Plasma Polymerization Research Articles

Permanent Plasma Surface Functionalization of Internal Surface Areas

AbstractSurface functionalization technologies of fibrous or porous materials are often considered relatively unstable with a shelf life of several weeks or months at most, evoked by heterogeneous treatment of their internal surface areas. Here, it is demonstrating that the fine balance of plasma etching, deposition, and oxidation involving different reactive species, strongly enhances penetration depth within complex structures. On this basis, capillary wicking is maintained over >10 years after plasma functionalization of a scaffold material used for biomedical engineering. Electrospun membranes of poly(ε‐caprolactone) are coated with an oxygen‐functional hydrocarbon layer, deposited in a competitive ablation and plasma polymerization process with CO2 and C2H4 as reactive gases. Chemical analysis immediately after coating, 9 months later, and after storing at ambient conditions for over 10 years, indicate a stable surface coating. Using defined geometries such as a cavity and an undercut, the underlying plasma interaction mechanisms are revealed, showing different synergies of energetic particles, depositing species with different surface reactivities, and oxidizing species. A concerted action of such species during plasma functionalization is key to enabling long‐term wetting properties. This has a major implication for the surface functionalization of scaffolds, textiles, membranes, or foams used in diverse fields.

Tailored Functionalization of Plasmonic AgNPs/C:H:N:O Nanocomposite for Sensitive and Selective Detection

ABSTRACTWe report here on the development of tailored plasmonic AgNPs/C:H:N:O plasma polymer nanocomposites for the detection of the pathogenic bacterium Borrelia afzelii, with high selectivity and sensitivity. Silver (Ag) nanoparticles, generated by a gas aggregation source, are incorporated onto a C:H:N:O plasma polymer matrix, which is deposited by magnetron sputtering of a nylon 6.6. These anchored Ag nanoparticles propagate localized surface plasmon resonance (LSPR), optically responding to changes caused by immobilized pathogens near the nanoparticles. The tailored functionalization of AgNPs/C:H:N:O nanocomposite surface allows both high selectivity for the pathogen and high sensitivity with an LSPR red‐shift Δλ > (4.20 ± 0.71) nm for 50 Borrelia per area 0.785 cm2. The results confirmed the ability of LSPR modulation for the rapid and early detection of (not only) tested pathogens.

(Invited) The Potential of Pulsed Low Temperature Plasmas for the Controlled Deposition of Plasma Polymer Ultrathin Films and Composite Nanomaterials (Invited)

Low temperature discharges with their unique non-equilibrium properties are often used in industrial processes for the deposition of ultra-thin (plasma) polymer films. Applications for this type of thin films range from protective coatings to their use in membranes, biosensors and batteries. However, the properties of these thin films are highly dependent on the choice of discharge parameters, both in terms of their surface topography and their chemical composition. This paper deals with the great potential of pulsed discharges for the controlled deposition of plasma polymer films. The influence of pulse frequency and duty cycle on the deposition process and the properties of the resulting thin films is discussed from a theoretical point of view and is illustrated by experimental results. The latter concern examples of experiments carried out with discharges operated with acetylene or aniline, as well as functional coatings on top of MoS2, 2D graphene or CNTs.The work was supported by the project PEGASUS (Plasma Enabled and Graphene Allowed Synthesis of Unique nano-structures), funded by the European Union’s Horizon research innovation program under Grant Agreement No. 766894; EU Graphene Flagship FLAG-ERA III JTC 2021 project VEGA (No. PR-11938) Project-ANR-21-GRF1-0004. Further support was obtained via ARD MATEX Centre-Val de Loire Region (projects Carbon2 and Carbon3) and project Orleans Metropole (both France).

