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 J?necke 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.     

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.     

Modulated Phases in the Ba2SiO4-Ca2SiO4 System of A2BX4, K2SO4-related Structures

Abstract

The A₂BX₄ family of K₂SO₄-related structures have long been of interest to crystal chemists, largely due to the numerous different polymorphs and complicated sequences of phase transitions they sometimes exhibit as a function of temperature. For most such A₂BX₄ compounds, there are essentially only two distinct structure types or parent structures — a high-temperature, ?hexagonal‘ form isomorphous to α-K₂SO₄ and a lower-temperature, orthorhombic form isomorphous to β-K₂SO₄. In addition to these two prototype structures, however, there often exist weakly distorted, or modulated, variants. In the case of the Ba_2-xCa_xSiO₄ system, five such modulated variants have been found via an electron diffraction study and characterized. The characteristic satellite extinction conditions associated with the weak satellite reflections have been used to determine displacement eigenvectors and atomic displacement patterns associated with each of the observed modulation wave-vectors. The widespread occurrence of modulated phases within the A₂BX₄ family of K₂SO₄-related structures suggests an almost chronic instability to displacive modulation.     

Effects of SO2 and SO3 on the Na2SO4 induced corrosion of nickel

The effects of SO₂ and SO₃ in the environment on the hot corrosion behavior of Ni in the temperature range 750–950°C has been studied. Below the melting point of Na₂SO₄ (884°C), rapid corrosion takes place by formation of a Na₂SO₄-NiSO₄ melt, which can penetrate the porous oxide scale and give rise to sulfide information by coming in contact with the metal. The distribution of the sulfides depends on the SO₂ level in the ambient gas. Continued corrosion occurs by a sulfidation-oxidation mechanism. At temperatures above the melting point of Na₂SO₄, accelerated degradation occurs via dissolution of the surface scale, followed by reprecipitation of the oxide in a nonprotective form.Deceased     

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.     

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.     

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.     

Initial atmospheric corrosion of zinc in presence of Na2SO4 and （NH4）2S04

Initial atmospheric corrosion of zinc in the presence of Na₂SO₄ and (NH₄)₂SO₄ was investigated via quartz crystal microbalance(QCM) in laboratory at relative humidity(RH) of 80% and 25 °C. The results show that both Na₂SO₄ and (NH₄)₂SO₄ can accelerate the initial atmospheric corrosion of zinc. The combined effect of Na₂SO₄ and (NH₄)₂SO₄ on the corrosion of zinc is greater than that caused by (NH₄)₂SO₄ and less than that caused by Na₂SO₄. Fourier transform infrared spectroscopy(FTIR), X-ray diffractometry(XRD) and scanning electron microscopy(SEM) were used to characterize the corrosion products of zinc. (NH₄)₂Zn(SO₄)₂, Zn₄SO₄(OH)₆·5H₂O and ZnO present on zinc surface in the presence of (NH₄)₂SO₄ while Zn₄SO₄(OH)₆·5H₂O and ZnO are the dominant corrosion products on Na₂SO₄-treated zinc surface. Probable mechanisms are presented to explain the experimental results.     

High temperature corrosion of Fe-Cr-Mn-alloys in H2-H2S and H2-H2O-H2S gas mixtures

The sulfidation of Fe-20% Cr-30% Mn, Fe-25%Cr-20%Mn and Fe-25% Cr was studied at 700°C in H₂-H₂S and the oxidation and sulfidation in H₂-H₂O-H₂S after preoxidation in H₂-H₂O. The sulfidation rate is strongly increased for the Mn-containing alloys, layers of (Mn,Cr)S and (Mn,Fe)Cr₂S₄ are formed. Also the oxidation rate is enhanced compared to Fe-25% Cr by formation of MnCr₂O₄ instead of Cr₂O₃. The sulfidation after preoxidation leads to internal and external sulfidation of the Mn-containing alloys. With increasing oxygen pressure p(O₂) = 10^?26…10^?22 atm. of the H₂-H₂O-H₂S mixtures the sulfidation is suppressed, for the higher oxygen pressure 10^?23 and 10^?22 atm. fast oxidation prevails under formation of MnCr₂O₄. Manganese cannot increase the sulfidation resistance of alloys, in spite of the stability and low degree of disorder of its sulfide, since the mixed sulfide (Mn,Cr)S is formed which has a high degree of disorder, high diffusivities and high growth rate according to the doping effect of trivalent Cr³⁺.     

