Herstellung und Eigenschaften stickstofflegierter,korrosionsbeständiger Stähle und Sonderstähle mit niedrigen Kohlenstoffgehalten

Production and properties of nitrogen alloyed, corrosion resistant steels and special steels with low carbon contents Alloying with nitrogen has favourable influence in particular on the mechanical properties of CrNiMo steels (X 2 CrNiMoN 17 12, materials No. 1.4406, X 2 CrNiMoN 17 13 5, materials No. 1.4439 und X 2 CrNiMoN 22 5, materials No. W.-Nr. 1.4462). This comes to bear when ambient temperature and low temperature strength and toughness are concerned. With respect to the corrosion behaviour the data concerning the effect of nitrogen are contradictory. It has become clear that nitrogen improves pitting corrosion resistance; this applies, however, only to pit initiation but not to pit growth. Stress corrosion cracking is not delayed by nitrogen but different results have been obtained with different media: while the duplex steel X 2 CrNiMoN 22 5 is attacked considerably faster than the corresponding nitrogen-free steel in 42% boiling magnesium chloride solution the time-to-failure of both steels are comparable in 30% boiling MgCl₂-solution. The nitrogen alloyed steels can be welded by all known welding procedures, provided fully austenitic welding rods are used.     

Selektive Korrosion von Duplexstahl. Teil 2: Lokale Korrosionserscheinungen an Duplexstahl X2CrNiMoN22‐5‐3 unter Einwirkung von Chloriden und mechanisches Verhalten in Abhängigkeit vom Gefügezustand

Selective corrosion of duplex stainless steel. Part 2: Localized corrosion manifestations under exposure of chlorides on duplex stainless steel X2CrNiMoN22‐5‐3 and mechanical behavior in dependence of the microstructure In completion to part 1 of this paper this part deals with interrelations between localized corrosion manifestations, mechanical properties and the microstructure of duplex stainless steel X2CrNiMoN22‐5‐3. The pit formation on duplex stainless steels is substantially determined by the distribution of the alloying elements within single phases and by defects in the oxide layer. The positive properties of molybdenum become ineffective at thicker oxide layers due to the fact, that molybdate, which is responsible for inhibition of pitting, can not be formed. Depletion areas caused by precipitations are preferential attack places for corrosion. The influence of chlorides for duplex stainless steels in rolled and welded conditions is characterized by a logarithmic dependence.     

双相不锈复合钢板埋弧自动焊

研究了Ｈ１１／Ｘ２ＣｒＮｉＭｏＮ２２．５双相不锈复合钢板埋弧自动焊工艺，焊接材料的选择及其焊接性。结果表明，复层焊缝的δ铁素体含量在３５％～４５％内，其焊接性优良。过渡层的焊接采用较弱焊接规范和单道焊工艺，以控制较小的稀释率和良好的焊缝成形，防止在与基层焊缝的熔合线附近产生大量马氏体组织和其它硬化相。Ｈ１１／Ｘ２ＣｒＮｉＭｏＮ２２．５双相不锈复合钢板埋弧自动焊焊接接头具有良好的力学性能，复层焊缝具有极为优良的抗晶间腐蚀和应力腐蚀的能力。本研究为煤气工程中汽化炉的制造选定了合适的焊接材料并制定了最佳埋弧自动焊工艺。     

Elektrochemische Methode zur Prüfung des Korrosionsverhaltens austenitischer CrNiMo-Stähle im Schweißnahtbereich

