Performance of Corrosion-Resistant Alloys in Concentrated Acids

Nickel alloys containing optimum amounts of chromium(Cr),molybdenum(Mo) and tungsten(W) are widely used in the chemical processing industries due to their tolerance to both oxidizing and reducing conditions.Unlike stainless steel(SS),Ni-Cr-Mo(W) alloys exhibit remarkably high uniform corrosion resistance in major concentrated acids,like hydrochloric acid(HCl) and sulfuric acid(H_2SO_4).A higher uniform corrosion resistance of Ni-Cr-Mo(W) alloys,compared to other alloys,in concentrated acids can be attributed to the formation of protective oxide film of Mo and W in reducing acids,and Cr oxide film in oxidizing solutions.The localized corrosion resistance of Ni-Cr-Mo(W) alloys,containing high amount Cr as well as Mo(or Mo + W),is also significantly higher than that of other commercially available alloys.The present study investigates the role of alloying elements,in nickel alloys,to uniform corrosion resistance in concentrated acids(HCl,HCl + oxidizing impurities and H2SO4) and localized corrosion performance in chloride-rich environments using ASTM G-48 test methodology.The corrosion tests were conducted on various alloys,and the results were analyzed using weight loss technique and electrochemical techniques,in conjunction with surface characterization tools.     

Evaluation of microstructure and electrochemical corrosion behavior of austenitic 316 stainless steel weld metals with varying chemical compositions

Austenitic stainless steel weld metals have, in general, inferior corrosion resistance compared with the base metals. This is due to the fact that the weld metal has an inhomogeneous and dendritic microstructure with microsegregation of major elements (i.e., Cr, Mo, and Ni) as well as minor elements (i.e., S and P) at the δ-γ interface boundaries. The nonuniform alloying element concentration around ferrite particles plays a major role in determining the electrochemical corrosion behavior of such weld metals. Although the presence of ferrite is considered to be detrimental as far as the localized corrosion is considered, its exact role in uniform corrosion is still not clear. The uniform corrosion behavior of an alloy is determined by the fundamental electrochemical parameters of the major alloying elements. In this study, an attempt has been made to correlate the microstructure and uniform corrosion behavior of type 316 stainless steel weld metals with varying concentrations of Cr and Mo, and different ferrite contents. From the empirical equations obtained during the analysis of the electrochemical corrosion data, an attempt has been made to understand the role of Cr, Mo, and ferrite in altering the electrochemical corrosion parameters of the weld metal. Based on the extensive microstructural characterization, a dissolution model for the weld metal in the moderately oxidizing medium has been proposed.     

Corrosion behavior of Ni-Cr-base commercial alloys in flowing Ar-42.6%O2-14.7%Br2 gas mixture at 700°C

Corrosion behavior of Ni-Cr-Base commercial alloys has been investigated in an argon-42.6% oxygen-14.7% bromine gas mixture at 700°C which was one of the environments encountered in the UT -3 thermochemical water decomposition reaction process to produce hydrogen. The test alloys were Inconel 600, Hastelloy C-276, Inconel 625, and Nimonic 80A. Two-dimensional thermodynamic phase stability diagrams were constructed for nickel, chromium, iron, tungsten, cobalt, titanium, and aluminium to predict the condensed corrosion products that are stable with respect to the representative alloying elements when the alloy is exposed to the argon-42.6% oxygen-14.7% bromine gas mixture at 700°C. The oxides were thermodynamically stable phases with respect to the corresponding metals. Post-reaction treatment of test alloys included discontinuous mass-change measurements, scanning electron microscopy (SEM), electron probe micro-analysis (EPMA) for morphological and compositional investigation of the corrosion products, and the X-ray diffraction (XRD) for phase identification. XRD identified oxides and spinels as corrosion products but low-melting metal bromides were also detected for all alloys with deleterious effects on high-temperature properties of these alloys during exposure to the environment. The poor corrosion resistance of Inconel 600 and Hastelloy C-276 was mainly caused by the cracking and spalling of iron and nickel-rich oxides and further growth of various metal bromides beneath the oxide scale following prolonged exposure. Inconel 625 and Nimonic 80A alloys performed better than Inconel 600 and Hastelloy C-276, mainly because of their aluminium alloying element and lower iron content.     

