Synthesis of High-Entropy Alloys with a Tailored Composition and Phase Structure Using a Single Configurable Target.

Previously, refractory high-entropy alloys (HEAs) with high crystallinity were synthesized using a configurable target without heat treatment. This study builds upon prior investigations to develop nonrefractory elemental HEAs with low crystallinity using a novel target system. Different targets with various elemental compositions, i.e., Co20Cr20Ni20Mn20Mo20 (target 1), Co30Cr15Ni25Mn15Mo15 (target 2), and Co15Cr25Cu20Mn20Ni20 (target 3), are designed to modify the phase structure. The elemental composition is varied to ensure face-centered cubic (FCC) or body-centered cubic (BCC) phase stabilization. In target 1, the FCC and BCC phases coexist, whereas targets 2 and 3 are characterized by a single FCC phase. Thin films based on targets 1 and 2 exhibit crystalline phases followed by annealing, as indicated by X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. In contrast, target 3 yields crystalline thin films without any heat treatment. The thin-film coatings are classified based on the atomic size difference (δ). The δ value for the target with the elemental composition CoCrMoMnNi is 9.7, i.e., ≥6.6, corresponding to an HEA with an amorphous phase. However, the annealed thin film is considered a multiprincipal elemental alloy. In contrast, δ for the CoCrCuMnNi HEA is 5, i.e., ≤6.6, upon the substitution of Mo with Cu, and a solid solution phase is formed without any heat treatment. Thus, the degree of crystallinity can be controlled through heat treatment and the manipulation of δ in the absence of heat treatment. The XRD results clarify the crystallinity and phase structure, indicating the presence of FCC or a combination of FCC and BCC phases. The outcomes are consistent with those obtained through the analysis of the valence electron concentration based on X-ray photoelectron spectroscopy. Furthermore, a selected area electron diffraction analysis confirms the presence of both amorphous and crystalline structures in the HEA thin films. Additionally, phase evolution and segregation are observed at 500 °C.

Design and Development of High-Entropy Alloys with a Tailored Composition and Phase Structure Based on Thermodynamic Parameters and Film Thickness Using a Novel Combinatorial Target.

This study presents a novel synthesis route for high-entropy alloys (HEAs) and high-entropy metallic glass (HEMG) using radio frequency (RF) magnetron sputtering and controlling the HEA phase selection according to atomic size difference (δ) and film thickness. The preparation of HEAs using sputtering requires either multitargets or the preparation of a target containing at least five distinct elements. In developing HEA-preparation techniques, the emergence of a novel sputtering target system is promising to prepare a wide range of HEAs. A new HEA-preparation technique is developed to avoid multitargets and configure the target elements with the required components in a single target system. Because of a customizable target facility, initially, a TiZrNbMoTaCr target emerged with an amorphous phase owing to a high δ value of 7.6, which was followed by a solid solution (SS) by lowering the δ value to 5 (≤6.6). Thus, this system was tested for the first time to prepare TiZrNbMoTa HEA and TiZrNbMoTa HEMG via RF magnetron sputtering. Both films were analyzed using X-ray diffraction (XRD), X-ray photoelectron spectroscopy, field emission scanning electron microscopy cross-sectional thickness, and atomic force microscopy (AFM). Furthermore, HEMG showed higher hardness 10.3 (±0.17) GPa, modulus 186 (±7) GPa, elastic deformation (0.055) and plastic deformation (0.032 GPa), smooth surface, lower corrosion current density (Icorr), and robust cell viability compared to CP-Ti and HEA. XRD analysis of the film showed SS with a body-centered cubic (BCC) structure with (110) as the preferred orientation. The valence electron concentration [VEC = 4.8 (<6.87)] also confirmed the BCC structure. Furthermore, the morphology of the thin film was analyzed through AFM, revealing a smooth surface for HEMG. Inclusively, the concept of configurational entropy (ΔSmix) is applied and the crystalline phase is achieved at room temperature, optimizing the processing by avoiding further furnace usage.

The Surface Properties of Implant Materials by Deposition of High-Entropy Alloys (HEAs).

High-entropy alloys (HEAs) contain more than five alloying elements in a composition range of 5-35% and with slight atomic size variation. Recent narrative studies on HEA thin films and their synthesis through deposition techniques such as sputtering have highlighted the need for determining the corrosion behaviors of such alloys used as biomaterials, for example, in implants. Coatings composed of biocompatible elements such as titanium, cobalt, chrome, nickel, and molybdenum at the nominal composition of Co30Cr20Ni20Mo20Ti10 were synthesized by means of high-vacuum radiofrequency magnetron (HVRF) sputtering. In scanning electron microscopy (SEM) analysis, the coating samples deposited with higher ion densities were thicker than those deposited with lower ion densities (thin films). The X-ray diffraction (XRD) results of the thin films heat treated at higher temperatures, i.e., 600 and 800 °C, revealed a low degree of crystallinity. In thicker coatings and samples without heat treatment, the XRD peaks were amorphous. The samples coated at lower ion densities, i.e., 20 µAcm-2, and not subjected to heat treatment yielded superior results in terms of corrosion and biocompatibility among all the samples. Heat treatment at higher temperatures led to alloy oxidation, thus compromising the corrosion property of the deposited coatings.