Nonlinear optical parameters and electronic properties of plasma polymerized methyl acrylate thin films

Plasma polymerized methyl acrylate (PPMA) thin films were fabricated on a borosilicate glass substrate at a plasma power of 28 W to study nonlinear optical parameters and electronic properties. X-ray Diffraction analysis confirmed the amorphous nature of the PPMA films, while Attenuated total reflectance Fourier transform infrared spectroscopy indicated monomer fragmentation due to plasma polymerization. Field emission scanning electron microscope images of the films display a water wave-like structure. PPMA films demonstrated thermal stability up to approximately 574 K in both N2 and air environments. The values of direct band gap energies increase from 3.30 to 3.41 eV with increasing film thicknesses, whereas the Urbach energy values show in an opposite manner. The Wemple-DiDomenico model was employed to analyze both the oscillator energies ranging from 5.54 to 6.44 eV and the dispersion energies ranging from 10.56 to 12.89 eV. The static linear refractive index showed typical dispersion behavior, with film thickness conforming to Moss's rule. The nonlinear refractive index and 2nd and 3rd order nonlinear susceptibilities decrease with increasing the studied films. The lattice dielectric constant values exceeded the high-frequency dielectric constant, indicating the presence of lattice vibrations and free carriers. Electronic parameters are fluctuating with increasing film thickness. The observed changes in nonlinear optical parameters and electronic properties highlight the potential of PPMA films for applications in photovoltaic and optoelectronics.

Synthesis, Biological Evaluation and Reversal of Sulfonated Di- and Triblock Copolymers as Novel Parenteral Anticoagulants.

Despite targeting different coagulation cascade sites, all Food and Drug Administration-approved anticoagulants present an elevated risk of bleeding, including potentially life-threatening intracranial hemorrhage. Existing studies have not thoroughly investigated the efficacy and safety of sulfonate polymers in animal models and fully elucidate the precise mechanisms by which these polymers act. The activity and safety of sulfonated di- and triblock copolymers containing poly(sodium styrenesulfonate) (PSSS), poly(sodium 2-acrylamido-2-methylpropanesulfonate) (PAMPS), poly(ethylene glycol) (PEG), poly(sodium methacrylate) (PMAAS), poly(acrylic acid) (PAA), and poly(sodium 11-acrylamidoundecanoate) (PAaU) blocks are synthesized and assessed. PSSS-based copolymers exhibit greater anticoagulant activity than PAMPS-based ones. Their activity is mainly affected by the total concentration of sulfonate groups and molecular weight. PEG-containing copolymers demonstrate a better safety profile than PAA-containing ones. The selected copolymer PEG47-PSSS32 exhibits potent anticoagulant activity in rodents after subcutaneous and intravenous administration. Heparin Binding Copolymer (HBC) completely reverses the anticoagulant activity of polymer in rat and human plasma. No interaction with platelets is observed. Selected copolymer targets mainly factor XII and fibrinogen, and to a lesser extent factors X, IX, VIII, and II, suggesting potential application in blood-contacting biomaterials for anticoagulation purposes. Further studies are needed to explore its therapeutic applications fully.

Swellable Plasma Polymer Films for Use in Hydrogel-Based Biomedical Devices

Swellable Plasma Polymer Films for Use in Hydrogel-Based Biomedical Devices

Fluorine-free superhydrophobic surfaces by atmospheric pressure plasma deposition of silazane-based suspensions

Atmospheric plasma is used to deposit superhydrophobic fluorine-free thin films onto a substrate. In this process, a suspension of micron size silica particles in a silazane based precursor is deposited in a single step using a dielectric barrier discharge plasma jet moving above the substrate. Thanks to an optimized configuration between the suspension injection and the plasma jet, the silazane precursor can be polymerized on the substrate surface but also, on silica particles to form additional micro size particles. The experimental parameters for optimal deposition are discussed, with emphasis on those leading to the formation of this dual roughness surface caused by the arrangement of both silica particles and particles generated from the precursor plasma polymerization. The combination of these two different length scales for the roughness leads to a decreased wettability of the coated substrate and a water contact angle larger than 150°.