Effect of Constituent Elements on the Corrosion Resistance of Single-Phase CoCrFeNi High-Entropy Alloys in NaCl SolutionEI北大核心CSCD

High entropy alloys (HEAs) origin from a new alloy design concept with multi-principal elements, which have attracted significant interests in the past decade. The high configurational entropy in HEAs results in simple solid solutions with fcc and bcc structures. Especially, the single solid solution CoCrFeNi alloy exhibits excellent properties in many aspects, such as mechanical properties, thermal stability, radiation resistance and corrosion resistance. The excellent corrosion resistance of CoCrFeNi alloy is ascribed to the single-phase structure and uniform element distribution coupled with much higher Cr content than stainless steel. The single-phase structure and uniform element distribution can prevent the occurrence of localized corrosion, and higher Cr content can protect the alloy surface better with the form of oxidation film. Moreover, the corrosion resistance of CoCrFeNi-based HEAs, such as CoCrFeNiAlx, CoCrFeNiCux, CoCrFeNiTix, have also been extensively investigated. In most CoCrFeNi-based HEAs, the elements of Co, Cr, Fe and Ni are with equal-atomic ratio. However, the equal-atomic ratio is not necessary to obtain satisfactory properties and to ensure the single fcc structure in Co-Cr-Fe-Ni system. Accordingly, it is essential to further consider the effect of alloying elements on the corrosion resistance in Co-Cr-Fe-Ni HEA. In this work, the effect of Co, Fe and Ni elements on the corrosion resistance of single fcc Co-Cr-Fe-Ni system with concentrated constitution but different atomic ratios in 3.5% NaCl solution are investigated by using LSCM and EIS. The potentiodynamic polarization results indicate that the increase of Fe and the decrease of Ni will decrease the passivation current density of the alloys when the Co and Cr contents are equal. With the increase of Co and the decrease of Ni, the alloys show smaller passivation current density and better corrosion resistance when the Fe and Cr contents are equal. With the decrease of Co and the increase of Fe and Ni, the alloys show higher corrosion potential and smaller corrosion tendency when the Cr content is constant. These results will be helpful for the design of corrosion resistant HEAs in NaCl aqueous solution.     

Effect of alloying elements on the behaviour of TiAl-based alloys

TiAl-based alloys containing Nb, Mo and Cr have been produced by induction melting both under an Ar atmosphere and in vacuum. Fracture toughness and isothermal oxidation tests at 900 °C have been performed on a number of alloys in order to evaluate the effect of alloying elements on both fracture toughness and hot corrosion. The results highlighted that there is an alloy composition range that could allow to obtain a good compromise between high temperature oxidation resistance and fracture toughness. In fact only for a selected Al/Ti ratio and a limited content of alloying elements it is possible to attain the alloy microstructural control and, for Mo free alloys, good protectiveness against oxidation.     

不锈钢在含有溴离子的醋酸溶液中的腐蚀

采用浸泡试验及电化学试验,对304、254 SMO和HastelloyC－276三种材料在醋酸和含有Br^-离子的醋酸溶液中的腐蚀行为进行了测试。用SEM和XPS分析点蚀形貌。结果发现材料表面所形成的钝化膜中含有Cr2O3和MoO2,对材料起保护作用。     

合金元素对铸造Fe-Cr铁素体不锈钢耐浓硫酸腐蚀性能的影响

采用电化学技术、浸泡腐蚀及能谱分析等研究了合金元素对铸造Fe-Cr铁素体不锈钢耐浓硫酸腐蚀行为的影响。结果表明:随铬含量的增加,Fe-Cr合金的耐浓硫酸腐蚀性能增强,单一的铬合金化不能使Fe-Cr合金在60℃,98%H2SO4中自钝化;钼能促进Fe-Cr25-Mo合金的钝化和自钝化,随钼含量的增加,Fe-Cr25-Mo合金的耐浓硫酸腐蚀性能增强;辅助合金元素镍、铜可促进Fe-Cr25Mo2合金的钝化和自钝化,而钛、铌的影响不大。     

Einfluß der Legierungselemente auf die Passivierung und die Korrosionsbeständigkeit der Legierungen auf Eisen-Chrom-Basis

Influence of alloying elements on the passivation and the corrosion resistance of iron chromium base alloys The authors investigated the influence of cathodic alloying (with 0.1–0.5% Pd) on the passivation and the corrosion resistance of alloys of the system FeCr(25–100% Cr) and 25% Cr steels containing Mn, Ni, Mo and N; the experiments have been carried out in hot concentrated sulfuric acid and diluted hydrochloric acid solutions. It has been found that the addition of Pd as a cathodically active component considerably increases the autopassivation tendency as well as the corrosion resistance of the alloys under the particular conditions. Mn gives rise to improved autopassivation of austenitic and austenitic ferritic CrNi and CrNiMo steels, since it is catodically active, too. Cr steels cathodically alloyed with Pd acquire resistance to hydrochloric acid, too.     

