Interactions between polysulphides and stainless steel materials

Ability of polysulphide to enhance the potential of digester materials (S30400, S31603, S32205, S32304) was studied in the impregnation stage of the pulping process. Polysulphides were generated by adding elemental sulphur to alkaline sulphide solutions. Polysulphide levels 0.3–0.48, 1.25–2, 5–8 and 12.5–20 g/l enhanced the potentials of the steels by 70, 90, 170 and 190 mV, respectively. The polysulphide concentrations were calculated values, because concentrations of polysulphides are very difficult to measure in kraft liquors. No weight changes were observed, but slight accumulation of sulphur onto surfaces, particularly onto S31603 was seen in X‐ray fluorescence analysis. Otherwise, differences in behaviour among the steel materials were minimal.     

Interactions of sulphur anions and stainless steels at kraft pulp digesting temperature

Interactions of certain stainless steels (S30400, S31600, S31803, S32304) and sulphur anions, separately and in combination, at concentrations typical of kraft liquors were investigated using XRF and CER techniques. IC, ISE and ABC titration were applied in the modelling of behaviour of the sulphur anions. Nickel and sulphur enriched to the steel surfaces in all experiments. Abilities of molybdenum and chromium to remain in the surfaces appeared to be better than those of iron. Adhesion of sulphur onto austenitic grades was probably stronger than that of the duplex grades. Sulphide and combination of sulphur anions formed durable films, but films formed by thiosulphate possessed some gliding properties. For the solution, real amount of the sulphide was less than the added amount. Thiosulphate had a tendency to convert into sulphite.     

Localized corrosion of (lean) duplex stainless steels in immersion units of urban wastewater treatment plants

With lower alloying cost and higher mechanical properties, lean duplex stainless steels can be an alternative to the more commonly used austenitic stainless steels. However, these alloys are still not the preferred choice, probably due to a lack of field experience. A study was thus initiated in view of defining the limits of use of selected (lean) duplexes for urban wastewater treatment units. The present paper shows the localized corrosion performance of selected lean duplexes in chloride contaminated solutions. The results are compared with austenitic S30403 and S31603 and with the more standard duplexes S82441 and S32205. The effect of welding was also investigated. Exposures in field municipal wastewater plants were conducted for 1 year in low and high chloride content units. The results show that lean duplexes S32101 and S32202 can be used as alternatives to S30403 and S31603 in low chloride electrolytes. At 500 ppm of chloride content, duplex stainless steel S32304 showed better corrosion resistance than S30403 and S31603. For higher chloride contents (1000 ppm and above) the standard duplexes S82441 and S32205 shall be preferred.     

Localized corrosion of lean duplex stainless steels in H2S-containing wet atmosphere from urban wastewater treatment units

With lower alloying costs and higher mechanical properties, lean duplex stainless steels can be a good alternative to the more commonly used austenitic stainless steels. A study was initiated to define the limits of the use of lean duplex stainless steels for urban wastewater treatment (WWT) units. This paper gives and discusses the corrosion results in an aerated wet atmosphere containing H₂S at different levels. Exposures were performed both at laboratory scale and in the field WWT plant for 1 year. A specific probe was also designed to study the corrosion process below water condensate film contaminated with H₂S. Under such conditions, the properties of stainless steel were strongly modified with an enhanced risk of localized corrosion. The results obtained on lean duplex materials (UNS S32101, S32202, and S32304) are compared with austenitic UNS S30403 and UNS S31603 and with the more standard duplexes UNS S82441 and UNS S32205. The results show that lean duplexes can be used in aerated wet atmospheres in case of moderate contamination of H₂S (<10 ppm) and chloride (<200 ppm). For higher contaminations (e.g., H₂S around 100 ppm/chloride around 1000 ppm) the duplex S32205 should be preferred.     

Effect of laser surface melting on intergranular corrosion behaviour of aged austenitic and duplex stainless steels

In the present study, the effect of laser surface melting (LSM) on intergranular corrosion behaviour of aged austenitic stainless steels (UNS S30400, S31603, S32100 and S34700) and aged duplex stainless steels (UNS S31803 and S32950) were investigated. LSM of the aged stainless steels was carried out using a 2.5 kW CW Nd:YAG laser. The microstructure of the aged stainless steels after LSM depends on their compositions. After LSM, the aged austenitic stainless steels mainly contain austenite (γ) with some ferrite (δ) as the minor phase, but the carbide phases are completely eliminated. For the aged duplex stainless steels after LSM, δ becomes the major phase and the δ/γ phase balance is disturbed, whereas the sigma (σ) phase is eliminated. The degree of sensitization (DOS) and corrosion morphology of the aged stainless steels before and after LSM were determined by the double loop electrochemical potentiokinetic reactivation (DL-EPR) using a potentiostat and SEM observation, respectively. Desensitization of the aged stainless steels has been successfully achieved by LSM and their intergranular corrosion resistance is found to be significantly enhanced as reflected by the decrease in DOS due to dissolution of the carbides or σ phase, which reduced Cr depletion or the possibility of solute segregation at the grain or phase boundaries, despite the presence of δ and disturbance of δ/γ phase balance.     

