Polyethylene Terephthalate Surface Research Articles

Construction of antithrombotic and antimicrobial ultra-thin structures on a polyethylene terephthalate implant via the surface grafting of heparin brushes.

It remains a challenge to endow a polymeric material with antithrombotic ability by surface grafting without disturbing the bulk properties of the substrate. Heparin-based functional structures of less than 80 nm were fabricated and covalently grafted on a polyethylene terephthalate surface via carbene chemistry (Hep-g-PET). Heparin was oxidized with the minimum antithrombrin sequence retained, creating an aldehyde group on the chain terminus. Oxidized heparin was then covalently attached to a poly(amidoamine) (PAMAM)-grafted PET substrate. The interface between blood and PET was improved by the surface functionality, and the amount of attached platelets decreased to 29 ± 12.1% of its initial value. The bulk properties of the functionalized film were hardly influenced, and the visible light transmittance remained more than 96%. The tethered structures also showed the ability to kill attached S. aureus and E. coli efficiently. The functionalized membrane showed negligible ex vivo cell cytotoxicity and a low hemolysis ratio. Hep-g-PET was implanted in between rat skin and muscle, and showed an outstanding histological response and antimicrobial ability. The influences of the graft thickness and the heparin chain length were explored. The strategies reported in this work may help to improve the design of polymeric implant bio-devices.

Enhancement of hydrophilicity and color strength in plasma treated PET with water vapor post-exposure using a new in-line pilot scale DBD plasma

Due to its low hydrophilicity, direct sublimation inkjet printing on woven polyester fabric surfaces is challenging. This research experimentally studies the efficacy of dielectric barrier discharge (DBD) roll-to-roll plasma treatment with or without water vapor post-exposure as a novel method to modify polyethylene terephthalate (PET) surfaces to enhance hydrophilicity, color performance, and printing quality. The Response Surface Methodology (RSM) was used to design experiments, and the optimum conditions were analyzed through statistical calculations. Their results were examined using Optical Emission Spectroscopy (OES), Atomic Force Microscopy (AFM), field emission scanning electron microscopy (FESEM), Energy Dispersive X-ray (EDX), X-ray Photoelectron Spectroscopy (XPS), and Attenuated Total Reflectance Fourier Transform Infra-Red spectroscopy (ATR-FTIR) tests. Qualitative and quantitative tests for color performance and wicking test used for hydrophilicity assessment confirms the effectiveness of this Green inline pretreatment for industries to enhance direct sublimation inkjet printing quality on PET by a decrease in absorption time from 12051 to 202 s and an increase in the color depth to 12.49%, 25.89 and 18.07% for Cyan, Magenta and Key (black) respectively. One of the stable optimum conditions in which three printed colors: Cyan, Magenta, and Black (Key), show high-quality color performance is at 15 processing rounds, 2 m/min velocity in the absence or presence of water vapor post-exposure. Water vapor post-exposure exhibits a beneficial, economic effect along with plasma treatment. The results show that the chemical modification aspect of this treatment plays a more significant role in printing quality enhancement than its morphological modification.

Highly Efficient and Reliable Organic Light–Emitting Diodes Enabled by a Multifunctional Hazy Substrate for Extreme Environments

AbstractAs transparent, flexible, and wearable organic electronics degrade under normal outdoor environmental conditions (e.g., water vapor, oxygen, and UV light) and extreme environments, including washing or rain, a customized encapsulation technology is required to improve device reliability. Herein, a simple process is presented for fabricating multifunctional hazy substrates (MFHSs) with excellent gas diffusion barrier (GDB), flexibility, UV reflectance, light scattering, and waterproof properties. First, a spiky polyethylene terephthalate (PET) surface is produced with 76.0% optical haze through ion‐beam treatment followed by the formation of a hydrophobic layer to achieve a waterproof effect (contact angle: 153.3°). Then, a multifunctional multibarrier film is fabricated based on a nano‐laminated distributed Bragg reflector and functional polymer on the functional PET substrate to serve as a GDB and UV filter. This multibarrier film has excellent mechanical and chemical stabilities, in addition to having a water vapor transmission rate of 10−6 g m−2 day−1 and UV transmittance of <3%. The so‐fabricated MFHS not only increases the device efficiency by 73% but also enables a highly flexible and environmentally stable organic light–emitting diode. The surface treatment and encapsulation technologies developed in this study are expected to increase the lifetime of organic devices and facilitate high outdoor usability.

