The irradiation response of ZrC ceramics under 10 MeV Au3+ ion irradiation at 800 ºC

The microstructural evolution was characterized for ZrC ceramics irradiated with 10 MeV Au³⁺ ions at 800 °C. Post-irradiation examination showed that ZrC did not amorphize at doses up to 30 displacement per atoms (dpa). Concurrent oxidation of ZrC was found to occur during ion irradiation. Coarsening of the defective microstructure, as a function of dose, was revealed by transmission electron microscopy analysis. Black dot defects were observed at low doses (0.5 dpa), and tangled dislocation networks were formed at 5 dpa and above. Diffraction analysis showed a change in the defect structure occurred at doses close to ∼2.5 dpa. The evolution of lattice parameter with dose indicated that uptake of adventitious oxygen could occur in specimens irradiated at high doses. Raman spectroscopy analysis indicated an increase in non-stochiometry after irradiaton. This work identified specific relationships between dose and microstructure after irradiation, revealing the mechanisms of damage production in ZrC_x ceramics.     

In-situ synthesis of zirconium oxycarbide by electroreduction of ZrO2/C in molten salt

Homogenous ZrC_xO_y powders have been successfully synthesized by in-situ electro-reduction of solid ZrO₂–C composite precursors in molten CaCl₂. The effect of applied cell voltage and molar ratio of ZrO₂ to C on preparation of ZrC_xO_y were investigated. The reduction pathway of the composite electrode was studied based on the analysis of intermediate products using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that ZrO₂ is firstly converted to CaZrO₃. The resulting CaZrO₃ is then reduced to ZrC_xO_y. The ZrC_xO_y formation is dramatically influenced by electrolysis voltage and molar ratio of ZrO₂ to C: a higher cell voltage and lower molar ratio of the ZrO₂ to C are more preferable for the formation of ZrC_xO_y powder. Homogenous ZrC_xO_y powders with particle size of ~100 nm are synthesized by ZrO₂/C starting elemental powders in CaCl₂ molten salt at 1123 K for more than 3 h, when the cell voltage is 3.0 V and the molar ratio of the ZrO₂ to carbon starting materials is 1:1.0.     

Impact of H+ ion beam irradiation on Matrimid®. II. Evolution in gas transport properties

Ion beam irradiation is an easily controlled method to modify the chemical structure and microstructure of polymers including the fractional free volume, free volume distribution and chain mobility, thus altering the gas transport properties of the irradiated polymers. The previous paper focused on the impact of H⁺ ion beam irradiation on chemical structural evolution of the polyimide Matrimid®. This paper focuses on the impact of H⁺ ion beam irradiation on microstructure and gas permeation properties of Matrimid®. Irradiation at low ion fluence resulted in slight decreases in permeabilities for five gases (i.e., He, CO₂, O₂, N₂, and CH₄) with increases in permselectivities for some gas pairs (e.g., He/CH₄ and He/N₂). In contrast, irradiation at relatively high ion fluences resulted in simultaneous increases in permeabilities and permselectivities for most gas pairs (e.g., He/CH₄, He/N₂, O₂/N₂, and CO₂/CH₄). While Matrimid® has bulk gas permeation properties that are below the range of commercially interesting polymers, samples irradiated at high ion fluences exhibited significant improvement in gas separation performances. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1670–1680, 2007     

TEM Study of the High‐Temperature Oxidation Behavior of Hot‐Pressed ZrB2–SiC Composites

The oxidation behaviors of ZrB₂‐ 30 vol% SiC composites were investigated at 1500°C in air and under reducing conditions with oxygen partial pressures of 10⁴ and 10 ^{? 8} Pa, respectively. The oxidation of ZrB₂ and SiC were analyzed using transmission electron microscopy (TEM). Due to kinetic difference of oxidation behavior, the three layers (surface silica‐rich layer, oxide layer, and unreacted layer) were observed over a wide area of specimen in air, while the two layers (oxide layer, and unreacted layer) were observed over a narrow area in specimen under reducing condition. In oxide layer, the ZrB₂ was oxidized to ZrO₂ accompanied by division into small grains and the shape was also changed from faceted to round. This layer also consisted of amorphous SiO₂ with residual SiC and found dispersed in TEM. Based on TEM analysis of ZrB₂ – SiC composites tested under air and low oxygen partial pressure, the ZrB₂ begins to oxidize preferentially and the SiC remained without any changes at the interface between oxidized layer and unreacted layer.     

