Thermodynamics of the Na2SO4-K2SO4-CoSO4 system and their relevance to low-temperature hot corrosion

Thermodynamic calculations and experiments were performed to determine the SO₃ partial pressures and temperatures at which K₂SO₄-CoSO₄ binary mixed liquid phases form on CoO and Co₃O₄ in the presence of K₂SO₄. The calculations and experiments are in excellent agreement. Similar calculations were also made of the compositions at the liquidus surface and the associated SO₃ partial pressures for the K₂SO₄-Na₂SO₄-CoSO₄ ternary system. These calculations show that the presence of K₂SO₄ substantially reduces the SO₃ partial pressures required to stabilize a liquid salt phase on the surface of oxidized cobalt alloys at 600–800°C. Consequently, at these temperatures the hot corrosion in coal-fired systems, where K levels are high, is expected to be worse than in oil-fired systems, where K levels are low. This prediction was confirmed by experiments in a pressurized fluidized bed coal combustor and in an atmospheric pressure burner rig.     

The effect of K2SO4 additive in Na2SO4 deposits on low temperature hot corrosion of iron-aluminum alloys

To understand the effect of K₂SO₄ additive in an Na₂SO₄ deposit on low temperature hot corrosion, the corrosion behavior of Fe-Al alloys induced by Na₂SO₄+K₂SO₄ was compared to that by Na₂SO₄ alone, and sulfation of Fe₂O₃ in the presence of either Na₂SO₄ or Na₂SO₄+K₂SO₄ was studied. It was found that K₂SO₄ additive promoted the low temperature hot corrosion, but did not change the corrosion-mechanism. Experimental results refuted the prior suggestions that the accelerated hot corrosion resulted either from the formation of K₃Fe(SO₄)₃ or from the stimulation of sulfation of Fe₃O₃. The earlier formation of the eutectic melt caused the accelerated hot corrosion, or in other words, the K₂SO₄ additive shortened the induction stage of hot corrosion.     

Microstructure and desorption properties study of catalyzed NaAlH4

NaAlH₄ catalyzed by Ce(SO₄)₂ and LaCl₃ have been studied by PCT (Pressure-Content-Temperature) experiment and SEM (Scanning Electron Microscope) test method. The results show that doping with Ce(SO₄)₂ and LaCl₃ increases markedly the desorption amount of NaAlH₄. In the first desorption stage, NaAlH₄ doped with LaCl₃ display larger amount of hydrogen release than NaAlH₄ doped with Ce(SO₄)₂, while, the desorption rate of the latter is obviously faster than the former. SEM analysis shows that heating could make NaAlH₄ form a kind of porous structure. The further study indicates that different dopants have different effects on the microstructure of NaAlH₄.     

The identification of the sulfide NaCrS2 in nickel-base superalloys during corrosion in sulfate melts

The sulfide NaCrS₂ has been identified in the internal corrosion zone of several nickel-base superalloys under basic fluxing conditions at very negative potentials in a 90% Na₂SO₄-10% K₂SO₄ melt at 1173 K. It can also be formed in the presence of carbon-contaminated sulfate. NaCrS₂ can dissolve some Ti, Al, Ni, and Co; other elements, e.g., K, Mo, W, Nb, Ta, and Zr, could not be detected.     

Effect of Na2SO4 and Water Vapor on the Corrosion of Ti3SiC2

The corrosion behavior of polycrystalline Ti₃SiC₂ was studied in the presence of Na₂SO₄ deposit and water vapor at 900°C and 1000°C. The mass gain per unit area of the samples superficially coated with Na₂SO₄ exposed to water vapor was slightly lower than that of the samples corroded without water vapor. The microstructure and composition of the scales were investigated by SEM/EDS and XRD. Pores were observed in the corroded sample surfaces. The main corrosion phases on the sample surface were identified by XRD as TiO₂, Na₂Si₂O₅ and Na₂TiO₃. After Ti₃SiC₂ corroded in the presence of the Na₂SO₄ deposit and water vapor, the scale had a three-layer microstructure, which was different from the duplex corrosion scale formed on Ti₃SiC₂ beneath the Na₂SO₄ film without water vapor. Because water vapor penetrated the corrosion layer and then reacted with SiO₂ to form volatile Si(OH)₄, an intermediate porous and TiO₂-enriched layer formed in the corrosion layer.     