Supercritical CO2 Assisted Ni-P Electroless Plating of PET Components with Complex 3D Structures

There is an increasing demand of methodologies to metallize complex polymer materials for application in electronics such as wearable devices and robotic products. In various metallization methods, electroless plating is a powerful and promising approach to meet this demand. The present conventional electroless plating requires pretreatment steps to deposit catalyst onto surfaces of polymer materials, which results in damages to their surfaces and also deformation of their shape because of the usage of strong acidic solvents. Furthermore, the adhesion strength between the polymer material and the metal layer is insufficient. To overcome these problems, a catalyzation step using supercritical carbon dioxide (sc-CO2) as the solvent is proposed.[1] The sc-CO2-assisted catalyzation enables a deep impregnation of catalysts into the polymer material without the pretreatment step, and this enhances the adhesive properties of the deposited metal on the polymer. By the sc-CO2-assisted catalyzation, electroless Ni-P plating of polyethylene terephthalate (PET) is realized. [1] Metallization of polymer materials with complex 3D structures is a more attractive topic, but it is widely accepted to be more difficult than film structures. Also, application the electroless plating via sc-CO2-asssited catalyzation to 3D-structured polymer materials remains unexplored. In this presentation, we report Ni-P plating of PET samples having complex 3D structures by the sc-CO2-assisited catalyzation process.A PET based material with a concavo-convex structure was designed and fabricated by the processing machine as shown in Figs. 1(a)–(b). Sc-CO2-assisted catalyzation process was performed in a high pressure reactor[1] containing palladium (II) hexafluoroacetylacetonate (Pd(C5HF6O2)2) as the palladium catalyst source at 70 °C under 15 MPa for 2 h. After the catalyzation process, the reactor was cooled to room temperature while maintaining the pressure in the reactor, and then the pressure in the reactor was reduced to atmospheric pressure. The collected PET sample from the reactor was kept under ambient atmosphere for two weeks, and then it was subjected to electroless Ni-P plating at 70 ℃ for 10 min.Fig. 1(c) shows the PET sample obtained after the sc-CO2-assisted catalyzation process followed by the post-treatment process. The volume of the catalyzed PET sample was scarcely changed. On the other hand, the post-treatment processes performed under the different conditions were found to cause undesired swelling and white turbidity of the PET sample, presumably because of microbubbles derived from residual CO2 in the PET. Fig. 1(d) shows an image of Ni-P successfully metallized on the PET surface. The electrical resistance of the Ni-P/PET material was 8.7 Ω, which is acceptable for electronic device applications. From these results, we concluded that sc-CO2-assisted catalyzation is applicable to metallization of PET materials with complex 3D structures. Reference [1] P.-W. Cheng, C.-Y. Chen, T. Ichibayashi, T.-F.M. Chang, M. Sone, S. Nishimura, J. Supercrit. Fluids 180 (2022) 105455. Figure 1

Sulfation of furcellaran and its effect on hemocompatibility in vitro

In this study, furcellaran (FUR) obtained from Furcellaria lumbricalis was firstly employed for sulfation via various methods, including SO3-pyridine (SO3∙Py) complex in different aprotic solvents, chlorosulfonic acid and sulfuric acid with a “coupling” reagent N,N′-Dicyclohexylcarbodiimide. Structural characterization through FT-IR, GPC, XPS and elemental analyses confirmed the successful synthesis of 6-O-sulfated FUR derivates characterized by varying degrees of sulfation (DS) ranging from 0.15 to 0.91 and molecular weight (Mw) spanning from12.5 kDa to 2.7 kDa. In vitro clotting assays, partial thromboplastin time (aPTT), thrombin time (TT), and prothrombin time (PT) underscored the essential role of sulfate esters in conferring anticoagulant activity whereas FUR prepared via chlorosulfonic acid with DS of 0.91 reached 311.4 s in aPPT showing almost 4-fold higher anticoagulant activity than native FUR at the concentration 2 mg/mL. MTT test showed all tested samples decreased cell viability in a dose dependent manner while all of them are non-cytotoxic up to the concentration of 0.1 mg/mL. Furthermore, sulfated derivates deposited onto polyethylene terephthalate surface presented substantial decrease in platelet adhesion, as well as absence of the most activated platelet stages. These findings support the pivotal role of O-6 FUR sulfates in enhancing hemocompatibility and provide valuable insights for a comparative assessment of effective sulfating approaches.

