An official website of the United States government
Superhard boron-carbon materials are of prime interest due to their non-oxidizing properties at high temperatures compared to diamond-based materials and their non-reactivity with ferrous metals under extreme conditions. In this work, evolutionary algorithms combined with density functional theory have been utilized to predict stable structures and properties for the boron-carbon system, including the elusive superhard BC5 compound. We report on the microwave plasma chemical vapor deposition on a silicon substrate of a series of composite materials containing amorphous boron-doped graphitic carbon, boron-doped diamond, and a cubic hard-phase with a boron-content as high as 7.7 at%. The nanoindentation hardness of these composite materials can be tailored from 8 GPa to as high as 62 GPa depending on the growth conditions. These materials have been characterized by electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, X-ray diffraction, and nanoindentation hardness, and the experimental results are compared with theoretical predictions. Our studies show that a significant amount of boron up to 7.7 at% can be accommodated in the cubic phase of diamond and its phonon modes and mechanical properties can be accurately modeled by theory. This cubic hard-phase can be incorporated into amorphous boron-carbon matrices to yield superhard materials with tunable hardness values.
more »
« less
Effects of Silicon Content on the Microstructures and Mechanical Properties of (AlCrTiZrV)-Six-N High-Entropy Alloy Films
A series of (AlCrTiZrV)-Six-N films with different silicon contents were deposited on monocrystalline silicon substrates by direct-current (DC) magnetron sputtering. The films were characterized by the X-ray diffractometry (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and nano-indentation techniques. The effects of the silicon content on the microstructures and mechanical properties of the films were investigated. The experimental results show that the (AlCrTiZrV)N films grow in columnar grains and present a (200) preferential growth orientation. The addition of the silicon element leads to the disappearance of the (200) peak, and the grain refinement of the (AlCrTiZrV)-Six-N films. Meanwhile, the reticular amorphous phase is formed, thus developing the nanocomposite structure with the nanocrystalline structures encapsulated by the amorphous phase. With the increase of the silicon content, the mechanical properties first increase and then decrease. The maximal hardness and modulus of the film reach 34.3 GPa and 301.5 GPa, respectively, with the silicon content (x) of 8% (volume percent). The strengthening effect of the (AlCrTiZrV)-Six-N film can be mainly attributed to the formation of the nanocomposite structure.
more »
« less
- PAR ID:
- 10179111
- Date Published:
- Journal Name:
- Entropy
- Volume:
- 21
- Issue:
- 1
- ISSN:
- 1099-4300
- Page Range / eLocation ID:
- 75
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
ReMo binary alloy films with a maximum Mo content of 25 at. % are successfully electrodeposited using high concentration acetate solutions in the presence of citric acid. The electrochemical behavior of the ReMo alloy is studied using cyclic voltammetry and anodic stripping methods. Different techniques, including electron microscopy, x-ray diffraction, and four-point probe resistance measurements at cryogenic temperature, are used to characterize the surface morphology, crystal structure, and superconducting critical temperature of alloys, respectively. While all films exhibit a crystalline hcp phase after 700 °C annealing, the film with the highest 25 at. % Mo content shows a second crystalline cubic phase. Mo doping preserves the enhanced superconducting transition temperature (Tc) in electrodeposited amorphous Re films and improves the stability of Tc against thermal annealing at a temperature of 200 °C. This is the first successful demonstration to use a dopant to stabilize the enhanced Tc of electrodeposited films, enabling the fabrication and operation of superconducting connectors above the intrinsic Tc of the materials.more » « less
-