Plasma Coating for Hydrophobisation of Micro- and Nanotextured Electrocatalyst Materials

The need for sustainable energy solutions is steering research towards green fuels. One promising approach involves electrocatalytic gas conversion, which requires efficient catalyst surfaces. This study focuses on developing and testing a hydrophobic octadiene (OD) coating for potential use in electrocatalytic gas conversion. The approach aims to combine a plasma-deposited hydrophobic coating with air-trapping micro- and nanotopographies to increase the yield of electrocatalytic reactions. Plasma polymerisation was used to deposit OD films, chosen for their fluorine-free non-polar properties, onto titanium substrates. We assessed the stability and charge permeability of these hydrophobic coatings under electrochemical conditions relevant to electrocatalysis. Our findings indicate that plasma-deposited OD films, combined with micro-texturing, could improve the availability of reactant gases at the catalyst surface while limiting water access. In the presence of nanotextures, however, the OD-coated catalyst did not retain its hydrophobicity. This approach holds promise to inform the future development of catalyst materials for the electrocatalytic conversion of dinitrogen (N2) and carbon dioxide (CO2) into green fuels.

Investigating the Influence of the Substrate Temperature and the Organic Precursor on the Mechanical Properties of Low‐Pressure Plasma Polymer Films

ABSTRACTThis work aims to investigate the influence of the substrate temperature on low‐pressure plasma polymerization processes. Emphasis is placed on the mechanical properties and growth mechanism of the plasma polymer films (PPFs). For this purpose, two precursors are considered, differing only by their unsaturation degree: 2‐propen‐1‐ol (CH2═CH–CH2–OH) and propan‐1‐ol (CH3–CH2–CH2–OH). Although propan‐1‐ol‐based PPFs behave like hard elastic solids, 2‐propen‐1‐ol‐based coatings evolve from a liquid film to an elastic solid on increasing the substrate temperature. This behavior is understood considering the evolution of the glass transition temperature of PPFs. The latter is correlated with the cross‐linking degree of the polymeric network governed by the energy density of bombarding ions on the growing film.

Electrophoretic Deposition of Multi‐Walled Carbon Nanotubes: The Key Role of Plasma Functionalization and Polymerization

ABSTRACTThe electrophoretic deposition of multi‐walled carbon nanotubes (MWCNTs) has been well‐researched; however, preparatory steps lead to MWCNT coating contamination and deposits often have weak adhesion to the substrate. This work targets these two weaknesses. First, MWCNTs were functionalized by nonthermal, radiofrequency plasma, producing oxygenated MWCNTs (O‐MWCNTs), with which water‐based suspensions were prepared. Second, an ethane‐based plasma polymer was applied on the metallic substrate as an interlayer to improve coating adhesion. O‐MWCNT coatings were produced at 5–40 V for 1–60 min. Homogeneous coatings with thicknesses up to 10 µm were achieved, the composition was 90‐95 at% carbon with the balance element being oxygen, and coating adhesion without damage was confirmed for shear stresses up to 16 Pa.

Plasma Polymerization of Vegetable Oils onto Paper Substrates of Varying Porosity for Improved Hydrophobicity

AbstractPaper finishing, in particular, coating paper with desired barrier functions is well‐developed as of today. However, due to large amounts of material and process energy as well as the use of non‐renewable resources for such coatings, common technologies are not sustainable. Given the increasing importance of paper in manifold applications, more sustainable routes with low‐energy processes as well as biogenic material alternatives are highly needed. To address this challenge, a solvent‐free and material‐efficient approach is proposed to bio‐based paper coatings by depositing chia oil‐based plasma polymers using a jet‐induced sliding discharge concept at atmospheric pressure. Depending on the amount of coating and the paper porosity, this treatment retards water absorption. Coating visualization is enabled through confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). Like chia oil, safflower oil, and olive oil show the ability to hydrophobize paper and the great potential within plasma polymerized vegetable oils to make the paper coating more sustainable.