Interfacial mechanical properties of graphene on randomly rough PET substrate surface: A molecular dynamics study

In this work, molecular dynamics (MD) simulations are performed to create a series of polyethylene terephthalate (PET) substrates with random roughness, and the morphological characteristics and interfacial bonding of graphene on the real rough PET surface are first simulated. The results show that the interfacial mechanical behavior of graphene freely adhered to the PET roughness is influenced by the surface profile. Besides causing the non-conformal contact, the rough surface hinders the propagation of bending waves from the graphene corner regions during the adhesion and weakens their overlap. The increased surface roughness weakens interfacial adhesion and inhibits interfacial sliding, leading to the formation of larger morphological defects such as wrinkles. Furthermore, the measurement of the interfacial adhesion energy of graphene/PET substrate is achieved by the shaft loaded blister test (SLBT), which for the first time is used to simulate the interfacial debonding of graphene on rough PET surfaces. For low surface roughness, interfacial adhesion dominates the debonding behavior and the blister boundary preferentially extends along the interfacial defect area. For high surface roughness, the increasingly serious non-conformal contact makes the blister more likely to instability and enter the stage where normal and shear interactions are coupled.

The enhancement of waste PET particles enzymatic degradation with a rotating packed bed reactor

Polyethylene terephthalate (PET) is widely used, and biodegradation of waste PET results in a residue-free process, generating recyclable products, thereby contributing to the advancement of a more recyclable plastics lifecycle. Extensive research has been conducted on the modification and evolution of enzyme for PET degradation. As a solid-liquid heterogeneous reactions of PET degradation, the slow diffusion rate of the enzyme from liquid to solid PET surface leading to a slow reaction rate. Enhancement of mass transfer would accelerate PET degradation. Rotating packed bed (RPB) is a mass transfer enhancement reactor, but shear strength generated by the enzyme molecule knocking on rotator of RPB leads to enzyme denaturation. To address this issue, shear strength resistance agents were introduced in this study. With the protection of β-cyclodextrin combined with kieselguhr, PET particle degradation rate of 95% was achieved under the optimum conditions in 24 h, which was improved by 30% compared to that in stirred tank reactor. The results of this work demonstrated that the mass transfer greatly influenced the PET biodegradation process. RPB combined with the function of shear strength resistance agents could greatly improve the efficiency of the biodegradation process. This study provides a reference for the scaling up of PET degradation, and holds significant promise in the broader context of combatting plastic pollution challenges and advancing sustainable solutions for plastic waste.

On the Effect of Non-Thermal Atmospheric Pressure Plasma Treatment on the Properties of PET Film.

The aim of the work was to investigate the effect of non-thermal plasma treatment of an ultra-thin polyethylene terephthalate (PET) film on changes in its physicochemical properties and biodegradability. Plasma treatment using a dielectric barrier discharge plasma reactor was carried out in air at room temperature and atmospheric pressure twice for 5 and 15 min, respectively. It has been shown that pre-treatment of the PET surface with non-thermal atmospheric plasma leads to changes in the physicochemical properties of this polymer. After plasma modification, the films showed a more developed surface compared to the control samples, which may be related to the surface etching and oxidation processes. After a 5-min plasma exposure, PET films were characterized by the highest wettability, i.e., the contact angle decreased by more than twice compared to the untreated samples. The differential scanning calorimetry analysis revealed the influence of plasma pretreatment on crystallinity content and the melt crystallization behavior of PET after soil degradation. The main novelty of the work is the fact that the combined action of two factors (i.e., physical and biological) led to a reduction in the content of the crystalline phase in the tested polymeric material.

