Liquid exfoliation of ultrasmall zirconium carbide nanodots as a noninflammatory photothermal agent in the treatment of glioma.

Photothermal therapy (PTT), like other clinical translational tumor ablation techniques, requires a temperature increase above 50 °C to cause necrosis and death of tumor cells. Although the tumor can be eliminated rapidly by PTT, the inflammatory response is triggered by the large amounts of released reactive oxygen species (ROS). Therefore, liquid exfoliation was used to create ultrasmall zirconium carbide nanodots (NDs) with an average diameter of approximately 4.5 nm as noninflammatory/anti-inflammatory photosensitizers for PTT of glioma. Ultrasmall ZrC NDs showed excellent photothermal stability and biocompatibility but no obvious toxicity. Moreover, the ultrasmall ZrC NDs effectively ablated glioma at relatively low concentrations and inhibited tumor migration and proliferation in vitro and in vivo. Furthermore, the excellent ROS-scavenging ability of ultrasmall ZrC NDs suppressed the inflammatory response to PTT. Intriguingly, we found that ZrC had the capability of performing CT imaging. We demonstrated that the ultrasmall ZrC NDs created in this study could effectively and safely treat glioma without inflammation.

Zirconium Carbide Mediates Coke-Resistant Methane Dry Reforming on Nickel-Zirconium Catalysts.

Graphitic deposits anti-segregate into Ni0 nanoparticles to provide restored CH4 adsorption sites and near-surface/dissolved C atoms, which migrate to the Ni0 /ZrO2 interface and induce local Zrx Cy formation. The resulting oxygen-deficient carbidic phase boundary sites assist in the kinetically enhanced CO2 activation toward CO(g). This interface carbide mechanism allows for enhanced spillover of carbon to the ZrO2 support, and represents an alternative catalyst regeneration pathway with respect to the reverse oxygen spillover on Ni-CeZrx Oy catalysts. It is therefore rather likely on supports with limited oxygen storage/exchange kinetics but significant carbothermal reducibility.

Influence of Laser Beam Power on Microstructure and Microhardness of Fe/ZrC Coatings Produced on Steel Using Laser Processing-Preliminary Study on the Single Laser Tracks.

This paper presents preliminary tests of the parameter analysis of the Fe/ZrC coatings production process and the obtained properties. The effects of laser beam power on the obtained microstructure, chemical composition and microhardness were investigated. The tests consisted of the production of composite coatings by laser processing of initial coatings made in the form of a paste on a steel substrate. During the tests, a diode laser with a rated power of 3 kW was used. The laser processing process was carried out using a constant scanning speed laser beam of 3 m/min and four different powers of the laser beam: 500 W, 700 W, 900 W, 1100 W. It was found that it is possible to create composite coatings on a steel surface, where the matrix is made of iron-based alloy and the reinforcing phase is ZrC carbide. It was also found that reinforcing phase content decreased as laser beam power increased. A similar relationship was found for microhardness. As laser beam power increases, the microhardness of the iron-based matrix decreases, finally reaching a value lower than the heat-affected zone. It was found that the amount of hard carbide phases in the iron-based matrix affects the total hardness of the coatings. Presented study concern Fe/ZrC coatings that have not previously been produced on steel by laser processing of precoating, which may be a new contribution in the field of metal surface engineering.

Formation of ZrC-SiC Composites from the Molecular Scale through the Synthesis of Multielement Polymers.

In the field of non-oxide ceramic composites, and by using the polymer-derived ceramic route, understanding the relationship between the thermal behaviour of the preceramic polymers and their structure, leading to the mechanisms involved, is crucial. To investigate the role of Zr on the fabrication of ZrC-SiC composites, linear or hyperbranched polycarbosilanes and polyzirconocarbosilanes were synthesised through either "click-chemistry" or hydrosilylation reactions. Then, the thermal behaviours of these polymeric structures were considered, notably to understand the impact of Zr on the thermal path going to the composites. The inorganic materials were characterised by thermogravimetry-mass spectrometry (TG-MS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). To link the macromolecular structure to the organisation involved during the ceramisation process, eight temperature domains were highlighted on the TG analyses, and a four-step mechanism was proposed for the polymers synthesised by a hydrosilylation reaction, as they displayed better ceramic yields. Globally, the introduction of Zr in the polymer had several effects on the temperature fragmentation mechanisms of the organometallic polymeric structures: (i) instead of stepwise mass losses, continuous fragment release prevailed; (ii) the stability of preceramic polymers was impacted, with relatively good ceramic yields; (iii) it modulated the chemical composition of the generated composites as it led, inter alia, to the consumption of free carbon.

