Auswahl der wissenschaftlichen Literatur zum Thema „Zr oxidation ratio“

AbstractMulti-component solid solutions with non-stoichiometric compositions are characteristics of ultra-high temperature carbides as promising materials for hypersonic vehicles. However, for group IV transition-metal carbides, the oxidation behavior of multi-component non-stoichiometric (Zr,Hf,Ti)Cx carbide solid solution has not been clarified yet. The present work fabricated four kinds of (Zr,Hf,Ti)Cx carbide solid solution powders by free-pressureless spark plasma sintering to investigate the oxidation behavior of (Zr,Hf,Ti)Cx in air. The effects of metallic atom composition on oxidation resistance were examined. The results indicate that the oxidation kinetics of (Zr,Hf,Ti)Cx are composition dependent. A high Hf content in (Zr,Hf,Ti)Cx was beneficial to form an amorphous Zr-Hf-Ti-C-O oxycarbide layer as an oxygen barrier to enhance the initial oxidation resistance. Meanwhile, an equiatomic ratio of metallic atoms reduced the growth rate of (Zr,Hf,Ti)O2 oxide, increasing its phase stability at high temperatures, which improved the oxidation activation energy of (Zr, Hf, Ti)Cx.

This study investigated the decomposition of high strength p-nitrophenol (PNP) of 2,000 mg/l (3,400 mg of COD/1,250 mg of TOC) by catalytic wet air oxidation. Multi-component heterogeneous catalysts were used as catalysts for this purpose. The study results using a batch reactor showed that catalyst “D” (Mn-Ce-Zr 22.4 g plus CuSO4 1.0 g; Mn-Ce-Zr-Cu [CuSO4]) was more effective (56˜74%) than catalyst “A” (Mn-Ce-Zr 22.4 g) under the given conditions (O2 partial pressure of 1.0 MPa; temperature of 170˜190°C; 30 min of reaction time). The best result was obtained when 2 g of Mn-Ce-Zr-Cu [CuSO4] was used per 1L of PNP aqueous solution. COD and TOC removal efficiencies were 18% and 23% without catalysts during 20 min of reaction at 190°C. They were improved to 79% and 71% with 2 g/L of Mn-Ce-Zr-Cu [CuSO4] under the same conditions. The ratio of BOD5/COD was measured to evaluate biodegradability. It was 0.05 without catalyst and increased to 0.33 with 2 g/L of Mn-Ce-Zr-Cu [CuSO4] for 20 min of reaction.

This work reports the results of the ultrasound-assisted hydrothermal synthesis of two sets of V2O5 dispersed on SBA-15 and Zr doped SBA-15 catalysts used for the oxidation of dibenzothiophene (DBT) in a model diesel via the combination of oxidation, catalysis, and extraction technical route. These catalysts contained Lewis acidity as major and Brønsted acidity as minor. The amount of acidity varied with the content of vanadia and zirconium doping. It was found that DBT conversion is very sensitive to the Lewis acidity. DBT conversion increased by increasing the vanadium content and correlated well with the amount of surface Lewis acidity. Under the optimal experimental condition (Reaction temperature: 60 °C, reaction time 40 min, catalyst concentration: 1 g/L oil; H2O2/DBT mole ratio = 10), the 30% V2O5/SBA-15 and 30% V2O5/Zr-SBA-15 catalysts could convert more than 99% of DBT. Two reaction pathways of DBT oxidation involving vanadia surface structure, Lewis acidity, and peroxometallic complexes were proposed. When the vanadia loading V2O5 ≤ 10 wt%, the oxidative desulfurization (ODS) went through the Pathway I; in the catalysts with moderate vanadia content (V2O5 = 20–30 wt%), ODS proceeded via the Pathways II or/and the Pathway I.