Beitrag zum physikalischen und korrosionschemischen Verhalten von IVa-Metallegierungen

The physical and corrosion-chemical behaviour of IVa metal alloys The stability of titanium in respect of non-oxidant acids can be considerably increased by alloying it with Zr, Hf, Nb, Mo or Re. In the case of Zr, Hf, Nb and Ta, a decisive improvement of the corrosion behaviour can only be attained if the At-percentage of these metals in the alloys exceeds 50 pC. In the case of molybdenum, a content from 20 pC upwards has already a markedly passivating effect. But the improvement in corrosion properties must be bought at the price of poorer machinability. A particularly effective alloying metal, even in small quantities, is Rhenium. An excellent corrosion resistance and, at the same time, good machinability can be attained with ternary Ti-Mo-Ta alloys (with Mo + Ta accounting for some 20 At-pC) and with a Ti-12Mo-1Re alloy. The alloying of titanium with Zr, Hf, V, Cr or Mo is apt to cause, in some cases, a considerable deterioration in the scaling resistance of titanium. Improvements can be obtained by using small quantities of Nb, W and particularly Ta. Ti-Ta alloys with Ta contents up to 10 At-pC still have a good scaling resistance at 900° C.     

Titan und Titanlegierungen – Korrosionsbeständige Werkstoffe in Rauchgasentschwefelungsanlagen (REA)

High performance materials for use in flue gas desulfurization In scrubber mixing zones, only Titanium alloys and Alloy C-276 are resistant to corrosion attack. Under acidic deposits in the quench zone Titanium Grade 7 is the only metal totally resistant to localized attack. “Wallpapering”, the use of thin corrosion resistant cladding, is a promising fabrication technique that reduces the high initial cost of using alloys like Titanium and Alloy C-276.     

Das Zeit-Temperatur-Ausscheidungs- und das Zeit-Temperatur-Sensibilisierungs-Verhalten von hochkorrosionsbeständigen Nickel-Chrom-Molybdän-Legierungen

Time-temperature-precipitation and time-temperature-sensitization behavior of highly corrosion resistant nickel-chromium-molybdenum alloys

1 Vortrag anläßlich der áHEMA 91, 9.–15. Juni 1991, Frankfurt/Main.

The time-temperature-precipitation diagrams and the resulting time-temperature-sensitization diagrams have been established and are presented for today's current nickel-chromium-molybdenum alloys C-4, C-276, 22 and the recently developed alloy 59. Compared to those materials alloy 625 behaves differently due to its high niobium content. In addition, also the precipitation and sensitization of alloy G-3 has been established. Under the materials considered alloy C-276 has the strongest tendency to precipitate the intermetallics Mu and P together with the carbide M₆C at intermediate temperatures, followed by the alloys 22 and 59. The tendency to sensitization in the sense of the 50 μm (2 mils) intercrystalline penetration criterion when exposed to the ASTM G-28, method A test solution is greatest with alloy C-276, and decreases over the alloys 22, 59 and G-3 to alloy 625. Sensitization is caused by precipitation of the intermetallics μ and P and the carbide M₆C in case of alloy C-276 and this is probably true also for the alloys 22 and 59. In case of the alloys C-4, G-3 and 625 sensitization is caused by carbide precipitation. A very high thermal stability in the sense of the 50 μm (2 mils) intercrystalline penetration criterion when exposed to oxidizing test solutions as ASTM G-28, method A may be realized most easily if the ratio Cr/(Mo + W) in the alloy is greater than 1.3. Such alloys are 59, 625 and G-3. The highly oxidizing test solutions being in use today for the evaluation of sensitization (ASTM G-28, method A and SEP 1877/II) are making sense only in case of the alloys being high in chromium (alloys 22, 59, 625) whereas they do not correspond to the fields of application in case of the lower chromium alloys (alloy C-276).     

Electrochemical behavior of Co-Cr and Ni-Cr dental cast alloys

The cast structures influencing the electrochemical corrosion behavior of Co-Cr and Ni-Cr dental alloys were studied using potentiodynamic polarization and AC impedance in 0.9% (mass fraction) NaCl solution at (37±1) °C. The phase and microstructure of the alloys that were fabricated using two different casting methods viz. centrifugal casting and high frequency induction casting, were examined using X-ray diffraction analysis, scanning electron microscopy and energy dispersive spectroscopy. The roles of alloying elements and the passive film homogeneity on the corrosion resistance of Co-Cr-Mo and Ni-Cr-Mo dental cast alloys were reviewed. The results of electrochemical study show that the dependence of corrosion resistance on the microstructure associated with the casting methods is marginal. The Co-Cr alloy exhibits more desirable corrosion resistance properties than the Ni-Cr alloy. There is severe preferential dissolution of Ni-rich, Cr and Mo depleted zones in the Ni-Cr alloy.     

