Preliminary Results of the Studies on Fractionation of Ytterbium Isotopes in Yb(III)-Acetate/Yb-Amalgam System

ABSTRACT

Preliminary data on the fractionation of ytterbium isotopes in a Yb(III)-acetate/Yb-amalgam exchange system were obtained. The light isotope was preferentially fractionated to the amalgam phase. The values of the unit separation gain per mass difference, ?, were found to be ?00054 for ^176/71Yb and ?00069 for ^176/174Yb. The difference, which amounted to 00015, may be taken as evidence for the occurrence of the so-called “even-odd” effect. It was also found that the chemical isotope shift of ytterbium was mirrored by the optical isotope shift in its atomic spectra.     

The CMAS corrosion behavior of high-entropy (Y0.2Dy0.2Er0.2Tm0.2Yb0.2)4Hf3O12 hafnate material prepared by ultrafast high-temperature sintering (UHS)

High-temperature molten calcium-magnesium-alumina-silicate (CMAS) corrosion has become a fatal factor for the failure of aero-engine thermal barrier coatings. In this study, a promising entropy-stabilized (Y_0.2Dy_0.2Er_0.2Tm_0.2Yb_0.2)₄Hf₃O₁₂ (5YH) hafnate was prepared by the emerging ultrafast high-temperature sintering (UHS), and its corrosion and wetting behavior of molten CMAS were investigated. For the corrosion mechanism, the precipitation of the high-entropy apatite phase promotes the formation of the HfO₂ phase, and it can improve the density and stability of the slow-growing reaction layer, hindering the further penetration of molten CMAS. At 1300 ℃, a reaction layer with a three-layered morphology is generated, resulting from the decreased viscosity of the molten CMAS. Moreover, computational analysis shows that molten CMAS on the 5YH surface has a larger contact angle (17°) than traditional YSZ (13°), and the spreading area is about 90 % of traditional YSZ, which benefits for its good CMAS corrosion resistance.     

主焦煤配入比例对焦炭热反应性的影响

在40kg焦炉上进行了多方案的配煤炼焦试验,并对单种煤及配合煤炼焦的焦炭热反应性进行了分析,结果表明,单种焦煤炼焦时25JM的反应后强度最好;配合煤中控制主焦煤的配入比例,适当配入14SM、1／2ZN或26FM后,焦炭的热反应性比单种焦煤炼焦的效果好。     

钙硅比对水热合成水化硅酸钙实验的影响研究

针对钙硅比对水化硅酸钙产品成分与结构影响较大的现象,为了分析这种影响规律,实验过程中按照不同钙硅比配入原料,采用水热合成法制备水化硅酸钙,实验最终得到了钙硅比对产物水化硅酸钙物相微观结构以及聚合度的影响规律.对实验产物进行XRD分析发现,随着钙硅比的升高,分析结果中出现了Tobermorite(托勃莫来石)以及硬钙硅石的相.通过对产物SEM分析发现,随着钙硅比的升高,产物颗粒表面微观结构变得疏松.通过红外分析发现,产物聚合度随着钙硅比的升高而降低.     

Development of a Self-Forming Ytterbium Silicate Skin on Silicon Nitride by Controlled Oxidation

A dense and uniform polycrystalline ytterbium silicate skin on silicon nitride ceramics was developed by a controlled oxidation process to improve the hot corrosion resistance of silicon nitride. The process consists of purposely oxidizing the silicon nitride by heating it at high temperatures. It was found that the ytterbium silicate phase was formed as an oxidation product on the surface of the silicon nitride when it was exposed to air at temperatures above 1250°C. The volume fraction of ytterbium silicate compared with that of SiO₂ on the silicon nitride surface increased with increasing oxidation time and temperature. The formation and growth of ytterbium silicate on the surface of silicon nitride is attributed to a nucleation and growth mechanism. Ultimately, a dense and uniform ytterbium silicate skin with 3–4 μm of skin thickness was obtained by oxidation at 1450°C for 24 h. The ytterbium silicate layer, formed by oxidation of the silicon nitride, is associated with the reaction of SiO₂ on the surface of silicon nitride with Yb₂O₃ introduced in the silicon nitride as a sintering additive. Preliminary tests showed that the ytterbium silicate skin appears to protect silicon nitride from hot corrosion. No observable evidence of a reaction between the skin and molten Na₂SO₄ was found when it was exposed to molten Na₂SO₄ at 1000°C for 30 min.     