In this study, the effect of scrap ratio on the mechanical and corrosion properties of Zr-1Nb-0.7Sn-0.1Fe alloy was studied. Oxygen content in the ingot cake increased rapidly with increasing fraction of scrap, which can be attributed to the surface oxide of scrap cake made of small pieces of turning, chips, etc. Iron content was not changed much, suggesting scrap materials was well reserved in the iron-free container. As-cast structure of Zr-1Nb-0.7Sn-0.1Fe alloy with the scrap:sponge ratio displayed basket-weave α phase and no appreciable change of the cast structure was observed with change of scrap fraction. The strength increases with increasing fraction of scrap, which can be attributed to the increase of oxygen content. The ductility decreased slightly with increase of scrap fraction. The increase of oxidation resistance with increasing fraction of scrap also can be linked to the increase of oxygen content.

We explore the unipolar resistance switching effect in sandwich structures based on Nb, Ta and Zr oxide thin films. The structures were fabricated by pulsed laser deposition and low temperature anodic oxidation methods. After electroforming process memory cells demonstrate reproducible switching between low and high resistance states with a resistance ratio around 102. Nonvolatile resistance storage was traced within 40 days. The low-temperature anodic oxidation of Nb was found to be suitable to fabricate flexible nonvolatile memory elements. The parameters of resistive switching are not degraded after 100000 flexing.

To study the fuel debris treatment at Fukushima Daiichi NPP, information on the behaviour of fuel and structural materials in severely damaged reactors, i.e., oxides and metals of uranium and zirconium is essential. Since sea water was introduced to the reactors, situation of fuel debris became different from that for TMI case. In this paper, phase relations of uranium and zirconium oxides were analyzed by powder XRD method at high temperatures. By the heat-treatment of the mixture of UO2 and ZrO2 (U:Zr=1:1) under 10 torr air, UO2 was oxidized to U3O8 over 800 oC, The UO2 like phase appeared again at 1350 oC which may be caused by the decomposition of U3O8. The oxidation behavior of the UO2-ZrO2 system was also investigated by using solid solution sample with different U/Zr ratios under different steam and oxygen pressures. The oxidation of the UO2-ZrO2 mixture seemed to be suppressed with decreasing U/Zr ratio. The behavior of fuel materials in the presence of seawater was also discussed as well as that for other structural materials.

It was investigated VPMeO catalysts (Me=Fe, Mo, Te, W, Ni, Ti, La, Bi, Zr і Ag) in oxidation of n-pentane. On these catalytic samples the main products of reaction are maleic (MA), phthalic (PhA), citraconic (CA) anhydrides, carbon oxides and in-significant quantity of acetic and of acrylic acids. It was established that a change of physical-chemical properties of the VPMeO catalysts affects a course of reaction of n-pentane oxidation. It was determined that the introduction of additives into the basic VPO composition and its content influences a phase composition, a morphol-ogy, acidic properties of catalyst surface, a crystallization temperature of active component and a oxidation degree of vanadium in it. It was established that addi-tives in the VPO sample may be distributed in two ways: a) evenly, high disperse (Fe, Te, Ni, Ag ions), b) with formation of X-ray amorphous additive phosphate phase (Ti, Bi, La, W, Zr ions). Additives that decrease temperature of the active phase formation of a catalyst and increase temperature of its oxidation (Fe, Ti, Bi, Zr ions) positively influence the life of exploitation of catalytic pattern without losing its se-lectivity in the n-pentane oxidation. Additives that reduce the O 1s-electrons energy and increase an oxygen content (O/(V+P+Me)) on the VPO composition surface en-hance the specific rate of the hydrocarbon oxidation. A growth of phosphorous con-tent on the surface of synthesized compositions also contributes to the increase of the time of their stable work. The influence of ratio of Bronsted and Lewis acid cen-ters on surface of the VPМеO pattern on a selectivity of anhydrides production was established. The growth of acidic centers content on the surface of patterns increas-es the CA selectivity. The rise of quantity of Lewis centers favors the PhA formation while the MA selectivity reduces in the reaction products. According to experimental data the modification of the VPO catalyst is affect its physical-chemical and cata-lytic properties. The change of defined physical-chemical properties allows to regu-late a process of the n-pentane oxidation in the direction of formation of one of the anhydrides.