Prodrug-Loaded Zirconium Carbide Nanosheets as a Novel Biophotonic Nanoplatform for Effective Treatment of Cancer.

Conventional chemotherapy and photothermal therapy (PTT) face many major challenges, including systemic toxicity, low bioavailability, ineffective tissue penetration, chemotherapy/hyperthermia-induced inflammation, and tumor angiogenesis. A versatile nanomedicine offers an exciting opportunity to circumvent the abovementioned limitations for their successful translation into clinical practice. Here, a promising biophotonic nanoplatform is developed based on the zirconium carbide (ZrC) nanosheet as a deep PTT-photosensitizer and on-demand designed anticancer prodrug SN38-Nif, which is released and activated by photothermia and tumor-overexpressed esterase. In vitro and in vivo experimental evidence shows the potent anticancer effects of the integrated ZrC@prodrug biophotonic nanoplatform by specifically targeting malignant cells, chemotherapy/hyperthermia-induced tumor inflammation, and angiogenesis. In mouse models, the ZrC@prodrug system markedly inhibits tumor recurrence, metastasis, inflammation and angiogenesis. The findings unravel a promising biophotonic strategy for precision treatment of cancer.

Microstructures of a SiC-ZrC Ceramic Fiber Derived from a Polymeric Precursor.

Continuous ceramic fiber comprising silicon carbide-zirconium carbide (SiC-ZrC) binary phases was obtained through melt spinning, electron-beam curing and pyrolysis of a pre-ceramic precursor of polyzirconocenecarbosilanes (PZCS). After pyrolysis and heat treatment, ZrC particles with mean diameters of 15-20 nm were formed and homogeneously dispersed in a matrix of fine crystalline ß-SiC with an average grain size of 6-10 nm. Concentration of Zr in the fiber varies from 14.88% to 17.45% by mass. Fibers consisting of near-stoichiometric ZrC and SiC with little free carbon can be obtained through pyrolysis decarbonization of the as-cured fiber in hydrogen from room temperature to 1000 °C, and subsequently heat treatment in argon up to 1600 °C for 1 h. High-temperature treatment of these amorphous inorganic fibers leads to crystallization of the binary phases of ß-SiC and ZrC. The removal of free carbon under hydrogen results in more rapid growth of ß-SiC and ZrC crystals, in which obvious aggregation of the dispersed ZrC particles among the continuous ß-SiC matrix can be ascribed to a fast migration of Zr cation.

Microstructure Evolution in ZrCx with Different Stoichiometries Irradiated by Four MeV Au Ions.

ZrCx ceramics with different stoichiometries were irradiated under a four MeV Au ion beam in doses of 2 × 1016 ions/cm2 at room temperature, corresponding to ~130 dpa. Grazing incidence, X-ray diffraction and transmission electron microscopy were performed to study the radiation damage and microstructure evolution in ZrCx ceramics. With the decrease in C/Zr ratio, the expansion of ZrCx lattice became smaller after irradiation. Some long dislocation lines formed at the near-surface, while, in the area with the greatest damage (depth of ~400 nm), large amounts of dislocation loops formed in ZrC, ZrC0.9 and ZrC0.8. With the increase in carbon vacancy concentration, the size of the dislocation loops gradually decreased. Few dislocation loops were found in ZrC0.7 after irradiation, and only black-dot defects were found in the area with the greatest damage. For the non-stoichiometric ZrCx, with the increase of the intrinsic vacancies, the number of C interstitials caused by irradiation decreased, and the recombination barrier of C Frenkel pairs reduced. The above factors will reduce the total number of C interstitials after cascade cooling, suppressing the formation and growth of dislocation loops, which is significant for the enhancement of the tolerance of radiation damage.

Carbides and Nitrides of Zirconium and Hafnium.

Among transition metal carbides and nitrides, zirconium, and hafnium compounds are the most stable and have the highest melting temperatures. Here we review published data on phases and phase equilibria in Hf-Zr-C-N-O system, from experiment and ab initio computations with focus on rocksalt Zr and Hf carbides and nitrides, their solid solutions and oxygen solubility limits. The systematic experimental studies on phase equilibria and thermodynamics were performed mainly 40-60 years ago, mostly for binary systems of Zr and Hf with C and N. Since then, synthesis of several oxynitrides was reported in the fluorite-derivative type of structures, of orthorhombic and cubic higher nitrides Zr3N4 and Hf3N4. An ever-increasing stream of data is provided by ab initio computations, and one of the testable predictions is that the rocksalt HfC0.75N0.22 phase would have the highest known melting temperature. Experimental data on melting temperatures of hafnium carbonitrides are absent, but minimum in heat capacity and maximum in hardness were reported for Hf(C,N) solid solutions. New methods, such as electrical pulse heating and laser melting, can fill the gaps in experimental data and validate ab initio predictions.