Reactions of chromium in SO2-containing atmospheres

The morphology and composition of scales formed on unalloyed chromium in atmospheres containing SO₂ at high temperatures have been studied. SEM images show chromium sulfides formed at the metal/scale interface. The results indicate that SO₂ may penetrate the scale as molecules, but the rate of this penetration is low. At 600°C formation of Cr₂(SO₄)₃ is also observed by SEM on the scale surface formed in SO₂+O₂/SO₃ mixtures.     

Properties of non-aqueous solutions of Ni(CF3SO3)2

The crystals prepared in Ni(CF₃SO₃)₂-CH₃OH and Ni(CF₃SO₃)₂-C₂H₅OH solutions are the solvated compound with four molecules of the respective solvents. The crystals prepared in Ni(CF₃SO₃)₂-CH₃CN, Ni(CF₃SO₃)₂-HCONH₂ and Ni(CF₃SO₃)₂-HCON(CH₃)₂ solutions are the solvated compound with six molecules of the respective solvent.Solvolysis does not take place in Ni(CF₃SO₃)₂-HCONH₂ solution. The apparent molecular volume ø of Ni(CF₃SO₃)₂ in Ni(CF₃SO₃)₂-non-aqueous solution at 30°C is affected by both the solvent and the concentration of Ni(CF₃SO₃)₂ in the solution, and reaches a constant value at a specific concentration of Ni(CF₃SO₃)₂ in each solvent. The constant value of ø becomes lower with increasing maximum electrical conductivity of the solution.It seems that the constant value of ø in Ni(CF₃SO₃)₂-non-aqueous solution is less than 193 cm³ mol^-1.     

Corrosion behavior of T24, T92, VM12, and AISI 304 steels exposed to KCl–NaCl–K2SO4–Na2SO4 salt mixtures

The corrosion mechanisms of T24, T92, VM12, and AISI 304 steels are studied under the influence of NaCl–KCl, NaCl–Na₂SO₄, and KCl–K₂SO₄ salt mixtures in a dry air atmosphere at 650°C for 15 days. NaCl–KCl was the most aggressive deposit and AISI 304 stainless steel exhibited the highest corrosion resistance. There was no relation between the Cr content of the ferritic steels and their corrosion resistance in NaCl–KCl. In contrast, the resistance of high-Cr steels was better when exposed to NaCl–Na₂SO₄ and KCl–K₂SO₄. The high-Cr and the low-Cr steels were more susceptible to NaCl–Na₂SO₄ and to KCl–K₂SO₄, respectively.     

A facile pathway to prepare ultrafine WC powder via a carbothermic pre-reduction followed by carbonization with CH4-H2 mixed gases

In the present work, ultrafine tungsten carbide (WC) powder with a high purity has been prepared by first roasting yellow tungsten trioxide (WO₃) and carbon black powder under argon atmosphere followed by the further carbonization reaction with CH₄-H₂ mixed gases. The effects of C/WO₃ molar ratio, CH₄ percentage in the CH₄-H₂ mixed gases on the phase composition, morphology and particle size of the products were discussed. The results revealed that when the C/WO₃ molar ratios were 2.5 and 2.6, nano tungsten carbide powder with the average particle sizes of 93 nm and 77 nm could be prepared. Whereas, when the C/WO₃ molar ratio was in the range of 2.7–3.5, the finally prepared WC has the particle size of 446–192 nm, and became smaller with the increase of C/WO₃ molar ratio. The percentage of CH₄ should be <15% to prepare WC with a low free carbon content. From the results of thermodynamic calculation, X-ray diffraction (XRD), FE-SEM, and infrared carbon‑sulfur analyzer, it was concluded that ultrafine tungsten carbide powders with a high purity could be successfully prepared by this method.     

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.     

Corrosion of nickel with small alloy additions of Si,Fe, and Mn in SO2+O2/SO3 at 700°C

The corrosion of nickel with alloy additions of Si, Fe, and/or Mn up to 4 wt% has been studied in SO ₂+O₂/SO₃ at 700°C. All alloy additions greatly improve the corrosion resistance of nickel in oxygen-rich atmospheres (O₂ with about 4% SO₂); the best improvements are achieved with Si, Fe+Si, and Fe+Mn+Si additions. High-purity nickel corrodes rapidly under these conditions; the scale then consists of NiO+Ni₃S₂, and the sulfide forms a three-dimensional network along the grain boundaries of the NiO grains and serves as the diffusion path for rapid outward migration of nickel. From studies of the microstructure and distribution of the alloying elements in the protective scales, it is proposed that the alloying additions exert their beneficial effects by accumulating/segregating at the grain boundaries of NiO (e.g., as silicates) and thereby influence the wetting characteristics and disrupt the sulfide network.     