Electrochemical method for testing of the corrosion behaviour of austenitic CrNiMo-stainless steel weldments Austenitic CrNiMo stainless steel welds can be more susceptible to pitting and crevice corrosion than the base material owing to segregation and precipitation in the heat affected zone, in the high temperature zone and in the welded zone. Suitable test methods are needed to optimize welding technology. Comparison of potential curves (DIN 50919), comparison of critical pitting corrosion temperatures in FeCl₃- or other model solutions, visual estimation after longterm corrosion tests with or without electrochemical load are discussed. A small measurement cell heated from the rear with circulating and temperature controlled electrolyte is shown. With its help separate areas of a weld can be electrochemically investigated. Welds of the materials X 2 CrNiMoN 17 12 2 (1.4406), X 2 CrNiMoN 17 13 5 (1.4439) and X 1 NiCrMoCu 31 27 4 (1.4563) are tested in acidic NaCl solutions in the range of 25 to 75°C. Critical pitting corrosion potentials are obtained for base materials, heat affected zone and weld material. An influence of the welding energy is probable, but cannot be proved in this case without statistical certainty.     

Kurzzeituntersuchungen zur Auswahl von rostbeständigen Cr-Stählen mit verbessertem Widerstand gegen Schwingungsrißkorrosion

Short-time investigations into the selection of stainless chromium steels with improved corrosion fatigue resistance Using the steel X 20 Cr 13 various short-time test methods have been tested for evaluating the corrosion fatigue susceptibility in concentrated air-saturated sodium chloride solution. In addition the steels X 15 CrNi17, X 35 CrMo 17, X 5 CrNiMoCuNb 14 5, X 4 CrNiCuNb 16 4, X 2 CrNiMoN 22 5 3, X 5 CrNiMoCu 25 5, X 8 CrNiMo 27 5 and X 1 CrNiMoNb 28 4 2 have been studied at room temperature of 80° C using crack propagation, constant straining and pitting corrosion methods. The two last mentioned steels are superiour under the test conditions.     

Selektive Korrosion von Duplexstahl. Teil 1: Aussagekraft herkömmlicher und neuartiger Methoden zur Untersuchung des Korrosionsverhaltens von Duplexstahl X2CrNiMoN22‐5‐3 unter besonderer Berücksichtigung der Mikrostruktur

Selective corrosion of duplex stainless steel. Part 1: Corrosion behaviour of duplex stainless steel X2CrNiMoN22‐5‐3 with special consideration of the microstructure This paper is dealing with investigations on interrelations between microstructure and corrosion behaviour of duplex stainless steel X2CrNiMoN22‐5‐3. With the application of conventional methods like Strauß‐ and Huey‐test it is not possible to describe correctly the corrosion behaviour. In contrary, by means of the development of the electrochemical potentiodynamic reactivation (EPR) method it is possible to give a reliable proof of corrosion susceptibility. The knowledge about the corrosion of duplex stainless steel was intensified by fundamental investigation of interrelations between precipitations and corrosion behaviour. By means of numerous investigations on the microstructure by means of SEM and TEM secondary phases were analysied and quantified and depletion areas created by precipitations were characterized.     

The effect of large heat input on the microstructure and corrosion behaviour of simulated heat affected zone in 2205 duplex stainless steel

In the simulated heat affected zone of 2205 duplex stainless steels, effects of large welding heat inputs on the microstructure and corrosion behaviour were investigated. Reformed austenite content increased with the coarsening of grain boundary austenite (GBA) and the growth of intragranular austenite (IGA) and Widmanstatten austenite (WA), thus improving the low temperature toughness and affecting corrosion state. Reduction of chromium nitrides contributed to better resistance to pitting corrosion. Moreover, the pitting corrosion and intergranular corrosion were improved resulting from the formation of more GBA and WA. The specimen with a Δt_8/5 of 100 s presents better comprehensive performance.     