Solvent‐Free Depolymerization of Plastic Waste Enabled by Plastic‐Catalyst Interfacial Engineering

AbstractDepolymerization of condensation polymers by chemolysis often suffers from the large usage of solvents and homogeneous catalysts such as acids, bases, and metal salts. The catalytic efficiency of heterogeneous catalysts is largely constrained by the poor interfacial contact between solid catalysts and solid plastics below melting points. We report here our discovery of autogenous heterogeneous catalyst layer on polyethylene terephthalate surfaces during the generally believed homogeneous catalytic depolymerization process. Inspired by the “contact mass” concept in industrial chlorosilane production, we further demonstrate that the construction of plastic‐catalyst solid‐solid interfaces enables solvent‐free depolymerization of polyethylene terephthalate by vapor phase methanolysis at relatively low temperatures. Trace amounts of earth‐abundant element (zinc) introduced by electrostatic adsorption is sufficient for catalyzing the depolymerization. The concept of plastic‐catalyst contact mass interfacial catalysis might inspire new pathways for tackling plastic waste problems.

Solvent-Free Depolymerization of Plastic Waste Enabled by Plastic-Catalyst Interfacial Engineering.

Depolymerization of condensation polymers by chemolysis often suffers from the large usage of solvents and homogeneous catalysts such as acids, bases, and metal salts. The catalytic efficiency of heterogeneous catalysts is largely constrained by the poor interfacial contact between solid catalysts and solid plastics below melting points. We report here our discovery of autogenous heterogeneous catalyst layer on polyethylene terephthalate surfaces during the generally believed homogeneous catalytic depolymerization process. Inspired by the "contact mass" concept in industrial chlorosilane production, we further demonstrate that the construction of plastic-catalyst solid-solid interfaces enables solvent-free depolymerization of polyethylene terephthalate by vapor phase methanolysis at relatively low temperatures. Trace amounts of earth-abundant element (zinc) introduced by electrostatic adsorption is sufficient for catalyzing the depolymerization. The concept of plastic-catalyst contact mass interfacial catalysis might inspire new pathways for tackling plastic waste problems.

Enzymatic Degradation of PET plastic

Polyethylene terephthalate (PET) plastic is one of the most commonly used polymers worldwide and found in high rates as environmental waste. Previous studies have shown that the degradation of plastics using commercial grade enzymes is possible and highly effective in lab settings. However, the effectiveness and rates of enzymatic plastic degradation at environmentally relevant conditions is less known. In this study, we set up a series of sacrificial incubation experiments using a commercial enzyme, Humicola insolens cutinase (HiC), to examine the effect of various environmental variables, including temperature, pH, and salinity, on the hydrolytic degradation of PET. This was performed by measuring the mass loss at different time points during degradation, dissolved organic carbon produced in solution by PET hydrolysis, the Fourier transform infrared (FTIR) spectra of the PET surfaces, and scanning electron microscope (SEM) images of the PET surfaces. The results indicate that the degradation rate is 15-times faster at 55 °C than at 40 °C at pH 8 (1.93 mg day-1 versus 0.13 mg day-1), giving an initial estimate for the activation energy of PET hydrolysis of 2.2 kJ mol-1. In the 55 °C experiment which ran for 10 days, there was a noticeable decrease in the plastic strength and deformation of the plastic after 1 week of degradation. In the 40 °C experiment (duration 16 weeks), FTIR spectral changes were observed as early as week 6, with peaks of interest at 2,970 cm-1, 2,350 cm-1, 1,240 cm-1 , and between 1,300-1,000 cm-1. Ongoing experiments with pH and salinity will provide insight into their effects on the PET degradation rate. Altogether, these results will provide a comprehensive framework for predicting PET degradation rates, and by extension, other plastics that are degraded by hydrolysis, at environmentally relevant pH, temperature, and salinity conditions. In addition, these results provide insight into the effect of degradation on the chemical spectra of plastics and microplastics.