-Type zirconium phosphate,-Zr(HPO4)2-.1.77H2O (-ZrP), crystalline cerium phosphate, Ce(HPO4)2.1.33 H2O (CePc), and [-Zr(HPO4)2]0.30 [Ce (HPO4)2]0.70 .2H2O composite were prepared and characterized by chemical, XRD, TGA, FT-IR and scanning electron microscopy(SEM). [-Zr(HPO4)2]0.30[Ce(HPO4)2]0.70/polyaniline, polyindole, polycarbazole, polyaniline-co-polyindole, polyaniline-co-polycarbazole composites were prepared via in-situ chemical oxidation of the monomers aniline, indole , carbazole, and (1:1moler ratio) of co-monomers aniline-indole, aniline- carbazole, respectively, that was promoted by the reduction of part of Ce(IV) ions present in the inorganic matrix. A possible explanation is part of CePc is attacked by the monomers, and the co-monomers, respectively, converted to cerium (III) orthophosphate (CePO4). The resultant novel composites were characterized by elemental (C,H,N) analysis, FT-IR, and (SEM). From elemental (C,H,N) analysis ,the amount of organic materials present in [-Zr(HPO4)2]0.30 [Ce (HPO4)2]0.70/ polyaniline, polyindole, polycarbazole composites were (23.44, 5.24 and 33.02 % in wt. ), respectively. The amount of resultant copolymers were (Pani 5.92, PIn 7.48 % in wt) and (Pani 1.42, PCz 2.48 % in wt ) These composites can be considered as novel conducting inorganic-organic composites, ion exchangers , solid acid catalysts and sensors.

