Academic literature on the topic 'Pinnick oxidation'

A computational study on Pinnick oxidation of aldehydes into carboxylic acids using density functional theory (DFT) calculations has been evaluated with the (SMD)-M06-2X/aug-pVDZ level of theory, leading to an important understanding of the reaction mechanism that agrees with the experimental observations and explaining the substantial role of acid in driving the reaction. The DFT results elucidated that the first reaction step (FRS) proceeds in a manner where chlorous acid reacts with the aldehyde group through a distorted six-membered ring transition state to give a hydroxyallyl chlorite intermediate that undergoes a pericyclic fragmentation to release the carboxylic acid as a second reaction step (SRS). 1 H NMR experiments and simulations showed that hydrogen bonding between carbonyl and t -butanol is unlikely to occur. Additionally, it was found that the FRS is a rate-determining and thermoneutral step, whereas SRS is highly exergonic with a low energetic barrier due to the Cl(III) → Cl(II) reduction. Frontier molecular orbital analysis, intrinsic reaction coordinate, molecular dynamics and distortion/interaction analysis further supported the proposed mechanism.

A primary study on the resistance to high-temperature-oxidation of 430 ferrite stainless steel and its oxidation process before and after the addition of RE elements was reported. Results show that the oxidation resistance of 430 ferrite stainless steel after adding RE is indeed great. The value of oxidation rate of Sample 1 (without adding RE) is 2.87 times higher than Sample 2, respectively at 1423K after oxidizeing for totally 144h. And the dense and adherent Cr2O3 scale and FeCr2O4 scale are formed and played the protection role to the 430 ferrite stainless steel. In the internal oxidation layer, the pinning effect of silicon dioxide is strengthened by RE.

The oxidation resistance of FeCrNi heat-resisting steel at 1150°C and 1200°C is analyzed and studied using XRD, SEM and EDS techniques. The results show that the oxidation resistance of the heat-resisting steel is improved remarkably after adding yttrium. The value of oxidation rate of experimental Sample 1 (without adding Y) is 3.25 times and 1.56 times higher than Sample 2, respectively at 1150°C and 1200°C after oxidizeing for totally 144h. On the surface of the heat-resisting steel containing Y, the dense and adherent Cr2O3 scale and FeCr2O4 scale are formed and played the protection role. In the internal oxidation layer, the pinning effect of silicon dioxide is strengthened by Y, and Y has a pining effect directly.

AbstractThe oxidation behavior of Fe-Si-Ce alloys with different Ce content at 1,173 and 1,273 K has been studied by means of optical microscope (OM), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscope (SEM). Results show that the Ce addition refines the grain size of Fe-Si alloys, and correspondingly the grain size of the oxides decreases, which increases the grain boundary concentration and promotes the short-path diffusion of the alloying elements and oxygen. During oxidation, the positive effect of the grain refinement on the oxidation behavior of the alloy is more obvious than negative effect, so the Ce addition improves the oxidation resistances of the Fe-3Si alloys. Compared to Fe-3Si-0.5Ce alloy, Fe-3Si-5.0Ce alloy has the larger mass gain for the preferential oxidation of the excessive content of Ce exceeding its beneficial effects. The rare earth Ce changes the oxidation mechanism of Fe-Si alloys. Oxygen penetrates the oxide scales and reacts preferentially with Ce-rich phases, which results in the pinning effect and improves the adhesion of the oxide scales.

Ni-(3~10) Ta and Ni-(3~10) Y alloys were fabricated by vacuum arc melting. The oxidation resistance of the alloys was studied by cyclic and isothermal oxidation tests at 800 °C in static air. The present work focused on the investigation of the effects of the alloying elements (Ta and Y) on the oxidation behavior of Ni-based alloys. The oxidation behavior of alloys was evaluated by mass gain, composition, as well as the microstructure of oxidized products. The experimental results indicated that Ta at a low content (3 wt %) had a positive role in enhancing oxidation resistance by decreasing the oxygen vacancy concentration of the oxide layer to prevent the inward diffusion of oxygen during oxidation, and the mass gain decreased from 2.9 mg·cm−2 to 1.7 mg·cm−2 (800 °C/200 h), while Y (3~10 wt %) degraded the oxidation resistance. However, it is worth mentioning that the pinning effect of Y2O3 increased the adhesion between the substrate and oxide layer by changing the growing patterns of the oxide layer from a plane growth to fibrous growth. Among the results, the bonding of the substrate and oxide layer was best in the Ni-3Y alloys.