Double tube configuration of atmospheric pressure plasma jet for deposition of organic coatings in open air

A double coaxial tube configuration of atmospheric pressure plasma jet (APPJ) was compared with a single tube one for open air plasma polymerization. The effectiveness on minimizing the influence of ambient air during the deposition process was shown for a double tube APPJ i.e. Ar gas fed into the outer glass tube acted as a shielding gas. The inner tube, acted as the powered electrode was fed with a mixture of Ar gas with the precursor, i.e., toluene vapor, a non-oxygen containing precursor. The dynamics of gas flow and its dependence on composition was investigated with a Schlieren imaging system. Coatings obtained with both configurations were analyzed by fourier transform infra-red (FTIR) and x-ray photoelectron spectroscopy (XPS). The results show clearly that the argon shielding gas largely protects the diffusion of oxygen in the deposition zone, giving rise to polymers with much less oxygen incorporated in their structure, and a good retention of the aromatic rings of toluene. Furthermore, the area of the treated zone and the chemical composition of the coating deposited is highly localized (1 mm) in the double tube giving dense stable carbon films while the deposition in the single tube much bigger (6 mm), and the deposited coatings are unstable and easily washed away. Hence, the results obtained with this innovative system provide a new path in plasma polymerization and continuous treatments of large surfaces, with improved coating stability and chemical retention.

Enhancing polyethylene‐based nanocomposites through ethylene plasma polymerization of carbon nanotubes and sequential ultrasound dispersion with melt mixing method

AbstractThis study investigates the enhancement of linear low‐density polyethylene (LLDPE) nanocomposites with multiwalled carbon nanotubes (CNT) at concentrations of 1, 3, and 6% w/w. To improve the interfacial interaction between the CNT and the polymeric matrix, CNT were treated using ethylene cold plasma (P‐CNT) in a rotary reactor. The incorporation of CNT into the polymer was carried out by a melt mixing process (MMP) and a sequential ultrasound dispersion method followed by melt mixing (UDM‐MMP). The thermal stability of nanocomposites with 6% P‐CNT increased by 45°C compared to pristine LLDPE. Electrical conductivity reached 2.5 × 10−2 S/cm for nanocomposites with 6% CNT. The elastic modulus increased from 519.52 MPa (LLDPE) to 714.63 MPa (6% CNT) and 795.43 MPa (6% P‐CNT), which further improving to 731.42 MPa (6% CNT) and 841.27 MPa (6% P‐CNT) using UDM‐MMP. Additionally, yield stress rose from 16.35 MPa to 21.28 MPa (6% CNT) and 22.06 MPa (6% P‐CNT), reaching 21.47 MPa and 22.28 MPa with UDM‐MMP. Tensile strength increased from 21.31 MPa to 25.15 MPa (6% CNT) and 25.9 MPa (6% P‐CNT), achieving 26.82 MPa (6% P‐CNT) with UDM‐MMP. These results highlight a significant improvement in conductivity, rigidity, and mechanical strength, emphasizing their potential for advanced applications.

Comprehensive study of plasma polymerization parameters on thiol-coated LDPE films for effective fibronectin adsorption targeting biomedical applications

In the realm of biomedical applications, biocompatible materials with optimized surface properties are crucial for facilitating cellular interactions. To attain the perfect balance of these properties, surface modification of non-toxic and stable bulk materials is often required. Within this context, this research aimed to improve the physiochemical and cell-responsive properties of a low-density polyethylene film. This was achieved by depositing thiol-rich coatings using a dielectric barrier discharge plasma reactor operating at medium pressures, with 1-propanethiol serving as polymerization precursor. The study systematically investigated the impact of key plasma polymerization parameters, including DBD chamber pressure, treatment time, and the combination of precursor flow rate and discharge power represented by the Yasuda parameter, to identify optimal plasma processing conditions for the formation of thiol-rich coatings. To characterize the coating thickness, hydrophilicity and surface chemical composition, atomic force microscopy, water contact angle measurements, and X-ray photoelectron spectroscopy were employed. The findings indicated that reducing the chamber pressure to 10 kPa led to more hydrophilic and thicker deposits possessing a higher sulphur content. Deposition time (5 to 15 min) also significantly impacted coating thickness and surface chemistry, where long times increased thickness, but also led to a reduced sulphur and increased oxygen content because of more pronounced etching. The optimal deposition time was therefore set at 10 min resulting in the deposition of dense coatings possessing a high number of sulphur-containing functionalities. The Yasuda parameter (W/FM) analysis demonstrated optimal thiol incorporation in combination with high coating stability at an intermediate W/FM value of 72 MJ/kg. Following the determination of the optimal plasma polymerization parameters, the effectiveness of thiol plasma polymerization and subsequent fibronectin immobilization for enhancing cell adhesion and proliferation was investigated. The thiol-coated substrates were found to exhibit superior protein immobilization, because of the high affinity for protein binding of the available thiol groups. To assess cellular responses, Schwann cells were cultured on uncoated and coated samples before and after fibronectin immobilization. The results revealed a superior cellular response of the thiol-coated samples after fibronectin immobilization, showing the highest cell viability and significantly enhanced cell adhesion and proliferation. Collectively, these results underscore the synergistic effect of thiol plasma polymerization and fibronectin immobilization in promoting the cellular response of LDPE substrates, thus highlighting their potential as a surface modification strategy of biomaterials.