Na2SO4- and NaCl-Induced hot corrosion of six nickel-base superalloys

The short-time hot-corrosion behavior of six industrial nickel-base superalloys was investigated with static deposits of Na₂SO₄ or NaCl or both in still air. The oxidation kinetics and scale morphologies were measured with traditional laboratory techniques-thermobalance, metallography, electron microprobe, and x-ray analyses. Susceptibility to hot corrosion was found to be correlated to the type of scale produced during simple oxidation. Alloys forming an A1₂O₃ scale were found to be susceptible to Na₂SO₄ deposits, independent of their chromium content. The quantity of Na₂SO₄ deposit dictated the nature of the attack and, under certain conditions, the refractory element alloy additions appeared to play an essential role. Alloys containing Cr₂O₃ or TiO₂ in the simple oxidation scale proved to be sensitive to NaCl attack. Again, the severity of the attack within the susceptible alloy group was not related to the chromium or titanium content. Although less intensive than the Na₂SO₄ -induced hot corrosion, NaCl contaminations provoked extensive spalling. All of the hotcorrosion types encountered in this study were interpreted in the light of existing theories.Supported by the Délégation Générale à la Recherche Scientifique et Technique.     

Ce(SO4)2浓度对电喷镀Ni-W-Ce合金镀层性能影响

为了研究Ce(SO4)2浓度与合金镀层表面性能的关系,采用喷射电沉积法制备了一系列Ni-W-Ce合金镀层工件。用扫描电镜(SEM)观察了镀层的表面结构,并用能谱仪(EDS)检测镀层中的元素组成。XRD分析表明,镀层存在晶格畸变。LEXT4100激光共焦显微镜观察磨损痕迹,发现磨损机理发生了变化。结果表明,添加Ce(SO4)2改善了涂层的表面微观形貌,当浓度为0.5g/L时,涂层的表面质量最佳。同时,显微硬度、耐磨性和耐腐蚀性随浓度的增加呈现先好后坏的规律。当Ce(SO4)2浓度为0.5g/L时,显微硬度达到峰值519.69HV0.1。此时,镀层耐磨性最好,其耐磨性表征参数均取得最小值。且镀层的耐蚀性也最好,腐蚀电位为-0.5537V,电弧电抗半径最小。     

Long term corrosion of X70 steel and iron in humid supercritical CO2 with SO2 and O2 impurities

Abstract

The corrosion of X70 steel and iron in supercritical CO₂/SO₂/O₂/H₂O environment were investigated after a 454 h exposure. Optical microscopy was applied to observe the morphology of etch pits and synthesise the three-dimensional morphology. X-ray diffraction and X-ray photoelectron spectroscopy were employed to detect the composition of product scales. Experimental results verified that the localised corrosion occurred on the X70 steel sample under corrosion product deposits. Ferrous sulphate, sulphur and iron sulphide were detected as the corrosion products.     

Corrosion behavior of select MAX phases in NaOH, HCl and H2SO4

In this paper we report on the electrochemical corrosion of select MAX phases, namely Ti₂AlC, (Ti,Nb)₂AlC, V₂AlC, V₂GeC, Cr₂AlC, Ti₂AlN, Ti₄AlN₃, Ti₃SiC₂ and Ti₃GeC₂ in 1 M NaOH, 1 M HCl and 1 M H₂SO₄ solutions. Polarization characteristics recorded in 1 M NaOH show that V₂AlC, V₂GeC and Cr₂AlC undergo active dissolution at potentials more positive than the corrosion potential, while Ti₂AlC, (Ti,Nb)₂AlC, Ti₃SiC₂ and Ti₃GeC₂ passivate. In the 1 M HCl solutions, Ti₂AlC, V₂AlC and V₂GeC actively dissolve; Ti₃SiC₂ and Ti₃GeC₂ passivate. Depending on potential, (Ti,Nb)₂AlC and Cr₂AlC showed trans-passive behavior. In 1 M H₂SO₄ solutions, Ti₂AlC, (Ti,Nb)₂AlC, Ti₃SiC₂ and Ti₃GeC₂ passivate, V₂AlC and V₂GeC show active dissolution, while Cr₂AlC exhibits trans-passive behavior. Ti₂AlN and Ti₄AlN₃ were passive in all solutions except in 1 M HCl, where Ti₂AlN showed trans-passive behavior. Given that the corrosion behavior of (Ti,Nb)₂AlC is unlike either Ti or Nb, the behavior of the former cannot be predicted from that of the latter.     