Vacancy ordering in zirconium carbide with different carbon contents

Zirconium carbide (ZrC_x) ceramics with different carbon contents were prepared by reactive hot-pressing. The rock-salt structure of ZrC_x was the only phase detected by x-ray diffraction of the hot pressed ceramics. The relative densities of ZrC_x decreased as carbon content increased, in general. The actual carbon contents were measured by completely oxidizing the ZrC_x ceramics to ZrO₂. For most compositions, the actual carbon contents were higher than nominal batched compositions, presumably due to carbon uptake from the graphite furnace and hot press dies. Selected area electron diffraction and neutron powder diffraction revealed the presence of carbon vacancy ordering in ZrC_x for 0.6 < x < 0.75. Rietveld refinement of the neutron diffraction patterns determined that the crystal structure of the ordered phase was hexagonal, and the carbon site occupancies were higher than nominal batched carbon stoichiometry.     

Comparative study of gamma and ion beam irradiation of polymeric nanocomposite on electrical conductivity

Poly(vinyl alcohol) (PVA) was used to prepare nanocomposites of multi‐wall carbon nanotubes (MWCNT) and functionalized carbon nanotubes (MWCNT‐NH₂) in existence of 2‐carboxyethyl acrylate oligomers (CEA). Radiation‐induced crosslinking of the prepared matrix was carried out via gamma and ion beam irradiation. A comparative study of gamma and ion beam irradiation effect on the electrical conductivity of nanocomposite was conducted. The gelation of the gamma irradiated matrix outperforms the ion beam irradiated matrix. The order of gelation is PVA > (PVA/CEA) > (PVA/CEA)‐MWCNT > (PVA/CEA)‐MWCNT‐NH₂. There is a significant reduction in the swelling of the nanocomposite. The formation of nanocomposites was confirmed by scanning electron microscopy, energy‐dispersive X‐ray (EDX) and FTIR examinations. The direct current electrical properties of PVA/nanocomposites are examined at room temperature by applying electric voltage from 1 to 20 V. The results revealed that the electrical conductivity is increased by adding the carbon nanotubes and irradiation by gamma and ion beam. At an applied electric voltage 20 V, in the electrical conductivity of the unirradiated PVA was from 9.20 × 10^?8 S cm^?1. After adding MWCNT an increase up to 4.70 × 10^?5 S cm^?1 was observed. While after ion beam irradiation, a further increase up to 9.30 × 10^?5 S cm^?1 was noticed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46146.     

The effect of the change of the structure on oxidative dehydrogenation of propane over cerium–zirconium catalysts

A series of pure CeO₂, ZrO₂, and CeZrO_x mixed metal oxide catalysts were prepared by a wetness impregnation method and were applied to the dehydrogenation of propane to propylene at 500°C and 0.1 MPa. The prepared catalysts were characterized by thermal gravimetric analysis (TGA), Brunauer, Emmett, and Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopes (TEM), Raman spectroscopy, and H₂-TPR. It was observed that the zirconium content of the solid solution of the mixed metal oxide catalyst was 5%–25%, while the zirconium content of the material with phase segregation was higher (50%). The addition of zirconium was proven to decrease the oxygen vacancy concentration on the catalyst surface and change the intensity of (111) crystal of cerium oxide in the catalysts. Among the prepared catalysts, the Ce_0.90Zr_0.10O_x catalyst with the maximum strength of the (111) crystal plane of cerium oxide exhibited the better catalytic oxidation performance for the dehydrogenation of propane to propylene. Compared with ZrO₂ in the blank experiment, the average propane conversion and propylene selectivity of the Ce_0.90Zr_0.10O_x catalyst were increased by 10.78% and 17.95%, respectively.     