Vergleichende Untersuchungen des SwRK-Verhaltens verschiedener Dampfturbinenschaufelstähle

Comparative investigations into the corrosion fatigue behaviour of different steam-turbine-blade steels Corrosion fatigue tests in NaCl-solution in the temperature range from ambient temperature to 150°C revealed a decrease of the corrosion fatigue strength of the steels X20Cr13 with 1% resp. 2.5% Mo, X4CrNiMo 16 5 1 and X2CrNiMoN 22 5 with increasing temperature; a minimum of the corrosion fatigue strength is reached at 150°C. At temperatures of about 80°C it was found an optimum corrosion fatigue behaviour of the Mo-alloyed steel X20CrMo13 2.5 in comparison with the other investigated steels. It was observed that crack initiation of the ferritic, Mo-alloyed steel is caused by Cl-induced pitting, of the soft martensitic steel by oxide inclusions and of the duplex steel by non metallic, brittle inclusions and/or by grain boundarys of the ferritic/austenitic microstructure. Crack initiation caused by pre-deformation at slip bands was observed on the duplex steel. All materials investigated failed at elevated temperatures. At temperatures higher than 80°C an optimum corrosion fatigue behaviour was not found.     

Localized corrosion properties of low interstitial ferritic,high purity austenitic and high chromium duplex stainless steels

Within the framework of a research aimed at characterizing the behaviour of new materials to pitting and crevice corrosion, an investigation has been made, using electrochemical techniques, of the following materials: ELI ferritic stainless steels (18 Cr-2 Mo-Ti; 21 Cr-3 Mo-Ti; 26 Cr-1 Mo); high chromium duplex stainless steel (Z 5 CNDU 21-08) and high chromium-nickel austenitic stainless steel (Z 2 CNDU 25-20); commercial austenitic stainless steels (AISI 304 L and 316 L) and laboratory heats of austenitic stainless steels with low contents of interstitials (LTM/18 Cr- 12 Ni, LTM/16 Cr- 14 Ni-2 Mo). It was possible to graduate a scale of resistance to pitting and crevice corrosion in neutral chloride solutions at 40 C; in particular the two experimental austenitic stainless steels LTM/18 Cr- 12 Ni and LTM/16 Cr- 14 Ni-2 Mo are at the same level as the AISI 316 L and 18 Cr-2 Mo-Ti, respectively. An occluded cell was developed and used for determining the critical potential for crevice corrosion (E_{localized corrosion}). For the steels under investigation E_{localized corrosion} is less noble than E_pitting especially for ELI ferritic 18 Cr-2 Mo-Ti and 21 Cr–3 Mo-Ti.     

Untersuchungen zum Korrosions- und Verschleißverhalten von hartstoffverstärkten „Duplexstahl“-Schutzschichten

Investigations on corrosion and wear behaviour of duplex stainless steel coatings reinforced with hardening components This paper is dealing with corrosion and wear resistance results of protective duplex stainless steel coatings (X2CrNiMoN25-10-4) made by two-powder-plasma weld surfacing with additional hardening components Cr₂C₃ and WC-WC₂. First the developing of a process technique was important which allows an exact addition of hardening components and an as low as possible dissolution of carbides. The microstructure did not show the typical ferritic-austenitic structure. The wear and corrosion resistance in sulphuric acid is very good and reveals the high quality of the protective coatings. However the corrosion resistance in synthetic sea water is considerable reduced. Low grain size and pre-heat temperatures of 100 °C have a positive influence on the corrosion resistance.     

Korrosion nichtrostender austenitischer Stähle in (kondensierender) chloridhaltiger Salpetersäure

Corrosion of austenitic stainless steels in (condensing) nitric acid containing chlorides The corrosion parameters involved in the behaviour of austenitic stainless steels and nickelbase alloys in chloride containing nitric acid are being stated. Investigation of the corrosion resistance of the austenitic stainless steel 1.4306, ESR grade for application in nitric acid, in nitric acid condensates containing small amounts of chlorides. The condensates were formed from boiling nitric acids of molarities 6 to 10 containing 15 to 45 mg chlorides/1. The calculated corrosion rates of < 1 μm/y can be considered rather small. Especially in cases of insufficient wetting of the heat exchanger surfaces, however, local roughening and pitting corrosion is to be expected, mostly under rust-colored, chloride-containing deposits. The intensity of pitting corrosion increases with increasing chloride contents of the nitric acid solutions that evaporate. The sealing surfaces consisting of steel 1.4306 and PTFE did not exhibit any crevice corrosion. Nitric acid grade ESR-1.4306 definitely does not suffice requirements as described in this paper. It is suggested to use stainless steels which exhibit an improved resistance against chlorides and, at the same time, a high resistance against nitric acid attack. The following steel grades may be considered: X 1 CrNi 25 21 (Mat. No. 1.4335), X 2 CrNiMoN 25 22 2 (Mat. No. 1.4466) and/or X 1 NiCrMoCuN 31 27 4 (Mat. No. 1.4563).     