Enhancing CMAS corrosion resistance of PS-PVD Si/Yb2Si2O7 EBCs via Al-modification

Enhancing the resistance to molten silicate corrosion is crucial for the long service life of environmental barrier coatings (EBCs). In this study, we used the Al-modification technique to enhance the CMAS corrosion resistance of Si/Yb₂Si₂O₇ coatings prepared by plasma spray-physical vapor deposition. The results show that the Al-modified Yb₂Si₂O₇ coating had higher resistance to CMAS corrosion than the Yb₂Si₂O₇ coating annealed at 1300 ℃ for 100 h, which is related to the refractory mullite and Yb₂Mg(AlO₂)₂O₃ generated during the CMAS exposure of Al-modified Yb₂Si₂O₇ coating. The Al-modified Yb₂Si₂O₇ coating also exhibited excellent resistance to oxygen penetration. The Al-modification technology provides the direction for the corrosion resistance of Yb₂Si₂O₇ system to CMAS.     

Lead Hafnate (PbHfO3) Perovskite Powders Synthesized by the Oxidant Peroxo Method

Perovskite lead hafnate (PbHfO₃, PH) nanoparticles that were free from halides and organics were synthesized via the oxidant peroxo method. Stoichiometric amounts of hafnium nitrate (HfO(NO₃)₂) and lead nitrate (PbHfO₃) were dissolved in a diluted hydrogen peroxide (H₂O₂) aqueous solution, which was slowly added to a solution of H₂O₂ and ammonia (NH₃) (pH 11). The lead–hafnium precipitate obtained was filtered and washed, to eliminate all nitrate ions. The precipitate was dried, ground, and calcined at temperatures of 400°–900°C. A tetragonal intermediate phase was identified using X-ray diffractometry and Raman spectroscopy during the calcination process, followed by the crystallization of the orthorhombic PH phase at ∼700°C.     

Calcium-magnesium-alumina-silicate (CMAS) resistant Ba2REAlO5 (RE = Yb,Er, Dy) ceramics for thermal barrier coatings

Calcium-magnesium-alumina-silicate (CMAS) attack has been a great challenge for the application of thermal barrier coatings (TBCs) in modern turbine engines. In this study, a series of prospective TBC candidate materials, Ba₂REAlO₅ (RE = Yb, Er, Dy), are found to have high resistance to CMAS attack. The rapid formation of a continuous crystalline layer on sample surface contributes to this desirable attribute. At 1250 °C, Ba₂REAlO₅ dissolve in the molten CMAS, accumulating Ba, RE and Al in the melt, which could trigger the crystallization of celsian, apatite and wollastonite crystals. Especially, the formation of the crystalline layer in the Ba₂DyAlO₅ sample is the fastest. This study also reveals that Ba is a useful element for altering CMAS composition to precipitate celsian. Thus, doping Ba²⁺ in yttria partially stabilized zirconia or other novel TBCs might be an attractive way of mitigating CMAS attack.     