Manipulating wettability of catalytic surface for improving ammonia production from electrochemical nitrogen reduction.

An electrochemical nitrogen reduction reaction (ENRR) is considered a promising alternative for the traditional Haber-Bosch process. In this study, we present a method for improving the ENRR by controlling the wettability of the catalyst surface, suppressing the hydrogen evolution reaction (HER) while facilitating N2 adsorption. Reduced-graphene oxide (rGO) with a hydrophobic surface property and a contact angle (C.A.) of 59° was synthesized through a high-density atmospheric plasma deposition. Two other hydrophilic and superhydrophobic surfaces with a C.A. of 15° and 150° were developed through additional argon plasma and heat treatment of as-deposited rGO, respectively. The ENRR results showed that the ammonia yield and Faradaic efficiency tended to increase with increasing hydrophobicity. Electrochemical measurements reveal that superhydrophobic rGO achieves a higher Faradaic efficiency (5.73 %) at -0.1 V (vs RHE) and a higher NH3 yield (9.77 µg h-1 cm-2) at -0.4 V (vs RHE) in a 0.1 M KOH electrolyte. In addition, the computational fluid dynamics simulation confirmed that the amount of time the N2 gas remains on the surface could increase by improving the hydrophobicity of the catalytic surface. This study inspires the development of the rGO electrocatalyst through surface wettability modification for boosting ammonia electrosynthesis.

Biological Effects of the Novel Mulberry Surface Characterized by Micro/Nanopores and Plasma-Based Graphene Oxide Deposition on Titanium.

PURPOSE: This paper presents a technique for developing a novel surface for dental implants using a combination of nitriding and anodic oxidation, followed by the deposition of graphene oxide using atmospheric plasma. The effects of various surface treatments on bacterial adhesion and osteoblast activation were also evaluated. METHODS: CP titanium (control) was processed into disk-shaped specimens. Nitriding was conducted using vacuum nitriding, followed by anodic oxidation, which was performed in an electrolyte using a DC power supply, to form the novel "mulberry surface." Graphene oxide deposition was performed using atmospheric plasma with an inflow of carbon sources. After analyzing the sample surfaces, antibacterial activity was evaluated using Streptococcus mutans and Porphyromonas gingivalis bacteria. The viability, adhesion, proliferation, and differentiation of osteoblasts were also assessed. Analysis of variance (ANOVA) with Tukey's post-hoc test was used to calculate statistical differences. RESULTS: We observed that the mulberry surface was formed on samples treated with nitriding and anodic oxidation, and these samples exhibited more effective antibacterial activity than the control. We also found that the samples with additional graphene oxide deposition exhibited better biocompatibility, which was validated by osteoblast adhesion, proliferation, and differentiation. CONCLUSION: The development of the mulberry surface along with graphene oxide deposition inhibits bacterial adhesion to the implant and enhances the adhesion, proliferation, and differentiation of osteoblasts. These results indicate that the mulberry surface and graphene oxide deposition together can inhibit peri-implantitis and promote osseointegration.

Heptamethine Cyanine Dye MHI-148-Mediated Drug Delivery System to Enhance the Anticancer Efficiency of Paclitaxel.

INTRODUCTION: Paclitaxel (PTX) is a conventional chemotherapeutic drug that effectively treats various cancers. The cellular uptake and therapeutic potential of PTX are limited by its slow penetration and low solubility in water. The development of cancer chemotherapy methods is currently facing considerable challenges with respect to the delivery of the drugs, particularly in targeting the tumor site without exerting detrimental effects on the healthy surrounding cells. One possibility for improving the therapeutic potential is through the development of tumor-targeted delivery methods. METHODS: We successfully synthesized paclitaxel-MHI-148 conjugates (PTX-MHI) by coupling PTX with the tumor-targeting heptamethine cyanine dye MHI-148. Synthesis and purification were characterized using the absorbance spectrum and the results of time-of-flight mass spectrometry. Cellular uptake and cytotoxicity studies were conducted in vitro and in vivo. RESULTS: PTX-MHI accumulates in tumor cells but not in normal cells, as observed by in vitro near-infrared fluorescent (NIRF) imaging along with in vivo NIRF imaging and organ biodistribution studies. We observed that MHI-148-conjugated PTX shows greater efficiency in cancer cells than PTX alone, even in the absence of light treatment. PTX-MHI could also be used for specific drug delivery to intracellular compartments, such as the mitochondria and lysosomes of cancer cells, to improve the outcomes of tumor-targeting therapy. CONCLUSION: The results indicated that PTX-MHI-mediated cancer therapy exerts an excellent inhibitory effect on colon carcinoma (HT-29) cell growth with low toxicity in normal fibroblasts (NIH3T3).