Effects of High-Energy Electron Beam Irradiation on the Properties of Flame-Retardant HDPE/EVA/Mg(OH)2 Composites

The mechanical properties of flame-retardant high-density polyethylene/ethylene vinyl-acetate copolymer/magnesium hydroxide (HDPE/EVA/Mg(OH)₂) composites for cable materials are usually poor due to the high loading of the filler. In this study, high-energy electron beam irradiation was applied to HDPE/EVA/Mg(OH)₂ composites in the presence of triallylisocyanurate, an irradiation sensitizer. The effects of high-energy electron beam irradiation on the properties of irradiated HDPE/EVA/Mg(OH)₂ composites were investigated through the measurements of gel content, limiting oxygen index, tensile testing, thermogravimetric analysis, and scanning electron microscope. The results showed that the thermal, mechanical and flame-retardant properties of the HDPE/EVA/Mg(OH)₂ composites were improved by using high-energy electron beam irradiation.     

Cross-diffusion phenomena within a ZrCx – Zr – ZrCx joint

This study uncovers process conditions for the homogenization of the interface zone formed by a diffusion bonding of ZrC_x (x = 1, 0.85 and 0.7) assisted by a Zirconium interlayer. The transitional metal interlayer is positioned between the ceramics mating surfaces _. The ability of Zr to form a homogenous joint with ZrC_x was verified for all the considered cases of ZrC_x. The homogenous joint domain forms under conditions of a particular range of values of (i) the concentration of carbon vacancies in the base ZrC_x ceramics, (ii) the bonding temperature, and (iii) the holding time, for a given thickness of the interlayer. The formation of a homogenous domain improves remarkably the mechanical properties of ZrC_x joints. It is established that the four-point bending strength and the nano-indentation hardness of the homogenous ZrC_x/Zr/ZrC_x joints can be as high as that of the base ceramics.     

Modeling gold/iron oxide interface system

The effect of gold particle size and Au/FeO _x interface on the electronic properties and catalytic activity using samples of Au/SiO₂/Si(100), Au/FeO _x /SiO₂/Si(100), FeO _x /Au/SiO₂/Si(100) has been modelled. Nanosize gold particles of varying size were fabricated by deposition of a 10 nm thick gold film onto SiO₂/Si(100) substrate by electron beam evaporation followed by modification using low energy Ar⁺ ion bombardment or Ar⁺ ion implantation. These modifications formed Au islands of decreasing size accompanied by the strong redistribution of the Au 5d valence band structure determined by ultraviolet and X-ray photoelectron spectroscopy (UPS, XPS) and increased activity in catalytic CO oxidation. The gold/iron oxide interface was prepared by deposition of iron oxide using pulsed laser deposition (PLD). The structural properties of gold and iron oxide were characterized by XPS, atomic force microscopy (AFM), transmission electron microscopy (TEM) and secondary ion mass spectroscopy (SIMS). Generally, the formation of gold/iron oxide interface increases the catalytic activity in CO oxidation regardless of the sequence of deposition, namely either Au/FeO _x /SiO₂/Si(100) or FeO _x /Au/SiO₂/Si(100) is formed. Furthermore, the interface formed is operative in determining the catalytic activity even if gold is not exposed to the surface, but it is located underneath the iron oxide layer. This is a promoting effect of the Au nanoparticles, which is more efficient than that of the bulk like Au films.     