Untersuchung der Interkristallinen Korrosion bei Duplexstählen mit Thioacetamid als Aktivator im EPR-Verfahren

Investigation of intercristalline corrosion of duplex stainless steels using thioacetamid as an activator for EPR-test To evaluate susceptibility of the duplex stainless steel (DSS) X2CrNiMoN22-5-3 to intergranular attack (IGA) using doubleloop (DL)-EPR-test, thioacetamid (TA) instead of KSCN has been taken as activator. TA has to suppress selective ferrite corrosion by keeping up good IGA-detection. Solution annealed rolled samples were hold at 650°, 750° and 850° over 3 to 600 min. Conditions: 0.5 M H₂SO₄ + 0.01 M KSCN, 70° or 2.5 × 10^?4 to 1 × 10^?2 M TA; 50°, 60° and 70°. For test evaluation the ratio i_R/i_P respectively q_R/q_P, has been used in connection with research of microstructure. Using optimal parameters TA enables EPR-test to detect IGA on DSS produced by X- and α-phase precipitations. The mechanism of effect of TA is discussed.     

Untersuchungen über den Einfluß des Gefügezustandes auf das Korrosionsverhalten hochlegierter,rost- und säurebeständiger Stähle in reiner sowie in chloridhaltiger Schwefelsäure

Corrosion Properties of High Alloyed Stainless Steels in Pure as well as in Chloride Containing Sulfuric Acid The corrosion behaviour of the high alloyed stainless steels material no. 1.4439 (X3CrNiMoN17135), 1.4539 (X2NiCrMoCu25205), 1.4503(X3NiCrMoCuTi2723) as well as the reference materials AlSI 316 L and alloy 825 was tested in diluted sulfuric acid (5, 10, 20 and 50%) at 50, 100 and 150°C. The test solutions additionally contained impurities as chlorides and cupric ions. On the material side the effect of various microstructures was checked as well: material as received (commercial production), solution annealed under laboratory conditions, cold deformed and for two selected steels electroslag remelted. Corrosion testing methods are: the immersion test will sheet coupons and the measurement of the weightloss; electrochemical testing, i.e. Current potential-and free corrosion potential-time-curves. No pitting corrosion is observed in the presence of chloride ions. In some cases the general corrosion rate is lowered if chloride ions are present. This beneficial effect of chloride ions, however, is observed only at low chloride concentrations (500 ppm). Annealing under laboratory conditions as well as electroslag remelting does not generally improve the corrosion resistance. A negative effect by cold deformation is only observed for standard stainless steel AlSI 316. Cupric ions added to the 20% sulfuric acid solution improve the corrosion resistance of all steels investigated to that extent, that they can be used in practice up to 100°C provided that the concentration of cupric ions in the solution is sufficiently high (2000 ppm). Electrochemical test results indicate that the positive effect of cupric ions is due to the shift of the free corrosion potential into the potential range of stable passivity. Copper alloyed stainless steels show the highest corrosion resistance.     