Ni/Cu定向结构涂层在不同浓度H2SO4中的耐蚀性能

为了研究Cu元素对Ni基合金定向结构涂层耐腐蚀性能的影响,向Ni60合金粉末中添加了5%Cu(质量分数,下同),制备了定向结构Ni60/Cu复合涂层。采用电化学试验和浸泡试验,评估了涂层在不同浓度H₂SO₄溶液中的电化学腐蚀特性和浸泡腐蚀性能,探讨了涂层在不同浓度H₂SO₄溶液中的腐蚀行为。结果表明,涂层在不同浓度H₂SO₄溶液中的腐蚀均表现为活化-钝化-过钝化的过程,电化学阻抗谱在整个时间常数内具有典型的容抗特征,H₂SO₄溶液浓度从5%增至80%时,电荷转移电阻先减小后增大,涂层的耐腐蚀性呈现先降低后升高的趋势。随着H₂SO₄溶液浓度的增加,涂层表面的腐蚀程度先加剧后逐渐减缓,且在H₂SO₄溶液浓度为40%时,腐蚀电位移至最负,腐蚀电流密度增至最大。但在H₂SO₄溶液浓度达到80...     

Synthesis and thermal conductivities of ZnIn2Te4 and CdIn2Te4 with defect-chalcopyrite structure

ZnIn₂Te₄ and CdIn₂Te₄ have a defect-chalcopyrite tetragonal crystal structure with structural vacancies. In order to investigate the effects of vacancies on the lattice thermal conductivity (κ_lat), single phase samples of ZnIn₂Te₄ and CdIn₂Te₄ were synthesized and their κ_lat values were examined in the temperature range from room temperature to 850 K. The κ_lat data for ZnIn₂Te₄ and CdIn₂Te₄ were compared with those of Zn- and Cd-series chalcopyrite compounds with no vacancies. The results revealed that the presence of vacancies alone in the defect-chalcopyrite structure does not result in effective phonon scattering.     

氨基功能化CoFe2O4-SiO2 磁性复合材料的制备及其在去除水中重金属离子的吸附性能

钴-铁氧体纳米粒子(CoFe₂O₄ NPs)通过改良的共沉淀法制备,CoFe₂O₄-SiO₂磁性复合材料通过st?ber法合成,为了吸附重金属离子CoFe₂O₄-SiO₂进行了氨基功能化。这种吸附剂的晶体结构、形貌、颗粒尺寸、化学组成和分子结构采用X射线衍射图谱(XRD)、扫描电子显微镜(SEM)以及傅里叶变换红外光谱(FTIR)进行表征。此复合材料具有优良的磁性能,由于其高的饱和磁化强度,磁铁可以将其在30秒内快速分离。同时,CoFe₂O₄ NPs的磁性能可以通过烧结温度进行调节,随烧结温度提高,磁性能增强。溶液的pH及反应时间对重金属离子吸附的影响进行了研究,此外此吸附剂对Cu (II)、Cd (II)、Mn (II) 和Zn (II)具有较高的吸附容量和去除率,这一结果使此复合材料可以潜在应用于废水中重金属离子的吸附上。     