The growth mechanisms of TiO2 film onto PET surfaces by atomic layer deposition

Atomic layer deposition (ALD) was used to coat a polyethylene terephthalate (PET) polymer substrate with TiO2 film. The TiO2 was grown onto the surface with better film coverage by using thicker ALD deposition. Further evaluation on the coated substrates indicated that the reactive sites of –C=O that existed on PET surface played a significant contribution to facilitating the initial ALD growth of the TiO2 thin film. The chemical composition of the coated substrates was characterised using energy dispersive X-ray spectroscopy, which showed that increasing the TiO2 film thickness increased the Ti element content. Two growth mechanisms, namely, diffusion growth and direct coordination through the precursor coordination with surface reactive sites of –C=O with product release occurred simultaneously in the initial growth of TiO2 coating onto PET polymer by ALD. The surface alteration of the coated ALD was characterised by Fourier transform infrared spectroscopy, which showed that the hydroxyl –OH groups emerged in the TiO2 ALD film.

Synergistic interlaminar strengthening of unidirectional carbon fiber-reinforced composites using carbon nanofiber-modified sizing on the surface of PET interleaves

A unidirectional carbon fiber-reinforced composite with excellent interlaminar fracture toughness (ILFT) was fabricated, analyzed, and evaluated. The composites were formed by inserting polyethylene-terephthalate (PET)-based thermoplastic veils between prepregs to enhance the ILFT. Carbon nanofiber (CNF)-modified coupling agents were spray-deposited onto the PET veil surface to minimize the reductions in the tensile strength and modulus of the composites caused by the use of thermoplastic veils and maximize the enhancements in the ILFT. The microfibers of the PET veils endowed the composites with delamination resistance, whereas the coupling agents and CNFs coated on the PET surface induced chemical bonding and mechanical interlocking with the epoxy matrix, respectively. Therefore, multiscale reinforcement mechanisms, including these mechanical and chemical interactions, generated a synergistic effect on the mechanical properties of the composites. Reductions in the tensile strength and modulus of the composites decreased by up to 104.7% and 100.8%, respectively, following the application of the CNF/coupling agent-modified PET interleaves, and their Mode-Ⅰ and Mode-Ⅱ ILFT values increased by up to 105.3% and 610.9%, respectively, compared with those of neat composites.

Fabrication of a Hot-Embossing Metal Micro-Mold through Laser Shock Imprinting.

As a technology for polymer surface fabrication, roll-to-roll hot embossing has been widely used because of its advantages, such as its low cost and high efficiency. However, the metal micro-mold is a major factor that determines the hot embossing of the polymer. In this study, a new metal micro-mold manufacturing method is proposed. The metal micro-mold is produced using laser shock imprinting (LSI) on the surface of metal foil. It has the characteristics of good thermal stability and high strength. During our LSI experiment, the strength of the mold increased after laser shocking. In this study, copper foils of different thicknesses were selected for LSI experiments. Through the analysis of the profile and forming depth of the microstructure, combined with the numerical simulation of the forming mechanism of copper foils with different thicknesses using ABAQUS software(Abaqus 2021), a copper foil with a flat back was selected as the final metal micro-mold. On this basis, copper molds with different microstructure shapes were created. Then, the mold was used in the hot-embossing experiment to manufacture the microstructure on the surface of polyethylene terephthalate (PET) and to study the fidelity and integrity of the molded microstructure. The deformation resistance of the copper mold under hot-embossing conditions was verified through a nano-indentation experiment. The final results show that the metal micro-mold produced via LSI had a high accuracy and molding stability and has potential applications in the field of roll-to-roll hot embossing.