Direct-Deposited Graphene Oxide on Dental Implants for Antimicrobial Activities and Osteogenesis.

OBJECTIVE: To determine the effects of graphene oxide (GO) deposition (on a zirconia surface) on bacterial adhesion and osteoblast activation. METHODS: An atmospheric pressure plasma generator (PGS-300) was used to coat Ar/CH4 mixed gas onto zirconia specimens (15-mm diameter × 2.5-mm thick disks) at a rate of 10 L/min and 240 V. Zirconia specimens were divided into two groups: uncoated (control; Zr) group and GO-coated (Zr-GO) group. Surface characteristics and element structures of each specimen were evaluated by field emission scanning electron microscope (FE-SEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and contact angle. Additionally, crystal violet staining was performed to assess the adhesion of Streptococcus mutans. WST-8 and ALP (Alkaline phosphatase) assays were conducted to evaluate MC3T3-E1 osteoblast adhesion, proliferation, and differentiation. Statistical analysis was calculated by the Mann-Whitney U-test. RESULTS: FE-SEM and Raman spectroscopy demonstrated effective GO deposition on the zirconia surface in Zr-GO. The attachment and biofilm formation of S. mutans was significantly reduced in Zr-GO compared with that of Zr (P < 0.05). While no significant differences in cell attachment of MC3T3-1 were observed, both proliferation and differentiation were increased in Zr-GO as compared with that of Zr (P < 0.05). SIGNIFICANCE: GO-coated zirconia inhibited the attachment of S. mutans and stimulated proliferation and differentiation of osteoblasts. Therefore, GO-coated zirconia can prevent peri-implantitis by inhibiting bacterial adhesion. Moreover, its osteogenic ability can increase bone adhesion and success rate of implants.

Synthesis of Graphene Oxide Using Atmospheric Plasma for Prospective Biological Applications.

INTRODUCTION: This paper presents a novel technique for the synthesis of graphene oxide (GO) with various surface features using high-density atmospheric plasma deposition. Furthermore, to investigate the use of hydrophobic, super-hydrophobic, and hydrophilic graphene in biological applications, we synthesized hydrophobic, super-hydrophobic, and hydrophilic graphene oxides by additional heat treatment and argon plasma treatment, respectively. In contrast to conventional fabrication procedures, reduced graphene oxide (rGO) formed under low pressure and high-temperature environment using a new synthesis method-developed and described in this study-offers a convenient deposition method on any kind surface with controlled wettability. METHODS: High density at atmospheric plasma is used for the synthesis of rGO and GO and its biocompatibility based on various wetting properties was evaluated using MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay, and the viability of cells in response to rGO and GO with various surface features was investigated. Structural integrity was characterized by Raman spectroscopy, FESEM and FE-TEM. Wettability was measured via contact angle method and confirmed with XPS analysis. RESULTS: We found that GO coating with a hydrophilic feature is more biocompatible than other surfaces as observed in case of fibroblast cells. We have shown that wettability-controlled by GO deposition-influences biocompatibilities and antibacterial effect of biomaterial surfaces. DISCUSSION: Measuring the contact angle, it is found that contact angle for hydrophobic is increased to 150.590 and reduced to 11.580 by heat and argon plasma treatment, respectively, from 75.880 that was initially in the case of hydrophobic surface. XPS analysis confirmed various oxygen-containing functional groups transforming as deposited hydrophobic surface into superhydrophobic and hydrophilic surface. Thus, we have proposed a new, direct, cost-effective, and highly productive method for the synthesis of rGO and GO-with various surface properties-for biological applications. Similarly, for the dental implant application, the Streptococcus mutans was used as an antibacterial effect and found that S. mutans grows slowly on hydrophilic surface. Thus, antibacterial effect was prominent on GO with hydrophilic surface.

In-Situ Deposition of Graphene Oxide Catalyst for Efficient Photoelectrochemical Hydrogen Evolution Reaction Using Atmospheric Plasma.

The vacuum deposition method requires high energy and temperature. Hydrophobic reduced graphene oxide (rGO) can be obtained by plasma-enhanced chemical vapor deposition under atmospheric pressure, which shows the hydrophobic surface property. Further, to compare the effect of hydrophobic and the hydrophilic nature of catalysts in the photoelectrochemical cell (PEC), the prepared rGO was additionally treated with plasma that attaches oxygen functional groups effectively to obtain hydrophilic graphene oxide (GO). The hydrogen evolution reaction (HER) electrocatalytic activity of the hydrophobic rGO and hydrophilic GO deposited on the p-type Si wafer was analyzed. Herein, we have proposed a facile way to directly deposit the surface property engineered GO.