Carbon vacancy ordering in zirconium carbide powder

Ordered carbon vacancies were detected in zirconium carbide (ZrC_x) powders that were synthesized by direct reaction. Zirconium hydride (ZrH₂) and carbon black were used as starting powders with the molar ratio of ZrH₂:C = 1:0.6. Powders were reacted at 1300°C or 2000°C. The major phase detected by x-ray diffraction (XRD) was ZrC_x. No excess carbon was observed by transmission electron microscopy (TEM) in powders synthesized at either temperature. Ordering of the carbon vacancies was identified by neutron powder diffraction (NPD) and further supported by selected area electron diffraction (SAED). The vacancies in carbon-deficient ZrC_x exhibited diamond cubic symmetry with a supercell that consisted of eight (2 × 2 × 2) ZrC_x unit cells with the rock-salt structure. Rietveld refinement of the neutron diffraction patterns revealed that the synthesis temperature did not have a significant effect on the degree of vacancy ordering in ZrC_x powders. Direct synthesis of ZrC_0.6 resulted in the partial ordering of carbon vacancies without the need for extended isothermal annealing as reported in previous experimental studies.     

Synthesis of well-dispersed PtRuSnOx by ultrasonic-assisted chemical reduction and its property for methanol electrooxidation

PtRuSnO_x supported on multi-wall carbon nanotubes (MWCNTs) was prepared by ultrasonic-assisted chemical reduction method. The as-prepared catalyst was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns indicate that Pt exists as the face-centered cubic structure, Ru is alloyed with platinum, while non-noble metal oxide SnO_x exists as an amorphous state. From TEM observation, PtRuSnO_x is well dispersed on the surface of MWCNTs with the particle size of several nanometers. The electrochemical properties of the as-prepared catalyst for methanol electrooxidation were studied by cyclic voltammetry (CV) and chronoamperometry (CA). The onset potential of methanol oxidation on PtRuSnO_x and PtRu catalysts is much more negative than that on Pt catalyst, shifting negatively by about 0.20 V, while the peak current density of methanol oxidation on PtRuSnO_x is higher than that on PtRu. Electrochemical impedance spectroscopy (EIS) studies also show that the reaction kinetics of methanol oxidation is improved with the presence of SnO_x. The addition of non-noble metal oxide SnO_x to PtRu promotes the catalytic activity for methanol electrooxidation and the possible reaction mechanism is proposed.     

Effects of intermediate energy heavy‐ion irradiation on the microstructure of rutile TiO2 single crystal

This study reports the microstructure evolution of single crystal rutile TiO₂ under 3 MeV Nb⁺ ion irradiation, with the irradiating ions incident on the {100} plane. A complex, multi‐layered microstructure evolution is observed with 4 distinct regions: (i) short‐range disorder in the first 60 nm below the specimen surface, (ii) dislocation loops oriented parallel to the incident ion beam direction, located along the increasing slope of the irradiation damage profile at ~60‐650 nm from the surface, (iii) loops oriented perpendicular to the incident ion beam direction, at depths encompassing the ion implantation and irradiation damage peaks ~650‐1250 nm, and (iv) a high density of nano‐scale atomic rearrangements with long‐range order, located at depths ~1250‐1750 nm. These results present evidence that multiple defect mechanisms occur during irradiation including ion channeling, nuclear stopping, and electronic stopping interactions as a function of depth and disorder accumulation.     

Surface reaction on polyvinylidenefluoride (PVDF) irradiated by low energy ion beam in reactive gas environment