Multivalent-copper-loaded layer-by-layer coating for antibacterial and instantaneous virucidal activity for protective textiles

Nanoarchitectured films are known for tailoring surface properties, while antimicrobial surfaces can reduce pathogen propagation in public spaces and on protective equipment. This study explores the layer-by-layer (LbL) method to create antiviral and antibacterial surfaces against disease transmission. Chitosan and carboxymethylcellulose films were assembled using LbL to incorporate ionic copper, a broad-spectrum antimicrobial agent, onto textile substrates, such as those used in furnishings and personal protective equipment. Film assembly conditions favored the conversion of Cu(II) into multivalent copper, immediately inactivating the MHV-3 virus, Gram-negative (E. coli), and Gram-positive (S. aureus) bacteria. Mechanical tests demonstrate that copper ions have a low impact on the coating and textile physical properties, such as elasticity, tensile strength, and film roughness, by promoting ionic crosslinking of chitosan in the film, while the coating kept air permeability. The coating hydrophilicity and copper release profile were also tuned by the deposition of additional hydrophobic barriers, such as L-alpha-phosphatidylcholine phospholipid or polydimethylsiloxane (PDMS) by spin-coating or plasma polymerization, respectively. Viral inactivation is achieved by the local release of copper ions in contaminated droplets. The coating may also act as a droplet-absorbing barrier, demonstrating the potential of these films for enhancing pathogen resistance and infection control in textile surfaces.

Osteosarcoma growth on trabecular bone mimicking structures manufactured via laser direct write

 This paper describes the direct laser write of a photocurable acrylate-based PolyHIPE (High Internal Phase Emulsion) to produce scaffolds with both macro- and microporosity, and the use of these scaffolds in osteosarcoma-based 3D cell culture. The macroporosity was introduced via the application of stereolithography to produce a classical “woodpile” structure with struts having an approximate diameter of 200 μm and pores were typically around 500 μm in diameter. The PolyHIPE retained its microporosity after stereolithographic manufacture, with a range of pore sizes typically between 10 and 60 μm (with most pores between 20 and 30 μm). The resulting scaffolds were suitable substrates for further modification using acrylic acid plasma polymerisation. This scaffold was used as a structural mimic of the trabecular bone and in vitro determination of biocompatibility using cultured bone cells (MG63) demonstrated that cells were able to colonise all materials tested, with evidence that acrylic acid plasma polymerisation improved biocompatibility in the long term. The osteosarcoma cell culture on the 3D printed scaffold exhibits different growth behaviour than observed on tissue culture plastic or a flat disk of the porous material; tumour spheroids are observed on parts of the scaffolds. The growth of these spheroids indicates that the osteosarcoma behave more akin to in vivo in this 3D mimic of trabecular bone. It was concluded that PolyHIPEs represent versatile biomaterial systems with considerable potential for the manufacture of complex devices or scaffolds for regenerative medicine. In particular, the possibility to readily mimic the hierarchical structure of native tissue enables opportunities to build in vitro models closely resembling tumour tissue.

Characterization of plasma polymerized acetonitrile film for fluorescence enhancement and its application to aptamer-based sandwich assay.