Rapid adsorption and enhanced removal of emodin and physcion by nano zirconium carbide.

In this study, nano zirconium carbide (n-ZrC) was synthesized by preceramic polymers method, and it was used to adsorb emodin and physcion from solutions for the first time. The prepared material was characterized by various technologies. The adsorption experiment was carried out to investigate the emodin and physcion removal performance. The results indicate that the pseudo-second-order kinetic model and the Langmuir model correlated satisfactorily to the experimental data, and the thermodynamic parameters are also calculated. Especially, n-ZrC can remove >95% of emodin or physcion in a minute under the optimal conditions, it is the fastest adsorption rate compared to other commonly used adsorbents (commercial zirconium carbide, activated carbon, C18, PSA, GCB and florisil). The adsorption mechanism was discussed, which suggests that Van der Waals' forces are the primary driving power during the adsorption process. Moreover, n-ZrC is stable at different pH and it can be reused at least fifteen times.

Carbon Nanofiber Arrays Grown on Three-Dimensional Carbon Fiber Architecture Substrate and Enhanced Interface Performance of Carbon Fiber and Zirconium Carbide Coating.

Carbon nanofibers (CNFs) were grown around the carbon fiber architecture through a plasma enhanced chemical vapor deposition method to enhance the interface performance between CF architecture substrate and ZrC preceramic matrix. The synthesized 3D CF hierarchical architectures (CNFs-CF) are coated with zirconium carbide (ZrC) ceramic to enhance their antioxidant property and high temperature resistance. The composition and the crystalline phase structure of the composite were detected with the X-ray photoelectron spectroscopy and X-ray diffraction. The results of scanning electron microscopy show that, the as-prepared CNFs and consistent ZrC ceramic coating are uniformly covered on the surface of carbon fiber architecture substrate. The ZrC ceramic products with excellent crystallinity were got from the pyrolysis of preceramic polymer at 1600 °C in inert atmosphere. Comparing with the untreated CF, the loading of ZrC ceramics around the CNFs-CF architecture surface are significantly increased. The thermal stability and mechanical property of CNFs-CF/ZrC nanocomposites have been promoted obviously compared with the CF/ZrC ceramic nanocomposite. The prepared CNFs-CF/ZrC ceramic nanocomposite is one of the potential candidate materials for the thermal protection application.

Zirconium Carbide Produced by Spark Plasma Sintering and Hot Pressing: Densification Kinetics, Grain Growth, and Thermal Properties.

Spark plasma sintering (SPS) has been employed to consolidate a micron-sized zirconium carbide (ZrC) powder. ZrC pellets with a variety of relative densities are obtained under different processing parameters. The densification kinetics of ZrC powders subjected to conventional hot pressing and SPS are comparatively studied by applying similar heating and loading profiles. Due to the lack of electric current assistance, the conventional hot pressing appears to impose lower strain rate sensitivity and higher activation energy values than those which correspond to the SPS processing. A finite element simulation is used to analyze the temperature evolution within the volume of ZrC specimens subjected to SPS. The control mechanism for grain growth during the final SPS stage is studied via a recently modified model, in which the grain growth rate dependence on porosity is incorporated. The constant pressure specific heat and thermal conductivity of the SPS-processed ZrC are determined to be higher than those reported for the hot-pressed ZrC and the benefits of applying SPS are indicated accordingly.

Spark Plasma Sintering of Commercial Zirconium Carbide Powders: Densification Behavior and Mechanical Properties.

Commercial zirconium carbide (ZrC) powder is consolidated by Spark Plasma Sintering (SPS). Processing temperatures range from 1650 to 2100 °C. Specimens with various density levels are obtained when performing single-die SPS at different temperatures. Besides the single-die tooling setup, a double-die tooling setup is employed to largely increase the actual applied pressure to achieve higher densification in a shorter processing time. In order to describe the densification mechanism of ZrC powder under SPS conditions, a power-law creep constitutive equation is utilized, whose coefficients are determined by the inverse regression of the obtained experimental data. The densification of the selected ZrC powder is shown to be likely associated with grain boundary sliding and dislocation glide controlled creep. Transverse rupture strength and microhardness of sintered specimens are measured to be up to 380 MPa and 24 GPa, respectively. Mechanical properties are correlated with specimens' average grain size and relative density to elucidate the co-factor dependencies.