Assessment of Microplastic Degradation in Bottom Sediments Using Raman Microspectroscopy and Atomic Force Microscopy

The assessed degradation of microplastics from bottom sediments of the Laptev Sea, the Weddell Sea, the Chukchi Sea and Peter the Great Bay, Sea of Japan, was studied using Raman microspectroscopy and atomic force microscopy (AFM). The degree of amorphous-crystallinity of polyethylene terephthalate (PET) was determined by the ratio of Raman mode intensities (I1095 cm–1 / I1115 cm–1). Changes in the topography and mechanical properties of the surface of polymer fragments were studied by AFM methods. It has been shown that the degradation of PET found in the bottom sediments of the Laptev Sea affects mainly its crystalline phase. The amorphous phase of PET is affected to a much lesser extent or not at all. The same changes in the phase composition of the PET surface have been shown after plastic exposure in a marine aquarium in silty sand from the Amur Bay (Peter the Great Bay, Sea of Japan). AFM data show an increase in PET surface roughness and a decrease in elasticу modulus (Young’s modulus) in bottom sediment samples. Raman microspectroscopy also shows signs of degradation of cellophane fragments from the Weddell Sea, polyvinyl chloride (PVC) from the Laptev Sea, and polyethylene (PE) from the Amur Bay.

Silanization of functionalized PET fabric to improve PET-nitrile rubber (NBR) adhesion; effects of functionalization type and silane concentration

Surface modification could increase affinity of PET fibers to polymer matrix by changing the interfacial physical interactions to covalent bonds. In this research, surface modification of a superfine polyethylene terephthalate (PET) fabric was performed by bis(triethoxysilylpropyl)tetrasulfide (TESPT). The surface grafting was performed at different silane concentrations (i.e. 1, 5 and 10X). Before silanization, the fabrics were functionalized using photochemical method (i.e. irradiation of UV light in presence of glutaric acid peroxide (GAP)) and also hydrolysis by Sodium hydroxide (NaOH). Due to functionalization, carboxyl and hydroxyl groups were formed on the PET surface that made it ready to condense with hydrolyzed silane molecules. The fabrics were characterized using FTIR, TGA, FE-SEM, XPS analysis for evaluation of grafting performances. XPS analysis confirmed the presence of new peaks of Si and S after surface modification with TESPT. Comparing the results of TESPT-grafted functionalized PETs, it was found that the silane grafting content on PET surface is dependent not only to the silane concentration but also to the functionalization method. Finally, the influences of silane grafting on the functionalized PET fabrics to NBR adhesion were evaluated using H-pull and T-peel tests. The results showed that silane grafted-carboxylated PET fabric illustrated more adhesion to NBR than silane grafted-hydroxylated PET (i.e. 33 and 12% improvement in the pullout strength and T-peel adhesion, respectively).

A Bilayer High-Temperature Dielectric Film with Superior Breakdown Strength and Energy Storage Density

HighlightsA bilayer dielectric film is prepared via coating boron nitride nanosheets (BNNSs) by solution casting on the surface of polyethylene terephthalate (PET) film.The BNNS layer acts as the efficient barrier layer to suppress the charge injection, thereby making the surface-modified PET films exhibit excellent breakdown strength and electrostatic energy storage performance.The surface coating methods are accessible and suitable for large-scale roll-to-roll process production of dielectric films.

Prevention of surface colonization and anti-biofilm effect of selected phytochemicals against Listeria innocua strain

This work aimed to determine the ability of Listeria innocua (L.i.) to colonize eight materials found in food-processing and packaging settings and to evaluate the viability of the sessile cells. We also selected four commonly used phytochemicals (trans-cinnamaldehyde, eugenol, citronellol, and terpineol) to examine and compare their efficacies against L.i. on each surface. Biofilms were also deciphered in chamber slides using confocal laser scanning microscopy to learn more about how phytochemicals affect L.i. The materials tested were silicone rubber (Si), polyurethane (PU), polypropylene (PP), polytetrafluoroethylene (PTFE), stainless steel 316 L (SS), copper (Cu), polyethylene terephthalate (PET), and borosilicate glass (GL). L.i. colonized Si and SS abundantly, followed by PU, PP, Cu, PET, GL, and PTFE surfaces. The live/dead status ranged from 65/35% for Si to 20/80% for Cu, and the estimates of cells unable to grow on Cu were the highest, reaching even 43%. Cu was also characterized by the highest degree of hydrophobicity (ΔGTOT = −81.5 mJ/m2). Eventually, it was less prone to attachment, as we could not recover L.i. after treatments with control or phytochemical solutions. The PTFE surface demonstrated the least total cell densities and fewer live cells (31%) as compared to Si (65%) or SS (nearly 60%). It also scored high in hydrophobicity degree (ΔGTOT = −68.9 mJ/m2) and efficacy of phytochemical treatments (on average, biofilms were reduced by 2.1 log10 CFU/cm2). Thus, the hydrophobicity of surface materials plays a role in cell viability, biofilm formation, and then biofilm control and could be the prevailing parameter when designing preventive measures and interventions. As for phytochemical comparison, trans-cinnamaldehyde displayed greater efficacies, with the highest reductions seen on PET and Si (4.6 and 4.0 log10 CFU/cm2). The biofilms in chamber slides exposed to trans-cinnamaldehyde revealed the disrupted organization to a greater extent than other molecules. This may help establish better interventions via proper phytochemical selection for incorporation in environment-friendly disinfection approaches.