A general model for the repassivation potential as a function of multiple aqueous species. 2. Effect of oxyanions on localized corrosion of Fe–Ni–Cr–Mo–W–N alloys

A recently developed model for predicting the repassivation potential has been applied to stainless steels and nickel-base alloys in aqueous environments containing chlorides and various inhibiting anions. The model accounts for the effects of solution chemistry and temperature on the repassivation of localized corrosion by considering competitive dissolution, adsorption, and oxide formation processes at the interface between the metal and the occluded site solution. An extensive database of repassivation potentials has been established for six alloys (UNS 31603, N06600, N06690, S31254, S32205, and UNS S41425) in contact with solutions that combine chlorides with hydroxides, molybdates, vanadates, sulfates, nitrates, and nitrites at various concentrations and temperatures. Also, repassivation potentials are reported for four alloys (UNS N08367, N08800, N06625, and N10276) in chloride solutions. The database has been used to establish the parameters of the model and verify its accuracy. The model quantitatively predicts the transition between concentrations at which localized corrosion is possible and those at which inhibition is expected. It is capable of predicting the repassivation potential over wide ranges of experimental conditions using parameters that can be generated from a limited number of experimental data. The parameters of the model have been generalized as a function of alloy composition, thus making it possible to predict the repassivation potential for alloys that have not been experimentally investigated.     

核电厂水池覆面用不锈钢钢板在硼酸水溶液中的点蚀行为

采用电化学方法研究了温度、Cl~-以及SO_4~(2-)含量对不锈钢板S30403、S32101和S32205在硼酸溶液中点蚀行为的影响。结果表明:3种材料的点蚀电位(Eb)和再钝化电位(Er)均随Cl~-含量的升高而降低,S32205不锈钢的点蚀电位和再钝化电位普遍高于S32101和S30403不锈钢的;存在临界温度(约60℃),当温度高于临界温度,S32205不锈钢的点蚀电位大幅降低,再钝化电位的临界温度介于40~60℃;SO_4~(2-)含量对3种材料点蚀电位和再钝化电位的影响不明显。S32205不锈钢的耐点蚀性能优于S32101和S30403不锈钢的,而S32101和S30403不锈钢的耐点蚀性能相当。     

The effect of CeCl3 inhibitor on the localized corrosion of stainless steel in chloride solutions

Stainless steels have been used extensively in many sectors such as medical and household appliances as well as construction. This has been primarily due to their high resistance to corrosion attacks, reasonable cost, and excellent mechanical properties. However, when placed in corrosive media stainless steel is susceptible to localized corrosion attacks, especially when placed in chloride solutions. The paper explores the issue of corrosion liability of austenitic (AISI 316) and duplex (UNS S32205) stainless steels in et aconditions of seawater environment as well as under the influence of an inhibitor in the same environmental conditions. The behavior of stainless steels was examined via electrochemical testing relying on DC and AC techniques, optical metallographic analysis, scanning electron microscopy, and X‐ray diffraction analysis. Duplex stainless steel showed better resistance to localized corrosion but a higher tendency toward general corrosion in all examined solutions. Cerium chloride in a chloride solution showed inhibiting properties for both the AISI 316 and the UNS S32205.     

Corrosion performance of selected stainless steels in brine from reverse osmosis desalination plants

Abstract

The corrosion performances of some commercial stainless steel alloys in the brine reject solution from a reverse osmosis sea water desalination plant was studied in terms of their pitting susceptibilities (investigated under aerated conditions at ambient temperature using a cyclic polarisation technique) and crevice corrosion resistances (evaluated in the plant over a 3 month exposure period using multiple crevice test assemblies). The alloys used were four austenitic steels, UNS S31603, UNSS 31703, UNS N08904, UNS S31254, a ferritic steel UNS S44635, and a duplex steel UNS S32550. Cyclic polarisation studies show that the pitting or breakdown potentials for S31603 and S31703 occurred at more active values than for N08904, S31254, S44635, and S32550 alloys, and indicated a reduced resistance to pitting corrosion. The multiple crevice tests show that the alloys S31603, S31703, and N08904 do suffer crevice corrosion in the brine reject solution at ambient temperature, while the S44635 S32550, and S31254 alloys showed considerably higher crevice corrosion resistance.     