On the reaction mechanism of nickel with SO2+O2/SO3

High-purity nickel has been reacted with 96% O₂+4% SO₂ at 700–900°C. The reaction has been studied at 700°C as a function of the total gas pressure (0.06–1 atm) and at 1 atm as a function of temperature (700–900°C). The reaction mechanism changes with the effective pressure of p(SO₃) in the gas. When NiSO₄ (NiO + SO₃ = NiSO₄) is formed on the scale surface, the scale consists of a two-phase mixture of NiO + Ni₃S₂; in addition, sulfur is enriched at the metal/scale interface. A main process in the reaction is rapid outward diffusion of nickel through the Ni₃S₂ phase in the scale; the nickel reacts with NiSO₄ to yield NiO, Ni₃S₂, and possibly NiS as an intermediate product. When NiSO₄ cannot be formed, the scale consists of NiO, and small amounts of sulfur accumulate at the metal/scale interface. It is proposed that the reaction under these conditions is primarily governed by outward grain boundary diffusion of nickel through the NiO scale, and in addition, small amounts of SO₂ migrate inward through the scale—probably along microchannels.     

Corrosion behaviour of mild steel in chloride solutions with Na2HPO4 additive and the development of antifreeze

ABSTRACT

Chloride salts can prevent roads from freezing in cold regions, together with severe corrosion on steel constructions. To develop an ecological and low-corrosive antifreeze, di-sodium hydrogenphosphate (Na₂HPO₄) was chosen as the additive into chloride salts. The addition of Na₂HPO₄ into either of the antifreezes of natural salt (N/S), NaCl, CaCl₂ or MgCl₂ can suppress the corrosion reaction of mild steel in the 3.0% antifreeze solution. Moreover, the addition of CaCl₂ or MgCl₂ into the antifreeze containing NaCl and 2.0% Na₂HPO₄ significantly decreased the corrosion rate. According to polarisation and XPS analyses, it is evident that the obtained low corrosion rates on mild steel are related to the suppressed cathodic and anodic reactions and the formation of a protective film containing Fe, P, O, Ca or Mg.

This paper is part of a supplementary issue from the 17th Asia-Pacific Corrosion Control Conference (APCCC-17).     

Accelerated oxidation of iron induced by Na2SO4 deposits in oxygen at 750°C—A new type low-temperature hot corrosion

Na ₂ SO ₄ -induced accelerated corrosion of iron in oxygen at 750°C was observed. EDX, XRD, SEM, EPMA and some chemical examinations were carried out to understand the corrosion mechanism. The accelerated oxidation was attributed to the formation of abundant sulfide which has a highly defected lattice and allows rapid diffusion of iron ions. The sulfide resulted in turn from the formation of a liquid phase which was a eutectic melt of Na ₂ SO ₄ and Na ₂ O. The formation of and other possible effects of the melt were discussed. The accelerated oxidation was compared with the usual low-temperature hot corrosion, showing that it has most of the characteristics of low-temperature hot corrosion except that it occurred under basic conditions developed by the removal of sulfur from the sulfate deposits instead of the usual acidic conditions established by the SO ₃ in the atmosphere.     

Evaluation of cyclic hot corrosion behaviour of detonation gun sprayed Cr3C2-25%NiCr coatings on nickel- and iron-based superalloys

In the present investigation, Cr₃C₂-NiCr cermet coatings were deposited on two Ni-based superalloys, namely superni 75, superni 718 and one Fe-based superalloy superfer 800H by detonation-gun thermal spray process. The cyclic hot-corrosion studies were conducted on uncoated as well as D-gun coated superalloys in the presence of mixture of 75 wt.% Na₂SO₄ + 25 wt.% K₂SO₄ film at 900 °C for 100 cycles. Thermogravimetric technique was used to establish the kinetics of hot corrosion of uncoated and coated superalloys. X-ray diffraction, FE-SEM/EDAX and X-ray mapping techniques were used to analyze the corrosion products for rendering an insight into the corrosion mechanisms. It was observed that Cr₃C₂-NiCr-coated superalloys showed better hot-corrosion resistance than the uncoated superalloys in the presence of 75 wt.% Na₂SO₄ + 25 wt.% K₂SO₄ film as a result of the formation of continuous and protective oxides of chromium, nickel and their spinel, as evident from the XRD analysis.     