Polyvinylidenefluoride (PVDF) was irradiated by a keV Ar⁺ ion in O₂ environment for improving adhesion between PVDF and Pt, and reaction between PVDF and the ion beam has been investigated by X‐ray photoelectron spectroscopy (XPS). The adhesion test between Pt and the modified PVDF was carried out by boiling test, in which the specimens were kept in boiling water for 4 h. Two failure modes (buckling up due to weak adhesion and crack formation due to strong adhesion) of Pt films have been observed in the system. Contact angle of PVDF was reduced to 31 from 75° by the irradiation of 1 × 10¹⁵ Ar⁺ ions/cm² with oxygen flow rate of 8 sccm. The surface of the irradiated PVDF became more rough as ion dose increased. The improved adhesion mechanism and identification of newly formed chemical species have been confirmed by Carbon 1s and Fluorine 1s X‐ray photoelectron core‐level spectra. The main reaction occurred at the irradiated PVDF surface is an ion‐beam‐induced oxidation accompanied with preferential sputtering of fluorine. Newly formed chemical species at interface are regarded as ester and carboxyl groups. Adhesion of the Pt–PVDF interface was improved by ion irradiation in O₂ environment. This improvement is originated from the presence of carbon—oxygen bonds on the irradiated PVDF surface. Comparison of failure modes on the irradiated PVDF at various conditions after the boiling test shows that adhesion of Pt film is largely affected by the product of ion‐assisted reaction. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 41–47, 1999     

Hot isostatic pressed pyrochlore glass-ceramics: Revealing structure insides at the reaction interface

As potential waste forms for immobilizing actinide-rich radioactive wastes, Eu₂Ti₂O₇ (Eu as a surrogate for minor actinides) pyrochlore glass-ceramics were fabricated via hot isostatic pressing (HIPing) at 1200°C. The structure and microstructure at the reaction interface between the glass-ceramic waste form and the stainless steel (SS) canister under HIPing conditions were carefully investigated with scanning electron microscopy (SEM), transmission electron microscopy (TEM), and synchrotron single crystal X-ray diffraction (SC-XRD). The interactions at the reaction interface led to the formations of a ~10-µm-thick Cr₂O₃ layer as the oxidation front of the SS and a layer of a mixed oxide phase (Eu_1.25SiCr_0.8Ti_1.2O_7.5) on the glass-ceramic side of the reaction interface. The crystal structure of such a unique mixed oxide phase was revealed indubitably with a combination of synchrotron SC-XRD and TEM assisted with a focused ion beam (FIB) SEM system. The improved structural understanding of the reaction interface will help to support the utilization of HIPing as a versatile hot consolidation process for the treatment of radioactive wastes.     

Properties of hydroxyapatite/zirconium oxide nanocomposites

Effects of zirconium oxide (ZrO₂) nanoparticles additive on the microstructure and physical properties of hydroxyapatite (HA) were investigated. The HA powder was derived from natural bovine bone by a sequence of thermal processes. The composites containing nanoparticles of ZrO₂ (0.2–1.0 vol%) were fabricated by a solid-state reaction mixed oxide method. All samples showed traces of HA, beta-tricalcium phosphate (β-TCP) and alpha-tricalcium phosphate (α-TCP) phases while the x≥0.1 samples also showed ZrO₂ phase. Amount of β-TCP and α-TCP phases tend to decrease with ZrO₂. The additive inhibited grain growth as a result of a decrease in grain size. However, the x=0.2 sample exhibited higher hardness value which is consistent with the density data. In addition, bioactivity test suggested that the additive promoted an apatite forming with the values of Ca/P close to the value obtained from HA.     

Highly Active SO4 2−/xTiO2–ZrO2 Catalysts for the Esterification Between Terephthalic Acid and 1,3-Propanediol

Poly (trimethylene terephthalate) (PTT) is considered as one of the excellent fiber materials in the twenty-first century. It was synthesized as early as in 1940s, but up to now, it is rather difficult to obtain the PTT with high molecular weight suitable for spinning, due to the absence of highly active catalysts. In this work, two series of catalysts, i.e., xTiO₂–ZrO₂ (x = 6, 8, 10, 15) and SO₄ ^2?/xTiO₂–ZrO₂ (x = 6, 8, 10, 15) were prepared, and used for the esterification of terephthalic acid (TPA) and 1,3-Propanediol (PDO). The synthesized catalysts were fully characterized by scanning electron microscope (SEM), infrared diffusion reflectance spectrum (IDRS), X-ray diffraction (XRD) and NH₃-temperature programmed desorption (NH₃-TPD) techniques. Based on the difference in acidities between xTiO₂–ZrO₂ and SO₄ ^2?/xTiO₂–ZrO₂ as indicated by characteristic results of IDRS and NH₃-TPD, SO₄ ^2?/xTiO₂–ZrO₂ have more Brønsted acid sites on their surfaces than xTiO₂–ZrO₂, as a result, SO₄ ^2?/xTiO₂–ZrO₂ had high activities for the esterification of TPA and PDO.     

