functionalization of polyvinylidene fluoride (PVDF) are reviewed and different mechanisms involved in the surface modification are presented and explained by the interaction of various reactive species and far ultraviolet radiation. Most authors used argon plasma but reported various results. The discrepancy between the reported results is explained by peculiarities of the experimental systems and illustrated by three mechanisms. More versatile reaction mechanisms were reported by authors who used oxygen plasma for surface modification of PVDF, while plasma sustained in other gases was rarely used. The results reported by various authors are analyzed, and correlations are drawn where feasible. The processing parameters reported by different authors were the gas pressure and purity, the discharge configuration and power, while the surface finish was predominantly determined by X-ray photoelectron spectroscopy (XPS) and static water contact angle (WCA). A reasonably good correlation was found between the surface wettability as probed by WCA and the oxygen concentration as probed by XPS, but there is hardly any correlation between the discharge parameters and the wettability.

Experimental and Numerical Study of the Effect of Surface Patterning on the Frictional Properties of Polymer Surfaces

Abstract We describe benchmark experiments to evaluate the frictional properties of laser patterned low-density polyethylene as a function of sliding velocity, normal force, and humidity. The pattern is a square lattice of square cavities with sub-mm spacing. We find that dynamic friction decreases compared to nonpatterned surfaces, since stress concentrations lead to early detachment, and that stick-slip behavior is also affected. Friction increases with humidity, and the onset of stick-slip events occurs in the high humidity regime. Experimental results are compared with numerical simulations of a simplified 2D spring-block model. A good qualitative agreement can be obtained by introducing a deviation from the linear behavior of the Amontons-Coulomb law with the load due to a saturation in the effective contact area with pressure. This also leads to the improvement of the quantitative results of the spring-block model by reducing the discrepancy with the experimental results, indicating the robustness of the adopted simplified approach, which could be adopted to design patterned surfaces with controlled friction properties.