Defects in the functional oxides play an important role in electronic devices like metal oxide semiconductor field effect transistors (MOSFETs) and resistive random-access memories (ReRAMs). The continuous scaling of CMOS has brought the Si MOSFET to its physical technology limit and the replacement of Si channel with Ge channel is required. However, the performance of Ge MOSFETs suffers from Ge/oxide interface quality and reliability problems, which originates from the charge traps and defect states in the oxide or at the Ge/oxide interface. The sub-oxide layers composed of GeII states at the Ge/GeO2 interface seems unavoidable with normal passivation methods like hydrogen treatment, which has poor electrical properties and is related to the reliability problem. On the other hand, ReRAM works by formation and rupture of O vacancy conducting filaments, while how this process happens in atomic scale remains unclear. In this thesis, density functional theory is applied to investigate the defect behaviours in oxides to address existing issues in these electronic devices. In chapter 3, the amorphous atomic structure of doped GeO2 and Ge/GeO2 interface networks are investigated to explain the improved MOSFET reliability observed in experiments. The reliability improvement has been attributed to the passivation of valence alternation pair (VAP) type O deficiency defects by doped rare earth metals. In chapter 4, the oxidation mechanism of GeO2 is investigated by transition state simulation of the intrinsic defect diffusion in the network. It is proposed that GeO2 is oxidized from the Ge substrate through lattice O interstitial diffusion, which is different from SiO2 which is oxidized by O2 molecule diffusion. This new mechanism fully explains the strange isotope tracer experimental results in the literature. In chapter 5, the Fermi level pinning effect is explored for metal semiconductor electrical contacts in Ge MOSFETs. It is found that germanides show much weaker Fermi level pinning than normal metal on top of Ge, which is well explained by the interfacial dangling bond states. These results are important to tune Schottky barrier heights (SBHs) for n-type contacts on Ge for use on Ge high mobility substrates in future CMOS devices. In chapter 6, we investigate the surface and subsurface O vacancy defects in three kinds of stable TiO2 surfaces. The low formation energy under O poor conditions and the +2 charge state being the most stable O vacancy are beneficial to the formation and rupture of conducting filament in ReRAM, which makes TiO2 a good candidate for ReRAM materials. In chapter 7, we investigate hydrogen behaviour in amorphous ZnO. It is found that hydrogen exists as hydrogen pairs trapped at oxygen vacancies and forms Zn-H bonds. This is different from that in c-ZnO, where H acts as shallow donors. The O vacancy/2H complex defect has got defect states in the lower gap region, which is proposed to be the origin of the negative bias light induced stress instability.

T-91 and P-91 are the oldest of a new class of creep-strength-enhanced ferritic steels (CSEF) approved for use in boilers and pressure vessels. These newer alloys develop high strength through heat treatment, a rapid cooling or quenching to form martensite, followed by a temper to improve ductility. As a result, these alloys offer a much higher allowable stress which means thinner sections provide adequate strength for high-temperature service. Most of the applications thus far have been a substitute for P-22/T-22. The primary advantages of T91 materials over conventional low-alloy steels are: higher allowable stresses for a given temperature, improved oxidation, corrosion, creep and fatigue resistance. T23 is also considered as a member of the family of CSEF steels. The alloying elements such as tungsten, vanadium, boron, titanium and niobium and heat treatment separate this alloy from the well defined T22 steel. Although, T23 is designated for tubing application, its piping counterpart P23 has a strong potential in header applications due to superior strength compared to P22 headers. Now that T-91 and P-91 have been in service for nearly 30 years, some shortcomings have become apparent. A perusal of the allowable stress values for T-91 shows a drop off in tensile strength above about 1150°F. Thus, start-up conditions where superheaters, and especially reheaters, may experience metal temperatures above 1200°F, lead to over-tempering and loss of creep strength. During welding, the temperature varies from above the melting point of the steel to room temperature. The heat-affected zone (HAZ) is defined as the zone next to the fusion line at the edge of the weld metal that has been heated high enough to form austenite, i.e., above the lower critical transformation temperature. On cooling, the austenite transforms to martensite. Next to this region of microstructural transformation, there is an area heated to just below the austenite formation temperature, but above the tempering temperature of the tube/pipe when manufactured. This region has been, in effect, over-tempered by the welding and subsequent post-weld heat treatment (PWHT). Over-tempering softens the tempered martensite with the associated loss of both tensile and creep strength. This region of low strength is subject to failure during service. Creep strength of T91 steel is obtained via a quenching process followed by controlled tempering treatment. Elements such as niobium and vanadium in the steel precipitate at defect sites as carbides; this is known as the ‘pinning effect’. Any subsequent welding/cold working requires a precise PWHT. Inappropriate and/or lack of PWHT can destroy the ‘pinning effect’ resulting in loss of creep strength and premature failures. Several case studies will be presented with the problems associated with T91/T23 materials. Case studies will be presented, with the results of optical microscopy, scanning electron microscopy, hardness measurements and energy dispersive spectroscopy analysis. One case study will discuss how the over-tempering caused a reduced creep strength, resulting in premature creep failure in a finishing superheater tube. A second case presents the carburization of a heat recovery steam generator (HRSG) superheater tube, resulting in reduced corrosion/oxidation resistance. A case study demonstrates how a short-term overheating excursion led to reheat cracking in T23 tubing. Another case will present creep degradation in T91 reheater steel tube due to high temperature exposures (over-tempering).