Supported copper–ceria catalysts for low temperature CO oxidation

In this investigation, CuO/CeO₂–M_xO_y (M_xO_y = Al₂O₃, ZrO₂ and SiO₂) nanocomposite oxide catalysts were prepared by deposition-precipitation and wet impregnation methods, and evaluated for CO oxidation. Catalysts were characterized by XRD, TEM, UV–vis DRS, BET surface area and H₂-TPR techniques. The synthesized catalysts exhibited high specific surface area, and uniform particle size distribution over the supports. The nanocrystalline texture of mixed metal oxides is clearly evidenced by TEM analysis. TPR and XRD results revealed synergetic interactions between copper oxide and ceria. Among various catalysts investigated, the CuO/CeO₂–Al₂O₃ combination exhibited excellent CO oxidation activity with T_1/2 = 374 K and 100% CO conversion at below 420 K.     

Effects of heavy-ion irradiation on Gd2Zr2O7 bearing simulated TRPO waste

Considering the urgent demand of nuclear waste disposal, a comprehensive study on the irradiation performance of nuclear waste forms is extremely necessary, especially on those containing multiple-nuclides with multiple-valence. The irradiation effects of Gd₂Zr₂O₇ pyrochlore bearing simulated trialkyl phosphine oxides (TRPO) waste (consisting of ZrO₂, MoO₃, RuO₂ and PdO) were studied in this work. Gd_10.685Mo_4.734Zr_28.924Ru_1.000Pd_1.745O_91.825 and Gd_8.883Mo_9.901Zr_33.760Ru_2.089Pd_3.644O_118.368 were irradiated by 1.5?MeV Xe²⁰⁺ to fluences from 1?×?10¹² to 1?×?10¹⁵ ions/cm² at room temperature. The results showed an irradiation induced disordering with slight micro-swelling. In addition, the ion irradiation tolerance of the solid solutions decreased as the TRPO waste content increased. The decrease and shift of Raman peaks indicated the structural disordering and inner stress after irradiation. The micromorphology and element distribution of the irradiated surface remained almost unchanged. The structural evolution from pyrochlore to fluorite and even amorphous structure were disclosed in this study.     

Alpha-particle irradiation effects on uranium-bearing Gd2Zr2O7 ceramics for nuclear waste forms

It is necessary to study the self-irradiation effects of nuclear waste forms under α-decay in the long term storage. In the present work, accelerated irradiation experiments were performed on (Gd_1-4xU_2x)₂(Zr_1-xU_x)₂O₇ (x = 0, 0.10, 0.14) samples using 0.5 MeV alpha-particle irradiation at fluences ranging from 1 × 10¹⁴ to 1 × 10¹⁷ ions/cm² at room temperature. Irradiation induced microstructural evolution was examined by grazing incidence X-ray diffraction (GIXRD), Raman spectroscopy and Field-emission scanning electron microscopy (FESEM). The results show that the main crystal structure is kept, however, weaker structural ordering is leaded as a result of intensified irradiation. And the radiation resistance is enhanced by the growing uranium content in the discussed range. Moreover, the irradiation effects as a function of depth have been discussed. Raman spectra reveal that the vibration intensity of atomic bonds are changed due to increased irradiation. In addition, the microtopography and element distribution have been kept after irradiation.