Acidic and basic fluxing of Ni-base superalloys in a 90Na2SO4-10K2SO4 melt at 1173 K

The influence of the electrode potential on the corrosion behavior of a series of Ni-base superalloys has been investigated in a (mole %) 90Na₂SO₄-10K₂SO₄ melt at 1173 K. Acidic fluxing occurs at positive potentials and basic fluxing at negative potentials. A protective scale is formed in an intermediate (neutral) potential range on high chromium-containing alloys such as IN-738LC, IN-939, IN-597, and IN-657. The breakthrough potentials for acidic and basic fluxing depend on the composition of the alloy. Alloys with low chromium contents such as IN-100 and IN-713LC do not form stable protective scales at any potential. Numerous sulfide phases have been identified in the scale and subscale, depending on potential, severity of attack, and material composition. NaCrS₂ only forms under basic fluxing conditions. Its presence can therefore be considered as an indication that basic fluxing conditions have existed.     

A study of the Ag(s)/Ag2SO4(l) high temperature reference electrode

Ag(s)/Ag₂SO₄(l) reference electrodes for use in hot corrosion research were fabricated and their properties were studied at 927°C (1200°K). The McDanel^TM MV 30 mullite tube was used as sheath of the reference electrode and concentrations of the tested electrolytes were varied from 0.1 to 10 m/o Ag₂SO₄ (l) + Na₂SO₄ (l). 10 m/o Ag₂SO₄ was always used as electrolyte in the reference electrode. The working electrodes with less than 2 m/o Ag₂SO₄ showed marked potential drift as the Ag₂SO₄ concentration was lowered, showing poor potential stability. However, the initial values of cell voltages obeyed Nernstian behavior for all range of Ag₂SO₄ concentrations in the working electrodes, which showed that Ag(s)/Ag₂SO₄(l) electrodes behaved reversibly. Galvanostatic polarization was performed on a pair of 10 m/o Ag₂SO₄ reference electrodes to test the reversibility. The polarizability was 3.5 mV/10 μA with no hysteresis loop on the polarization curve, showing that the reversibility was satisfactory. The potential of gold electrode in molten Na₂SO₄ was measured under pure oxygen atmosphere with 10 m/o Ag₂SO₄ electrode as a reference potential. The results showed that the potential of gold electrode could be explained by the 2 Na + SO₃ + 1/2 O₂ → Na₂SO₄ cell reaction.     

Role of platinum in the Na2SO4-Induced hot corrosion resistance of aluminum duffusion coatings

Electrochemical corrosion measurements have been carried out with Pt-containing and Pt-free Al-diffusion coatings on IN 738 LC in a 90Na₂SO₄+ 10K₂SO₄ (mol%) melt at 1173 K. Pt improves the resistance to basic fluxing while there are no significant differences between both coating types in their resistance to acidic fluxing. The corrosion resistance of the Pt-containing coating is also higher in the passive potential region where protective scales rich in Al₂O₃ are formed. The reason for the different behavior of both coating types appears to be related to the high corrosion resistance of the Pt-rich surface layer of the coating and an increased Al₂O₃ content in the scale of the Pt-containing type.     

Mechanism of Chromium Oxidation in SO2 at 3 × 104 Pa and 105 Pa

The kinetics, phase composition, and morphology of scales growing on chromium in SO₂ atmospheres were studied over the temperature range 1073–1273 K and SO₂pressures of 3×10⁴ Pa and 10⁵ Pa. It was found that the scales consist mainly of Cr₂O₃, with only small amounts of sulfur (probably CrS) detected next to the metallic substrate. Oxidation proceeds according to the linear rate law at 10⁵ Pa SO₂ whereas at 1173 and 1273 K at 3×10⁴ Pa SO₂ the parabolic rate law is followed. The transport phenomena were studied by means of radiotracer techniques as well as marker techniques. The oxide–sulfide scales grew mainly by outward diffusion of metal; however, inward transport of S₂ or SO₂ molecules was also observed. The mechanisms of sulfide and oxide formation are discussed on the basis of the experimental results.