Annealing temperature effect on the pitting corrosion resistance of plasma arc welded joints of duplex stainless steel UNS S32304 in 1.0 M NaCl

Pitting corrosion resistance of 2304 duplex stainless steels after autogenous plasma-arc welding and subsequent short-time post-weld heat treatment at different temperatures, determined by critical pitting temperature in 1.0 M NaCl solution, has been investigated. The results showed that the as-welded joint displayed impaired pitting corrosion resistance and that pitting preferentially occurred at ferrite grain in heat-affected zone near the fusion line. Short-time annealing treatment at 1020–1120 °C has a beneficial effect on the pitting corrosion resistance of welded joint. The most favorable annealing temperature for the analyzed welded joints was found to be 1080 °C, at which the joint restored the pitting corrosion resistance lost during welding entirely.     

Effects of cooling time and alloying elements on the microstructure of the gleeble-simulated heat-affected zone of 22% Cr duplex stainless steels

The effects of austenite stabilizers, such as nitrogen, nickel, and manganese, and cooling time on the microstructure of the Gleeble simulated heat-affected zone (HAZ) of 22% Cr duplex stainless steels were investigated. The submerged are welding was performed for comparison purposes. Optical microscopy (OM) and transmission electron microscopy (TEM) were used for microscopic studies. The amount of Cr₂N precipitates in the simulated HAZ was determined using the potentiostatic electrolysis method. The experimental results indicate that an increase in the nitrogen and nickel contents raised the δ to transformation temperature and also markedly increased the amount of austenite in the HAZ. The lengthened cooling time promotes the reformation of austenite. An increase in the austenite content reduces the supersaturation of nitrogen in ferrite matrix as well as the precipitation tendency of Cr₂N. The optimum cooling time from 800 to 500 °C (Δt _8/5) obtained from the Gleeble simulation is between 30 and 60 s, which ensures the austenite content in HAZ not falling below 25% and superior pitting and stress corrosion cracking resistance for the steels. The effect of manganese on the formation of austenite can be negligible.     

Corrosion‐technical properties of high‐strength stainless steels for the application in prestressed concrete structures

Experience with prestressed concrete over about half a century has indicated that the corrosion resistance of conventional prestressing steel does not always satisfy, especially the prestressing steels are susceptible to chloride attack (de‐icing salts) and hydrogen (hydrogen‐induced stress corrosion cracking). On the other hand corrosion agents, such as chloride, condensation water, can penetrate in the concrete and arrive at the surface of steels. Hence, corrosion damage of prestressing steels can happen and, in the extreme cases, the prestressed concrete structure collapsed resulting from the failure of the tendon. In this paper, consideration is made to use high‐strength stainless steels as prestressing tendon with bond in concrete. The high‐strength stainless steels of qualities 1.4301 (X5CrNi18‐10), 1.4401 (X5CrNiMo17‐12‐2), 1.4436 (X3CrNiMo17‐13‐3) and 1.4439 (X3CrNiMoN17‐13‐5) with sequence of increasing austenite stability were investigated. For application in prestressing tendon with bond in concrete the cold‐drawn high‐strength stainless steel of quality 1.4401 is an optimal proposition regarding its satisfactory resistance against pitting corrosion and stress corrosion cracking (SCC) in structure‐related corrosive conditions. The lower alloyed steel 1.4301 has an insufficient resistance against the chloride‐induced corrosion because of the lack of molybdenum and the content of deformation martensite due to the strong cold‐drawing of its unstable austenitic structure.     

Microstructure and pitting corrosion of similar and dissimilar stainless steel welds