Secondary austenite and chromium nitride precipitation in simulated heat affected zones of duplex stainless steels

Abstract

Primary and secondary intragranular austenite precipitation and its relationship with chromium nitride (Cr₂N) were studied in a simulated multipass heat affected zone (HAZ) of five duplex stainless steel alloys (UNS S32304, S32205, S32550, S32750, and S32760). The Gleeble thermal-mechanical simulator was used to perform short duration and high cooling rate ferritisation and reheating heat treatments. TEM and FEG-SEM analysis, coupled with a specially developed electrolytic etching technique, revealed the cooperative growth of secondary austenite and Cr₂N precipitation along the ferrite/austenite (α/γ) interfaces. Additionally, the observed close coexistence of intragranular nitride (Cr₂N) and intragranular secondary austenite suggests the heterogeneous nucleation of secondary austenite from the nitrides as supported by previously reported low energy nitride/austenite (Cr₂N/γ) interfaces for the observed orientation relationship between both phases. Based on these observations, a new mechanism is proposed for intragranular secondary austenite nucleation related to the intragranular nitride precipitates.     

High-temperature oxidation of duplex stainless steels S32101 and S32304 in air and simulated industrial reheating atmosphere

High-temperature oxidation of duplex stainless steels S32101 and S32304 was performed under three conditions: isothermal oxidation at 1050 °C in air and simulated industrial reheating atmosphere and in situ oxidation in air during the continuous heating to 1050 °C. Breakaway oxidation was found in S32101 but not in S32304, before which the weight gain per unit area was in parabolic relation to time. A triplex oxide layer of S32101 and a duplex-layer of S32304 oxidized for 120 min were observed, respectively. The initial oxidation phase was austenite for S32101 and ferrite for S32304 due to different manganese content.     

The chloride stress-corrosion cracking behavior of stainless steels under different test methods

Chloride-induced stress-corrosion cracking (SCC) is one of the failure modes of stainless steels. Highly alloyed austenitic stainless steels S32654, S31254, and N08028, and duplex grades S32750 and S31803 possess much improved resistance to SCC compared with S30400 and S31600 steels. With the development of a database, SSData, experimental data collected from calcium chloride tests, autoclave tests, and drop evaporation tests were evaluated. Stress-corrosion cracking data generated by autoclave tests agreed well with the practical service conditions and can be used to discriminate alloys for SCC resistance in sodium chloride solution. Drop evaporation test data can be used in situations where evaporation may occur and cyclic loading may be involved. The SCC resistance of alloys under each method increased with increasing molybdenum equivalent Mo + 0.25Cr + 0.1Ni. For a given alloy, the testing result depends on the stress state and environment; different test methods can give different ranking orders concerning SCC resistance. The performance of duplex stainless steels in a chloride-containing environment at higher temperatures was not as good as expected when dynamic loading was involved.     

Real time pit initiation studies on stainless steels: The effect of sulphide inclusions

It has long been accepted that manganese sulphide favours pitting on stainless steels. However, there are different standpoints on the most important mechanism for pit initiation; due to dissolution of sulphide inclusions, chromium depletion around the inclusion or mechanical rupture of the passive film by metal chlorides. Analysing the pitting potential and metastable pitting rates on different grades of stainless steels has rationalised the effect of sulphide content on pitting corrosion resistance. In situ atomic force microscopy (AFM) has been used in conjunction with conventional electrochemical techniques for imaging real time pit initiation events.     

Application of discrete distribution point heat source model to simulate multipass weld thermal cycles in medium thick plates

Abstract

An analytical solution to the heat flow differential equation has been proposed, which allows an adequate and simplified approach to multipass welding conditions in the heat affected zone. The solution is based on the medium thick plate temperature distribution initially proposed by Rosenthal. The model applies a discrete distribution of point heat sources localised on any point of the plate that is being welded. This approach allows changing the position of the heat sources in the groove from one pass to another, reproducing multipass welding conditions. Actual thermal cycles of multipass welding of AISI 304 and 2304 stainless steels were recorded and compared with simulated thermal cycles, which verified the agreement between the simulated and the actual HAZ thermal cycles. Microstructures of alloys UNS S32304 and UNS S32205 were reproduced in the Gleeble system using the calculated thermal cycles and their comparison with actual weld microstructures confirmed the utility of the proposed heat flow model for metallurgical weldability studies involving multipass welding.     