Titanium dioxide (TiO2)/nitrogen-doped graphene (NG) nanocomposite is prepared via a solvent-free hydrothermal reaction. The resulting TiO2/NG materials exhibit a reduction of the band gap energy compared to pristine TiO2 from 3.27 eV to 2.69 eV. These materials are characterized by scanning transmission electron microscopy (STEM), energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). To prepare biopolymer films with photocatalytic properties, TiO2 and NG are mixed with biodegradable chitosan and spin-coated on a silicon wafer. Film roughness and thickness are evaluated by atomic force microscopy (AFM). These films are then tested for ciprofloxacin photodegradation by irradiating with visible light. In comparison to the TiO2/chitosan films, the addition of NG substantially enhances photodegradation efficiency by up to 34% upon the addition of 5% w/w of NG. Furthermore, this film is shown to be a good substrate for biomarker detection using laser desorption ionization mass spectrometry (LDI-MS). In summary, this nanocomposite-biopolymer film provides good photocatalytic activity towards ciprofloxacin degradation and enhances the ionization efficiency of peptide biomarkers in LDI-MS owing to high efficiency of laser absorption/desorption. This nanocomposite film might be useful for environmental-related and medical application.more » « less
-
Polymer nanocomposite (PNC) films are of interest for many applications including electronics, energy storage, and advanced coatings. In phase-separating PNCs, the interplay between thermodynamic and kinetic factors governs the assembly of polymer-grafted nanoparticles (NPs), which directly influences material properties. Understanding how processing parameters affect the structure-property relationship of PNCs is important for designing advanced materials. This thesis provides insight by investigating a model PNC system of poly(methyl methacrylate)-grafted nanoparticles (PMMA-NPs) embedded in a poly(styrene-ran-acrylonitrile) (SAN) matrix. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was developed to quantify the distribution of NPs within PMMA-NP/SAN films, enabling precise 3D reconstruction of PNC structures. Experimental parameters such as primary ion beam angle and charge compensation were optimized to enhance secondary ion signals and depth resolution. Upon annealing in the twophase region, PMMA-NP/SAN films exhibited phase separation and surface segregation, leading to morphological evolutions characterized by atomic force microscopy (AFM), ToF-SIMS, water contact angle measurements, and transmission electron microscopy. By systematically exploring the effects of film thickness on PNC structures, we found that film thickness-induced confinement reduces lateral phase separation and enhances NP dispersion at the surface. A dimensional crossover from three to two dimensions was observed around 240 nm, below which surface-directed spinodal decomposition is suppressed. As a result of phase separation and surface segregation, six distinct bulk morphologies were identified, allowing for the construction of a morphology map correlating film thickness and annealing time. Among these morphologies, percolated structures were found to improve mechanical properties such as hardness and reduced modulus, as measured using AFM nanoindentation. Notably, interconnected networks show the highest hardness and modulus at both low and high force loadings. Additionally, Marangoni-induced hexagonal honeycomb patterns were observed in spin-coated as-cast PMMA-NP/SAN films. By changing to a less volatile solvent, these defects were eliminated, demonstrating the importance of solvent selection in achieving uniform and high-quality thin films. These findings demonstrate the potential for precise control of surface-enriched and phase-separated microstructures in PNC films through tailoring processing conditions. This thesis advances the understanding of processing-structure-property relationships in PNCs, providing a foundation for designing highly functional materials with broad industrial applications.more » « less
-
The present work focuses on the synthesis of a vanadium nitride (VN)/carbon nanocomposite material via the thermal decomposition of vanadyl phthalocyanine (VOPC). The morphology and chemical structure of the synthesized compounds were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Fourier transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD), and X-ray photoemission spectroscopy (XPS). The successful syntheses of the VOPC and non-metalated phthalocyanine (H2PC) precursors were confirmed using FTIR and XRD. The VN particles present a needle-like morphology in the VN synthesized by the sol-gel method. The morphology of the VN/C composite material exhibited small clusters of VN particles. The XRD analysis of the thermally decomposed VOPC indicated a mixture of amorphous carbon and VN nanoparticles (VN(TD)) with a cubic structure in the space group FM-3M consistent with that of VN. The XPS results confirmed the presence of V(III)-N bonds in the resultant material, indicating the formation of a VN/C nanocomposite. The VN/C nanocomposite synthesized through thermal decomposition exhibited a high carbon content and a cluster-like distribution of VN particles. The VN/C nanocomposite was used as an anode material in LIBs, which delivered a specific capacity of 307 mAh g−1 after 100 cycles and an excellent Coulombic efficiency of 99.8 at the 100th cycle.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/e21010075