Effects of K2O-Li2O doping on surface and catalytic properties of Fe2O3/Cr2O3 system

The effects of K₂O and Li₂O-doping (0.5, 0.75 and 1.5 mol%) of Fe₂O₃/Cr₂O₃ system on its surface and the catalytic properties were investigated. Pure and differently doped solids were calcined in air at 400-600 °C. The formula of the un-doped calcined solid was 0.85Fe₂O₃:0.15Cr₂O₃. The techniques employed were TGA, DTA, XRD, N₂ adsorption at −196 °C and catalytic oxidation of CO oxidation by O₂ at 200-300 °C. The results revealed that DTA curves of pure mixed solids consisted of one endothermic peak and two exothermic peaks. Pure and doped mixed solids calcined at 400 °C are amorphous in nature and turned to α-Fe₂O₃ upon heating at 500 and 600 °C. K₂O and Li₂O doping conducted at 500 or 600 °C modified the degree of crystallinity and crystallite size of all phases present which consisted of a mixture of nanocrystalline α- and γ-Fe₂O₃ together with K₂FeO₄ and LiFe₅O₈ phases. However, the heavily Li₂O-doped sample consisted only of LiFe₅O₈ phase. The specific surface area of the system investigated decreased to an extent proportional to the amount of K₂O and Li₂O added. On the other hand, the catalytic activity was found to increase by increasing the amount of K₂O and Li₂O added. The maximum increase in the catalytic activity, expressed as the reaction rate constant (k) measured at 200 °C, attained 30.8% and 26.5% for K₂O and Li₂O doping, respectively. The doping process did not modify the activation energy of the catalyzed reaction but rather increased the concentration of the active sites without changing their energetic nature.     

The Hot Corrosion of Fe-Mn-Al–C Alloy with NaCl/Na2SO4 Coating Mixtures at 750°C

The high-temperature corrosion behavior of Fe-30.1Mn-9.7Al-0.77C alloy initially coated with 2 mg/cm² NaCl/Na₂SO₄ (100/0, 75/25, 50/50, 25/75 and 0/100 wt.%) deposits has been studied at 750°C in air. The result shows that weight-gain kinetics in simple oxidation reveals a steady-state parabolic rate law after 3 hr, while the kinetics with salt deposits all display multi-stage growth rates. The corrosion morphology of the alloy with 100% Na₂SO₄ coating is similar to that of simple oxidation. NaCl acts as the predominant corrosion species for Fe-Mn-Al-C alloy, inhibiting the formation of a protective oxide scale. For the alloy coated with over 50% NaCl in salts, NaCl induces selective oxidation of manganese and results in the formation of secondary ferrite in the alloy substrate as well as void-layers with different densities of voids layer by layer in the secondary-ferrite zone.     

废旧锂离子电池中Li, Fe和V的回收及xLiFePO4-yLi3V2(PO4)3的制备

由于LiFePO_4和Li_3V_2(PO_4)_3材料的特征相近,制备方法类似,提供了一种从废旧LiFePO_4和Li_3V_2(PO_4)_3混合电池中回收Li、Fe和V,再制备xLiFePO_4-yLi_3V_2(PO_4)_3的方法。在空气气氛中600℃热处理1h后,去除粘结剂PVDF使活性物质与集流体分离。调节Li、Fe、V和P摩尔比,球磨、锻烧,配制不同比例的xLiFePO_4-yLi_3V_2(PO_4)_3(x:y=5:1,7:1,9:1)复合电极材料。表征了其形貌、结构和电化学性能,结果表明,回收制备的复合材料将同时具备LiFePO_4和Li_3V_2(PO_4)_3两种材料的电化学性能,能显著改善LiFePO_4的倍率性能。     

The first-class reciprocal quaternary system H3PO4-K2SO4-K3PO4-H2SO4-H2O application to fertilizer fabrication problems

The first-class reciprocal quaternary system H₃PO₄-K₂SO₄-K_3PO₄-H₂SO₄-H₂O has been carefully investigated at 25 and 75°C. Representations have been given using the Jänecke coordinates. Using the established diagrams as a base, a procedure is proposed for preparing specific fertilizers containing potassium and phosphate ions by reacting phosphate rock with aqueous solutions of KHSO₄, addition of calculated amounts of water to the reaction mixture, elimination of an insoluble products, and programmed water evaporation.