Abstract

Pitting Corrosion behaviour of similar and dissimilar metal welds of three classes of stainless steels, namely, austenitic stainless steel (AISI 304), ferritic stainless steel (AISI 430) and duplex stainless steel (AISI 2205), has been studied. Three regions of the weldment, i.e. fusion zone, heat affected zone and unaffected parent metal, were subjected to corrosion studies. Electron beam and friction welds have been compared. Optical, scanning electron microscopy and electron probe analysis were carried out to determine the mechanism of corrosion behaviour. Dissimilar metal electron beam welds of austenitic–ferritic (A–F), ferritic–duplex (F–D) and austenitic–duplex stainless steel (A–D) welds contained coarse grains which are predominantly equiaxed on austenitic and duplex stainless steel side while they were columnar on the ferritic stainless steel side. Microstructural features in the central region of dissimilar stainless steel friction welds exhibit fine equiaxed grains due to dynamic recrystallisation as a result of thermomechanical working during welding and is confined to ferritic stainless steel side in the case of A–F, D–F welds and duplex stainless steel side in the case of D–A welds. Beside this region bent and elongated grains were observed on ferritic stainless steel side in the case of A–F, D–F welds and duplex stainless steel side in the case of D–A welds. Interdiffusion of elements was significant in electron beam welding and insignificant in friction welds. Pitting corrosion has been observed to be predominantly confined to heat affected zone (HAZ) close to fusion boundary of ferritic stainless steel interface of A–F electron beam and D–F electron beam and friction weldments. The pitting resistance of stainless steel electron beam weldments was found to be lower than that of parent metal as a result of segregation and partitioning of alloying elements. In general, friction weldments exhibited better pitting corrosion resistance due to lower incidence of carbides in the microstructure.     

Influence of sigma-phase formation on the localized corrosion behavior of a duplex stainless steel

Because of their austenitic-ferritic microstructures, duplex stainless steels offer a good combination of mechanical and corrosion resistance properties. However, heat treatments can lower the mechanical strength of these stainless steels as well as render them susceptible to intergranular corrosion (IGC) and pitting corrosion. In this study, a low-carbon (0.02%) duplex stainless steel is subjected to various heat treatments at 450 to 950 °C for 30 min to 10 h. The heat-treated samples then undergo ASTM IGC and pitting corrosion tests, and the results are correlated with the microstructures obtained after each heat treatment. In the absence of Cr₂₃C₆ precipitation, σ-phase precipitates render this duplex stainless steel susceptible to IGC and pitting corrosion. Even submicroscopic σ-phase precipitates are deleterious for IGC resistance. Longer-duration heat treatments (at 750 to 850 °C) induce chromium diffusion to replenish the chromium-depleted regions around the σ-phase precipitates and improve IGC resistance; pitting resistance, however, is not fully restored. Various mechanisms of σ-phase formation are discussed to show that regions adjacent to σ-phase are depleted of chromium and molybdenum. The effect of chemical composition (pitting resistance equivalent) on the pitting resistance of various stainless steels is also noted.     

Influence of chemical composition on the pitting corrosion resistance of non-standard low-Ni high-Mn-N duplex stainless steels

The pitting corrosion resistance of a new family of duplex stainless steels has been evaluated. These non-standard duplex stainless steels are characterised by low Ni content and high N and Mn levels. Potentiodynamic polarisation scans in NaCl solution have been carried out to determine pitting potentials. A crevice-free cell has been used to perform the electrochemical tests.An exponential equation is obtained in the regression analysis between the pitting potential and chemical composition which allows an estimate of the pitting resistance of these new duplex stainless steels.     

Determination of the weaker phase in the pitting corrosion of non‐standard low‐Ni high‐Mn‐N duplex stainless steels

In this paper, the use of Energy Dispersive Spectrometry (EDS) is proposed to determine the partition coefficients of the elements of a new family of duplex stainless steels that are characterized by having low contents of nickel, together with high levels of manganese and nitrogen. From the values of the partition coefficients, the chemical compositions of the constituting phases have been determined, in order subsequently to calculate the value of the Pitting Resistance Equivalent Number (PREN) of each phase. The proposition put forward in this study is that the phase having the lower PREN determines the pitting corrosion behaviour of these types of steels. Results obtained by means of optical and scanning electron microscopy have provided confirmation that the pitting corrosion behaviour of these new materials gets determined by the resistance of the weaker phase and consequently by the phase having the lower PREN value. Lastly it has been proved possible to determine the existence of an exponential relationship between the alloys pitting potential (Ep) and the weaker phase PREN; this can be utilized for the low‐nickel duplex stainless steels design in which the pitting corrosion resistance is controlled.