This thesis aims to provide the thermal condition of melt pool convection by CFD simulation, which is important to the assessment of the invessel melt retention (IVR) strategy widely adopted in Generation III pressurized water reactors (PWRs). As a severe accident mitigation measure, the IVR strategy is realized through external cooling of the lower head of a reactor pressure vessel (RPV). To achieve the coolability and retention of the corium pool in the RPV lower head, the heat flux at the outer surface of the vessel should be less than the critical heat flux (CHF) of boiling around the lower head. Under such condition, the integrity of the RPV is guaranteed by the adequate thickness of the unmelted vessel wall. The thesis work starts from the selection and validation of a turbulence model in the CFD computational tool chosen (Fluent). Afterwards a numerical model is set up for estimation of melt pool heat transfer of a reference PWR with the power capacity of 1000 MWe, including a mesh sensitivity study. Based on the numerical model of a twolayer melt pool, four tasks are carried out to investigate the effects of Zr oxidation ratio, Fe content, and radiation emissivity on heat flux profiles, as well as the focus effect under extreme conditions. Selection and validation of the turbulence model are conducted by comparing the simulation results of different turbulence models with the DNS data on the convection of volumetrically heated fluid layer bounded by rigid isothermal horizontal walls at equal temperature. The internal Rayleigh numbers of the flow reach up to 10e6. The comparison shows a good agreement of the SST k-ω turbulence model results with the DNS data. The simulations with the Zr oxidation ratio of 0, 0.2 and 0.5, correspondingly, the oxide layer of 1.389m, 1.467m and 1.580m, and the metal layer of 0.705m, 0.646m and 0.561m in height, show that, the temperature of the oxide layer will increase with Zr oxidation ratio, while the temperature of the metal layer will decrease resulting in more heat transfer through the oxide layer sidewall and less top radiation. Nevertheless, the effect of the Zr oxidation ratio is not pronounced in the range of 00.5. The simulations with the Fe mass of 22t, 33t and 45t, and respective height of the metal layer of 0.462m, 0.568m and 0.646m, show that, the inner metal layer will significantly increase the temperatures of both the metal layer and the oxide layer. The percentage of heat transfer at the oxide layer sidewall will increase to supplement the reduction of that at the metal layer. The simulations with the radiation emissivity of 0.2, 0.35, 0.45 and 0.7 show that, the emissivity below 0.45 has an impact on heat transfer, and the temperatures and sidewall heat flux of both the oxide layer and the metal layer will increase with decreasing emissivity. The impact is negligible when the emissivity is above 0.45. The simulations under the hypothetically extreme conditions with either an adiabatic top boundary or a very thin metal layer show the focusing effect may occur, i.e., the heat flux through the metal sidewall is larger than that in the oxide layer. But the local high heat flux is flattened by the vessel wall with good heat conductivity. In summary, the simulations demonstrate that, except for the cases under extreme conditions, the heat fluxes of the melt pools in all other cases are significantly lower than the CHF of external cooling of the lower head. Therefore, the safety margin of the IVR strategy of the PWR chosen is seems sufficient. However, due to some limitations (e.g., simplification and assumptions) in the simulation cases and coupling of different influential factors, as indicated by the present study, the precise predictions of heat flux under all scenarios are still difficult. Therefore, the conclusions could not be generalized to the other conditions or other configurations of the molten pools. By discussing the model and simplifications/assumptions adopted in this work, the improvement directions of the numerical model and other perspectives are proposed at the end of the thesis.
Denna avhandling syftar till att tillhandahålla det termiska tillståndet för smältbassängskonvektion genom CFD-simulering, vilket är viktigt för bedömningen av IVR-strategin som allmänt antagits i tryckvattenreaktorer (PWR) i Generation III. Som en åtgärd för att mildra allvarliga olyckor realiseras IVR-strategin genom extern kylning av det nedre huvudet av ett reaktortryckkärl (RPV). För att uppnå kylbarhet och kvarhållning av koriumbassängen i det nedre RPV-huvudet bör värmeflöde vid den yttre ytan av kärlet vara mindre än det kritiska värmeflödet (CHF) som kokar runt det nedre huvudet. Under sådant tillstånd garanteras RPV: s integritet av den osmälta kärlväggens tillräckliga tjocklek. Examensarbetet startar från valet och valideringen av en turbulensmodell i det valda CFD-beräkningsverktyget (Fluent). Därefter sätts en numerisk modell upp för uppskattning av smältbassängens värmeöverföring av en referens PWR med en effektkapacitet på 1000 MWe, inklusive en nätkänslighetsstudie. Baserat på den numeriska modellen för en tvålagers smältbassäng utförs fyra uppgifter för att undersöka effekterna av Zr-oxidationsförhållande, Fe-innehåll och strålningsemissivitet på värmeflödesprofiler, liksom fokuseffekten under extrema förhållanden. Val och validering av turbulensmodellen utförs genom att jämföra simuleringsresultaten för olika turbulensmodeller med DNS-data för konvektionen av volymetriskt uppvärmt fluidskikt avgränsat av styva isoterma horisontella väggar vid lika temperatur. De interna Rayleigh-siffrorna i flödet når upp till 10e6. Jämförelsen visar att SST k-ω turbulensmodellresultaten överensstämmer med DNS-data. Simuleringarna med Zr-oxidationsförhållandet 0, 0,2 och 0,5, motsvarande oxidskiktet på 1,389 m, 1,467 m och 1,580 m, och metallskiktet på 0,705 m, 0,664 m och 0,561 m i höjd, visar att temperaturen av oxidskiktet kommer att öka med Zr-oxidationsförhållandet, medan metallskiktets temperatur kommer att minska vilket resulterar i mer värmeöverföring genom oxidskiktets sidovägg och mindre toppstrålning. Ändå är effekten av Zr-oxidationsförhållandet inte uttalad i intervallet 00,5. Simuleringarna med Fe-massan på 22t, 33t och 45t och respektive höjd av metallskiktet på 0,462m, 0,568m och 0,664m visar att det inre metallskiktet avsevärt kommer att öka temperaturerna för både metallskiktet och oxiden lager. Andelen värmeöverföring vid oxidskiktets sidovägg ökar för att komplettera minskningen av den vid metallskiktet. Simuleringarna med strålningsemissiviteten 0,2, 0,35, 0,45 och 0,7 visar att emissiviteten under 0,45 påverkar värmeöverföringen, och temperaturerna och sidoväggens värmeflöde för både oxidskiktet och metallskiktet kommer att öka med minskande emissivitet. Effekten är försumbar när strålningen är över 0,45. Simuleringarna under de hypotetiskt extrema förhållandena med antingen en adiabatisk övre gräns eller ett mycket tunt metallskikt visar att fokuseringseffekten kan uppstå, dvs. värmeflödet genom metallsidan är större än det i oxidskiktet. Men det lokala höga värmeflödet plattas ut av kärlväggen med god värmeledningsförmåga. Sammanfattningsvis visar simuleringarna att, förutom fall under extrema förhållanden, är värmeflödet från smältpoolerna i alla andra fall betydligt lägre än CHF för extern kylning av nedre huvudet. Därför verkar säkerhetsmarginalen för IVR-strategin för den valda PWR tillräcklig. På grund av vissa begränsningar (t.ex. förenkling och antaganden) i simuleringsfall och koppling av olika inflytelserika faktorer, vilket indikeras av den aktuella studien, är de exakta förutsägelserna av värmeflöde under alla scenarier fortfarande svåra. Därför kunde slutsatserna inte generaliseras till de andra förhållandena eller andra konfigurationer av de smälta poolerna. Genom att diskutera modellen och förenklingar / antaganden som antagits i detta arbete föreslås förbättringsriktningarna för den numeriska modellen och andra perspektiv i slutet av avhandlingen.