Among biosensing systems for sensitive diagnoses fluorescence enhancement techniques have attracted considerable attention. This study constructed a simple multilayered structure comprising a plane metal mirror coated with a plasma-polymerized film (PPF) as an optical interference layer on a glass slide for fluorescence enhancement. Plasma polymerization enables the easy deposition of organic thin films containing functional groups, such as amino groups. This study prepared PPFs using acetonitrile as a monomer, and the influences of washing and the output powers of plasma polymerization on PPF thickness were examined by Fourier transform infrared spectroscopy. This is because controlling the PPF thickness is vital in fluorescence enhancement. Multilayered glass slides prepared using a silver layer with 84 nm-thick acetonitrile PPFs exhibited 11- and 281-fold fluorescence enhancements compared with those obtained from the substrates with a bare surface and only modified by the silver layer, respectively. Oligonucleotides labeled with a thiol group and cyanine5 were successfully immobilized on the multilayered substrates, and the fluorescence of the acetonitrile PPFs was superior to that of the allylamine and cyclopropylamine PPFs. Furthermore, an aptamer-based sandwich assay targeting thrombin was performed on the multilayered glass slides, resulting in an approximately 5.1-fold fluorescence enhancement compared with that obtained from the substrate with a bare surface. Calibration curves revealed the relationship between fluorescence intensity and thrombin concentration of 10-1000 nM. This study demonstrates that PPFs can function as materials for fluorescence enhancement, immobilization for biomaterials, and aptamer-based sandwich assays.

Combination of 3D Printing, Plasma Polymerization, and Bioactive Coatings Towards Fabrication of Eggshell Biowaste/Polycaprolactone Composite Scaffolds for Bone Regeneration

Combination of 3D Printing, Plasma Polymerization, and Bioactive Coatings Towards Fabrication of Eggshell Biowaste/Polycaprolactone Composite Scaffolds for Bone Regeneration

Hard transparent nanogradient coating for ultradurable omniphobic liquid-like surface

Omniphobic liquid-like surface (LLS) offers excellent dynamic liquid repellency owing to the highly mobile polymer chains mediating at the solid–liquid interface. These polymer chains, often achieved by surface grafting, are not durable against abrasion or oxidation, which seriously hinders their practical application. Here we report a new vapor-based approach to create transparent nanogradient coating for LLSs with unprecedented mechanical strength and durability. The nanogradient coating is composed of a sandwich structure with an ultrathin primer, a rigid bulk, and a nanocomposite surface with abundant polydimethylsiloxane-like chains, all of which achieved via sequential plasma polymerization of a linear and a cyclic siloxane. The plasma-polymerized cyclic siloxane enables coating good mechanical strength while the plasma-polymerized linear siloxane confers coating sub-nanometer roughness and excellent dynamic liquid repellency. The resultant coating exhibits contact angle hysteresis < 5° towards many low-surface-energy liquids, as well as good mechanical strength with the hardness exceeding 1 GPa and superior durability enduring 100,000 cycles of abrasion. The coating also survived industrial standard thermal and accelerated UV-aging tests without losing its liquid repellency and transparency. The reported method is facile, scalable, and substrate-independent, offering exciting new opportunities towards industrial fabrication and real-world application of LLS.

Amine plasma polymers deposited on porous hydroxyapatite artificial bone with bipolar pulsed discharges

A recent in vivo study [Kodama et al., Sci. Rep. 11, 1 (2021)] showed that porous artificial bones coated with amine-containing polymers deposited by plasma-enhanced chemical vapor deposition (PECVD) significantly enhanced bone regeneration. This article reports the chemical and physical properties of amine plasma polymers (PPs) formed under the same deposition conditions, including the film stability for up to two months, the effects of sterilization on the chemical compositions of the films, and the penetration of amine PPs into the inner surfaces of interconnected microscopic pores of the amine PP-coated porous artificial bone. It was found that, immediately after the plasma polymerization process, approximately 20% of nitrogen atoms on the surface of the deposited amine PP formed primary amines. However, the value decreased to approximately 5% over one month if the sample was exposed to ambient air. The relative concentration of primary amines also decreased to a similar value after the sample was sterilized by autoclaving or ethylene oxide gas. Molecular dynamics simulations were used to examine possible formation mechanisms of nitriles in deposit films under the PECVD conditions and found that ion impact can significantly reduce the nitrile content.