玻璃分相结构形态与MgO/CaO摩尔比的相互关系

本文研究MgO/CaO比值不同的两种玻璃的分相结构。结果发现高MgO/CaO比的玻璃在热处理的过程中分相液滴由连通结构逐渐长大而转变为孤立的液滴结构。而低MgO/CaO比的玻璃在热处理的过程中分相液滴则由小尺度的连通结构长大为大尺度的连通结构。     

Thermochemical Interaction of Thermal Barrier Coatings with Molten CaO–MgO–Al2O3–SiO2 (CMAS) Deposits

Thermal barrier coatings (TBCs) are increasingly susceptible to degradation by molten calcium–magnesium alumino silicate (CMAS) deposits in advanced engines that operate at higher temperatures and in environments laden with siliceous debris. This paper investigates the thermochemical aspects of the degradation phenomena using a model CMAS composition and ZrO₂–7.6%YO_1.5 (7YSZ) grown by vapor deposition on alumina substrates. The changes in microstructure and chemistry are characterized after isothermal treatments of 4 h at 1200°–1400°C. It is found that CMAS rapidly penetrates the open structure of the coating as soon as melting occurs, whereupon the original 7YSZ dissolves in the CMAS and reprecipitates with a different morphology and composition that depends on the local melt chemistry. The attack is minimal in the bulk of the coating but severe near the surface and the interface with the substrate, which is also partially dissolved by the melt. The phase evolution is discussed in terms of available thermodynamic information.     

MgO活性对新型水化硅酸镁水泥性能的影响

通过对原料轻烧氧化镁粉在不同温度下进行二次恒温煅烧1.5 h制备不同活性MgO,研究了不同活性MgO与硅灰(SF)和磷酸氢二钾(K₂HPO₄)所制备的新型水化硅酸镁水泥胶凝材料(又称水化磷硅酸镁水泥,MSPHC)的凝结时间、流动度、抗压强度、反应溶液pH值。结合X射线衍射(XRD)、热重分析(TG-DTG)和扫描电子显微镜(SEM)测试手段,分析其影响机理。结果表明:随着煅烧温度的升高,MgO衍射峰强度增大,MgO活性降低;活性越高的MgO制备的MSPHC净浆凝结时间越短且流动性越差,而活性适中MgO制备的MSPHC具有较好的力学性能。MSPHC最主要的水化产物是水化硅酸镁(M-S-H)凝胶,另外还有Mg(OH)₂和MgKPO₄·6H₂O(MKP)生成,原料轻烧氧化镁粉中的MgCO₃成分不参与体系反应。活性适中的MgO制备的MSPHC在28 d龄期内的水化产物M-S-H凝胶生成量最多,因此硬化体抗压强度最高。活性越高的MgO在MSPHC反应体系中溶解的速度越快,体系水化反应进程速度也越快。     

Excellent CMAS resistance of a newly developed equiatomic high entropy (Dy1/4Ho1/4Tm1/4Yb1/4)2Si2O7 ceramic pyrosilicate

In this work, novel equiatomic high entropy (Dy_1/4Ho_1/4Tm_1/4Yb_1/4)₂Si₂O₇ or (4RE_1/4)₂Si₂O₇ ceramic pyrosilicate was fabricated through a single solid solution method to use as environmental barrier coating. The SEM analysis of high entropy powders shows the homogenous mixing and XRD proves the formation of single β-phase after milling and sintering. The coefficient of thermal expansion was reported as (2.3–4.8 × 10⁻⁶ K⁻¹) from 400 K⁻¹ to 1723 K⁻¹. The ultra-low thermal diffusivity (0.4 mm² s⁻¹) and thermal conductivity (0.8 W/m°C) were reported at 1500 °C for this novel HE ceramic disilicate. The as fabricated (4RE_1/4)₂Si₂O₇ pyrosilicate shows an excellent CMAS resistant for even up to 48 h and negligible amount of Ca is able to penetrate in the substrate. Rare earth disilicate species with intermediate radii such as Tm³⁺ helps in maintaining phase stability along with passive element Yb³⁺ of smaller radii which also protect the interface from severe CMAS attack. However, the rare earth species with larger radii such as Dy³⁺ and Ho³⁺ actively take part in apatite formation leading to reduced corrosion activity of CMAS melt by changing its composition. This result confirms the application of (4RE_1/4)₂Si₂O₇ as a potential candidate to be used as protecting coating material in harsh combustion environments.     