An important accident management measure in PWRs is the injection of water to cool the degrading core, in which process the temperature and hydrogen production will significantly increase due to enhanced oxidation after shattering of zircaloy fuel rod. This phenomenon can be described by Zr oxidation model and shattering model. The process of Zr oxidation is usually represented by parabolic rate correlations. But, after consumption of primary β-Zr, or in steam starvation conditions, the correlation approach is restricted. Besides, using this approach, it is impossible to obtain detailed oxygen distribution in the cladding which impacts the detailed mechanical behavior, such as shattering of cladding. The shattering of cladding is mainly contributed by deep cracks penetrating the oxide layer as well as the adjacent metallic. In SCDAP/RELAP5, the shattering criterion is relevant to the thickness of β-Zr, the cladding temperature, and the cooldown rate. After shattering of cladding, the oxide scale is simply removed. This shattering criterion deviates from the experiment of Chung and Kassner when the maximum cladding temperature exceeds 1560 K, and the model can’t reveal the impact of the cladding surface temperature before cooldown on cladding conditions after shattered. An oxidation model based on reaction-diffusion equations at the temperature range from 923K to 2098K is developed in this study. By comparison with experimental data, the model shows reasonable results. Based on the oxidation model, the advanced shattering criterion is adopted, and a new empirical model to describe the cladding conditions after shattered is proposed. In present shattering model, R(T, m), which is the ratio between the area of new crack surfaces in the metal layer and the area of outer cladding surface, is the function of T (the temperature of the cladding surface before cooldown) and m (the thickness of the metal layer). With the help of single-rod QUENCH experiment, the preliminary expression of R(T, m) is obtained, and the results are in a good agreement qualitatively with the observation in this experiment. Further activities should focus on the impact of m and T on R(T, m), which needs more detailed single-rod experiments. Those developed models can be implemented into the SCDAP/RELAP5 code easily and used in the severe accident analysis in the future.