金属材料在液态Al-Mg合金中的腐蚀行为

本文对 Fe、Ni、Mo、Zr、Nb、Cr、V、Ta 等金属或以它们为基的合金进行了抗液态 Al-Mg 合金腐蚀试验.材料的耐蚀性系借助金相观察测定溶解扩散层厚度和测定蚀损这两项指标来予以评定的。结果表明绝大多数金属及其合金均不耐液态 Al-Mg 合金的腐蚀,仅 Nb 和合金化程度低的Nb 基合金(如 Nb-2Al,Nb-1Cr)以及 Ta 显示山具有良好的耐蚀性.     

Einfluss der Halbzeugform auf die Korrosionsbeständigkeit hochlegierter Ni‐Cr‐Mo‐Werkstoffe

Effect of semi‐finished products on the corrosion resistance of high‐alloyed Ni‐Cr‐Mo materials The corrosion resistance of different semi‐finished products of six superaustenitic steels and nickel based alloys in the condition of delivery was investigated in some typical standard corrosion tests. The resistance of sheets, plates, strips, seamless tubes and welded tubes to intercrystalline corrosion was tested according to ASTM G 28 methods A and B, as well the resistance to pitting corrosion according to ASTM G 48 method C. The nickel based alloys 625, C‐276 and alloy 59 are resistant to the FeCl₃‐test according to ASTM G 48 method C and therefore a differentiation of these types in regard to their localized corrosion resistance was achieved only in the more aggressive ‘Green‐Death’‐solution. The laboratory experiments confirmed that the corrosion resistance is identical for all semi‐finished products and that it shows only a slight dependence of the surface condition of the materials tested. Additionally, some typical industrial and practical applications of the six high performance materials are presented to demonstrate the excellent corrosion resistance in the manufactured condition.     

Statistics of oxidation resistance of Ni-(0-15)Co-(8-15)Cr-(0-5)Mo-(0-10)W-(3-8)Al-(0-5)Ti-(0-10)Ta-0.1C-0.01B superalloys at 1000℃ by compositional variations

The effects of alloying elements(Co,Cr,Mo,W,Al,Ti,and Ta) on the oxidation resistance of Ni-(0-15)Co-(8-15)Cr-(0-5)Mo-(0-10)W-(3-8)Al-(0-5)Ti-(0-10)Ta-0.1 C-0.01 B alloys were studied.The sample compositions were designed by the Box-Behnken method of design of experiments(DOE).The alloying elements show complicated effects on the mass gain due to oxidation,depending on the alloy composition.Al reduces the mass gain largely.The other elements except Al do not appear to exert a strong effect on the oxidation rate on average,but their influences are shown clearly in the alloys with a low Al content.Co,W,and Ta reduce the oxidation rate,while Cr,Mo,and Ti promote oxidation.Ta is the most effective element in reducing the oxidation rate of the alloy with a low Al concentration.It is confirmed that a continuous Al_2O_3 layer is essentially required for high oxidation resistance.The oxide scale of easily oxidized alloys has various oxides such as NiCr_2O_4,NiAl_2O_4,NiO,Cr_2O_3,CrTaO_4,and TiO_2.     

Seawater resistance of a second generation superaustenitic stainless steel

The first generation of superaustenitic 6Mo steels like 254 SMO® has been further developed into a new steel–654 SMO®–containing very high amounts of those alloying elements most beneficial for the resistance to localized corrosion. 654 SMO is compared with other stainless steels and nickel-base alloys in tests performed in various kinds of seawater. The new steel is much superior to the 6Mo steel under all conditions investigated and compares favourably with Alloy C–276 in most tests. The most corrosive condition among those investigated represents a seawater system where aerobic and anaerobic areas exist simultaneously.     