Formation of wettability gradient surface on polyethylene terephthalate by maskless argon microplasma jet writing for droplet self-driven application

The preparation of wettability gradient surface (WGS) has drawn increasing attention in diverse applications. However, the existing methods for WGS fabrication involve complex, costly and time-consuming procedures. In this paper, a novel, simple and efficient method is proposed for the preparation of wettability gradient surface (WGS) on polyethylene terephthalate (PET) film by maskless atmospheric pressure microplasma jet writing. By controlling the plasma processing parameters, the characteristics of the WGS could be controlled by using different duration time differences, nozzle distance differences and gas flow rate differences. Scanning Electron Microscope (SEM), Atomic Force Microscope (AFM) and Fourier Transform Infrared Spectroscopy (FTIR) were used to observe the surface morphologies and the chemical compositions of the PET surface before and after plasma treatment. It showed that the surface roughness increased and hydrophilic functional groups (such as COC and CO) were introduced into the PET surfaces after plasma writing, which was the main reason for the improvement of plasma treated PET surface wettability. WGS can be fabricated by synchronously controlling the plasma processing parameters during the direct writing processing and droplet self-driving could be successfully realized. The maximum self-driving distance of 1 μL water droplet could reach 4.76 mm in this work.

Diffuse reflectance spectroscopy (DRS) and infrared (IR) measurements for studying biofilm formation on common plastic litter polymer (LDPE and PET) surfaces in three different laboratory aquatic environments

Different species of microorganisms colonize the plastic surfaces and form biofilms depending on the aquatic environment. In the current investigation, characteristics of the plastic surface after exposure to three different aquatic environments based on visualization using scanning electron microscopy (SEM) and spectroscopic (diffuse reflectance (DR) and infrared (IR)) techniques were examined in laboratory bioreactors with time. For both materials, there were no differences observed in the ultraviolet (UV) region among the reactors and several peaks were observed with fluctuating intensities and without any trends. For light density polyethylene (LDPE), peaks indicating the presence of biofilm could be observed in the visible region for activated sludge bioreactor, and for polyethylene terephthalate (PET), freshwater algae biofilm was also visible. PET in freshwater bioreactor is the most densely populated sample both under the optical microscope and SEM. Based on the DR spectra, different visible peaks for LDPE and PET were observed but, in both cases, the visible region peaks (~ 450 and 670 nm) correspond to the peaks found in the water samples of the bioreactors. The difference on these surfaces could not be identified with IR but the fluctuations observed in the UV wavelength region were also detectable using indices obtained from the IR spectra such as keto, ester, and vinyl. For instance, the virgin PET sample shows higher values in all the indices than the virgin LDPE sample [(virgin LDPE: ester Index (I) = 0.051, keto I = 0.039, vinyl I = 0.067), (virgin PET: ester I = 3.5, keto I = 19, vinyl I = 0.18)]. This suggests that virgin PET surface is hydrophilic as expected. At the same time, for all the LDPE samples, all the indices demonstrated higher values (especially for R2) than the virgin LDPE. On the other hand, ester and keto indices for PET samples demonstrated lower values than virgin PET. In addition, DRS technique was able to identify the formation of the biofilm both on wet and dry samples. Both DRS and IR can describe changes in the hydrophobicity during the initial formation of biofilm but DRS can better describe the fluctuations of biofilm in the visible spectra region.