Epitaxial Growth of Nickel(II) Hydroxide on layer Silicate and Derived Nickel-(Layer Silicate) Nanocomposite

Nickel(II) hydroxide crystals were deposited on a substrate of layer silicates from the liquid phase by decomposing nickel(II) ammine complex solutions dispersed with expandable layer silicates; the (001) planes of the nickel(II) hydroxide aligned parallel to the basal (001) plane of the layer silicates. From these layer silicate complexes with nickel(II) hydroxide, nickel-coated layer silicate composite particulates were derived. Moreover, metal–ceramics alloys, composed of nickel containing uniformly dispersed layer silicates several tens of angstroms in thickness, were produced by sintering the metal-coated ceramic powders.     

Calcium-Magnesium-Aluminosilicate (CMAS) corrosion resistance of high entropy rare-earth phosphate (Lu0.2Yb0.2Er0.2Y0.2Gd0.2)PO4: A novel environmental barrier coating candidate

Single phase (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄ was synthesized, and its thermal properties and CMAS resistance were investigated to explore its potential as an environmental barrier coating (EBC) candidate. The high entropy phosphate (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄ displays a lower thermal conductivity (2.86 W m⁻¹ K⁻¹ at 1250 K) than all the single component xenotime phase rare-earth phosphates. Interaction of (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄ pellets with CMAS at 1300 °C led to the formation of a dense and uniformed Ca₈MgRE(PO₄)₇ reaction layer, which halted the CMAS penetration into the bulk pellet. At 1400 and 1500 °C the (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄-CMAS corrosion showed CMAS penetrating beyond the reaction layer into the bulk pellet via the grain boundaries, and SiO₂ precipitates remaining at the pellet surface. The effects of duration, temperature, and compositions on the resistance against CMAS corrosion are discussed within the context of optimizing materials design and performance of high entropy rare-earth phosphates as candidates for advanced EBC applications.     

Thermo-mechanical properties and CMAS resistance of (Ho0.4Yb0.3Lu0.3)2SiO5 solid solution for environmental barrier coating applications

Rare earth monosilicate (RE₂SiO₅) is one of the most promising candidates as an environmental barrier coating (EBC) for SiC_f/SiC ceramic matrix composites. But single-component RE₂SiO₅ is hard to meet the multiple and harsh performance requirements of EBC which brings a significant challenge to their applications. Based on our previous research on single-component RE₂SiO₅ ceramics, (Ho_0.4Yb_0.3Lu_0.3)₂SiO₅ solid solution was designed and successfully fabricated in this work. Doping of multiple RE elements endows (Ho_0.4Yb_0.3Lu_0.3)₂SiO₅ with excellent thermal insulation properties and matched thermal expansion coefficient with SiC_f/SiC substrates. In addition, it exhibits lower elastic modulus and comparable hardness than that of single-component RE₂SiO₅. (Ho_0.4Yb_0.3Lu_0.3)₂SiO₅ also presents good resistance to calcium-magnesium alumino-silicates (CMAS) corrosion. Rational composition design allows (Ho_0.4Yb_0.3Lu_0.3)₂SiO₅ to retain the merits of single-component RE₂SiO₅ while taking advantage of the solid solution effect. The results of this work suggest (Ho_0.4Yb_0.3Lu_0.3)₂SiO₅ as a promising EBC candidate.     