Wirkung von Cr,Ni, Mn,S, Mo und Cu auf Passivierungs- und Lochkorrosionseigenschaften der Stahlsorte X 6 CrNiTi 1810

The effect of Cr, Ni, Mn, S, Mo and Cu on the passivation and pitting corrosion behaviour of the steel type X 6 CrNiTi 1810 The influence of the alloying elements Cr and Ni as well as of the accompanying elements Mn, S, Mo and Cu in the varying range of the steel type X 6 CrNiTi 1810 (DIN 17440) on the characteristics of the passivation and the pitting corrosion in neutral and acidic 0.2 m NaCl solutions was studied. The characteristics were observed form potentiodynamically measured polarization curves (0.02 V min^?1). The selfpassivation is accelerated in the range Cr < Cu < Mo, Mn and S do not have any effect, Ni has a small negative effect. The resistance against pitting corrosion is promoted in the range Ni < Cr < Cu < Mo, Mn has nothing, S a negative effect. It seems to exist a relationship between the acceleration of the self-passivation and the increasing of the resistance against pitting corrosion with exception of S. The positive influence of accompanying elements on corrosion, machining and application properties can be technically utilized.     

Nicrofer 5923 hMo,ein neuer hochkorrosionsbeständiger Werkstoff für die Chemische Industrie,die Umwelttechnik und verwandte Anwendungen

Alloy 59, a new highly corrosion resistant material for the chemical process industry, environmental pollutioncontrol and related applications

1 Vortrag anläßlich der ACHEMA '91, Frankfurt/Main, 09.–15. Juni 1991.

A new nickel-chromium-molybdenum alloy, Alloy 59 has been designed to withstand severest corrosive conditions as encountered in chemical process industry and today's environmental pollution control systems. This alloy, which is composed of about 59% nickel, 23% chromium and 16% molybdenum is compared to the common NiCrMo-alloys Alloy C-276, Allo C-4, Alloy 22 and Alloy 625. Conditions of corrosion testing have been varied between oxidizing and reducing mineral acids combined with differing halide contaminations. Furthermore, corrosion data in hot concentrated sulfuric acid and in technical relevant solutions of flue gas desulfurization plants are given. The general resistance to corrosion in sulfuric acid and in hydrochloric acid is highlighted in isocorrosion diagrams. Alloy 59 has an excellent resistance to uniform and localized corrosion in all these environments. The new Alloy 59 clearly outperforms the other NiCrMo-alloys C-276, C-4 and 22 as well under oxidizing conditions as in the strongly reducing hydrochloric acid environment. The time-temperature-sensitization-diagram demonstrates the alloy's excellent thermal stability and reveals an improvement compared to Alloy 22 or the well-known Alloy C-276. Alloy 59, therefore, can be used in the as-welded condition without any additional solution annealing treatment. The excellent corrosion resistance is not impaired if the alloy is processed or fabricated to equipment even in larger sections. Weldability with a matching filler metal is without problems as demonstrated i.a. in the varestraint test.     

Relationship between phase composition and corrosion resistanceof Ni-Ti-Nb based shape memory alloys

1　ＩＮＴＲＯＤＵＣＴＩＯＮＮｉ Ｔｉ Ｎｂａｌｌｏｙｓ ,ｏｎａｃｃｏｕｎｔｏｆｔｈｅｉｒｓｈａｐｅｍｅｍ ｏｒｙａｎｄ ｐｈａｓｅｔｒａｎｓｆｏｒｍａｔｉｏｎｈｙｓｔｅｒｉｓｉｓ ,ｈａｖｅｂｅｅｎｐａｉｄａｔｔｅｎｔｉｏｎｂｙｒｅｓｅａｒｃｈｅｒｓｆｏｒｍａｎｙｙｅａｒｓａｎｄｐｒｏ ｐｏｓｅｄｆｏｒｖａｒｉｏｕｓａｐｐｌｉｃａｔｉｏｎｓ[1～ 5] .Ｔｈｅｒｅｓｕｌｔｓｓｈｏｗｔｈａｔｔｈｅｐｈａｓｅｔｒａｎｓｆｏｒｍａｔｉｏｎｈｙｓｔｅｒｉｓｉｓｄｕｅｔｏ β ＮｂｐａｒｔｉｃｌｅｓｉｎＮｉ Ｔｉｍａｔ…     

利用双层辉光等离子技术进行镍基耐蚀合金表面合金化的研究

研究了在 2 0钢和不锈钢基材上 ,利用双层辉光离子渗金属技术进行Ni Cr Mo Cu多元共渗表面合金化 ,采用电化学方法对两种基材表面形成的渗层在 5 %HCl中的腐蚀性能进行了测定。结果表明 :在两种基材上都能得到类似于源极HastelloyC - 2 0 0 0合金的表面合金渗层 ,在不锈钢表面上形成的渗层的耐蚀性能接近HastelloyC - 2 0 0 0合金并且优于Alloy 5 9合金 ,在 2 0钢表面上形成的渗层耐蚀性能优于不锈钢Cr18Ni9