Effects of Yb and Sc co-doping on the thermal properties and CMAS corrosion of garnet-type (Y3-xYbx)(Al5-xScx)O12 ceramics

Thermal barrier coatings with excellent thermal performance and corrosion resistance are essential for improving the performance of aero-engines. In this paper, (Y_3-xYb_x)(Al_5-xSc_x)O₁₂ (x = 0, 0.1, 0.2, 0.3) thermal barrier coating materials were synthesized by a combination of sol-gel method and ball milling refinement method. The thermal properties of the (Y_3-xYb_x)(Al_5-xSc_x)O₁₂ ceramics were significantly improved by increasing Yb and Sc doping content. Among designed ceramics, (Y_2.8Yb_0.2)(Al_4.8Sc_0.2)O₁₂ (YS-YAG) showed the lowest thermal conductivity (1.58 Wm^?1K^?1, at 800 °C) and the highest thermal expansion coefficient (10.7 × 10^?6 K^?1, at 1000 °C). In addition, calcium-magnesium- aluminum -silicate (CMAS) corrosion resistance of YS-YAG was further investigated. It was observed that YS-YAG ceramic effectively prevented CMAS corrosion due to its chemical inertness to CMAS as well as its unique and complex structure. Due to the excellent thermal properties and CMAS corrosion resistance, YS-YAG is considered to be prospective material for thermal barrier coatings.     

纤维素/聚乙二醇共混物中组分比例的变化对共混物Tg的影响规律及模型

应用DSC方法和经典的高分子共混物经验方程估算了纤维素/聚乙二醇共混物的玻璃化转变温度(Tg),并研究了Tg与两组分比例之间的关系。结果显示:该共混物的Tg随纤维素比例增加而降低,且明显低于两个独立组分的Tg,其规律为:Tg=A-B×Ln(WCell/WPEG)。与文献介绍的一些经典的高分子共混物Tg估算公式,如:Fox方程、Gordon-Taylor方程和Kwei方程相比较发现,其中惟有Fox方程似乎比较接近DSC实验导出的模型。     

Coarsening Behavior of Tricalcium Silicate (C3S) and Dicalcium Silicate (C2S) Grains Dispersed in a Clinker Melt

Microstructural evolution during the heat treatment of cement clinker was investigated. Two model specimens, which consisted of faceted tricalcium silicate (C₃S) and spherical dicalcium silicate (C₂S) grains dispersed in a liquid matrix, were prepared with 5 wt% of large seed particles. The seed particles of faceted C₃S grains grew extensively, whereas those of the spherical C₂S grains grew rather slowly, relative to the matrix grains. As a consequence, C₃S grains exhibited a bimodal size distribution that was typical of exaggerated grain growth, whereas C₂S grains retained a uniform and normal size distribution. These results suggest that the growth of faceted C₃S grains was controlled by the interface atomic attachment, such as two-dimensional nucleation, and that of spherical C₂S grains was controlled by diffusion through the liquid matrix. The dependence of growth mechanisms on grain morphology has been explained in terms of the atomistic structure of the solid/liquid interface.     

Al3+掺杂对硅酸三钙结构及水化活性的影响

利用X射线衍射仪、差示扫描量热-热重分析仪、红外光谱及微量热分析等,研究了Al3+掺杂对硅酸三钙C3S结构及活性的影响.结果表明:Al3+在C3S中固溶同时取代Ca和Si,并伴随少量Ca空位的形成保持电荷平衡.当Al2O3掺量高于0.5％(质量百分数,下同)时,Al取代Si比例增加.Al2O3掺量≤0.5％时仅使C3S晶胞参数改变,当掺量达1％时,可稳定T3晶型,符合离子稳定C3S多晶态规律.Al3+在C3S中固溶形成大量非本征缺陷,显著提高C3S早期水化反应活性.     

Reactivity of Ethyl Groups on a Sn/Pt(111) Surface Alloy

In order to probe the thermal stability and reactivity of ethyl intermediates on Pt-Sn alloy catalysts, we have synthesized these species by reaction of H atoms with adsorbed ethylene on a ( ) R30°-Sn/Pt(111) surface alloy. Adsorbed ethyl groups are stable until 376 are they react to evolve ethane, ethylene, and H₂. The activation energy for ethyl dehydrogenation is E_dehyd* 97 kJ mol, which is twice that reported on Pt(111). In addition, we place a lower limit of E_dehyd* 97 kJ mol on the barrier to ethyl hydrogenation on this alloy.