The influence of Mn compared to that of Cr,Mo and S on the resistance to initiation of pitting and crevice corrosion in austenitic stainless steels

A large number of production and laboratory heats in grades AISI 304 and 316 with normal and extremely low managanese and sulphur contents and a number of production heats in more highly alloyed austenitic stainless steels have been studied with regard to their resistance to initiation of pitting and crevice corrosion at various temperatures. The criteria for resistance to initiation was the potentiodynamic pitting potential in 0.1 M NaCl and synthetic seawater and the time to attack initiation for crevice corrosion in 0.5 and 5% NaCl solutions. A large number of production and laboratory heats in grades AISI 304 and 316 with normal and extremely low managanese and sulphur contents and a number of production heats in more highly alloyed austenitic stainless steels have been studied with regard to their resistance to initiation of pitting and crevice corrosion at various temperatures. The critieria for resistance to initiation was the potentiodynamic pitting potential in 0.1 M NaCl and synthetic seawater and the time to attack initiation for crevice corrosion in 0.5 and 5% NaCl solutions. The main aims of the study were to examine both the effect of manganese relative to that of chromium, molybdenum and sulphur and the effect of heat treatment and sulphide composition on steels with low manganese contents. Mathematical models for calculation of the pitting potentials have been constructed and multiple linear regression analysis gave the equations and their reliabilities. Lowering of the Mn content in austenitic stainless steels to 0.2% gives rise to a material of interest for constructions where pitting or crevice corrosion are judged to be the only potential types of attack, where operational disturbances leading to greatly increased corrosivity do not occur, where attack can not be tolerated, and where steel with normal managanese content has not exhibited fully satisfactory corrosion resistance. If the above conditions are fulfilled the low manganese content can be said to correspond to the same positive effect as is obtained by an addition of the least 1.5% Mo.     

UNS S32304双相不锈钢等离子弧焊接头的组织及其耐点蚀性能

采用恒电位临界点蚀温度(CPT)法,利用OM,SEM,EDX和恒电位极化技术等研究了等离子弧焊接对双相不锈钢UNSS32304焊接接头微观组织及其耐点蚀性能的影响.结果表明,焊接接头热影响区和熔合区微观组织较母材相比发生了显著变化,两相比例严重失衡,铁素体所占比例均大于70%;两区域微观组织形态发生明显变化.且在铁素体晶粒内及两相相界处析出大量氮化物;焊接接头的耐点蚀性能明显下降,点蚀优先发生在高温热影响区所在的铁素体晶粒内.     

Reduction in area and appearance of hydrogen-assisted fracture surfaces of cathodically charged differnt Low-alloy sulphur containing steels

The present work is concerned with the role of sulphidic inclusions in hydrogen-assisted cracking of low-alloy steels with different sulphur contents. The steels were previously cathodically charged in sulphuric acid solution. Evaluating the susceptibility to hydrogen-assisted cracking in terms of the reduction in area values, the high sulphur steel is less susceptible than the low sulphur steel. The fracture surface of the low sulphur steel appears rather brittle, with local quasi-cleavage fractures around large intergranular fracture facets. In contrast, the fracture surface of the high sulphur steel is characterized predominantly by the microvoid coalescence mode, with a great number of manganese sulphide inclusions. The difference between the two sulphur steels is based upon the concept that the interfaces between sulphidic inclusions and matrix act as trapping sites for hydrogen and thus hydrogen is uniformly distributed over the sulphidic inclusions.     

High temperature corrosion behaviour of a new Ni-30Fe-10Al-Cr-Alloy

The high temperature corrosion behaviour of a new duplex nickel-base alloy containing about 30 mass% iron, 10 miss% aluminium and 8 mass% chromium was determined in both air and hot process gases containing methane/hydrogen, sulphur dioxide and hydrogen sulphide, respectively. It was found that the corrosion resistance against carburisation, sulphidation and oxidation was excellent due to the formation of a dense, protective alumina scale. The adherence of the alumina scale was increased by an addition of 0.1 mass% hafnium. The concentration of chromium was found to have a remarkable impact on the oxidation and high temperature corrosion resistance. Alloys without chromium showed increased corrosion rates in both air and sulphur-containing gas atmospheres due to the initial formation of nickel oxides. In sulphidising SO₂- and H₂S- containing gases at least 4 mass% chromium are required to stabilise the formation of alumina and to prevent the formation of nickel/sulphur compounds.     

Cr对钢耐海水腐蚀性的影响

获得了５种含铬低合金钢在海水中暴露１、２、４、８（７）年的腐蚀数据,讨论Ｃｒ对钢耐海水腐蚀的影响,铬钢的耐海水腐蚀性不仅与Ｃｒ的含量有关,还与其他复合合金元素有关。短期浸泡时,钢的耐海水腐蚀性随铬含量（无其他合金元素复合）增加而提高。长期浸泡,Ｃｒ对钢的耐海水腐蚀性有害,约１％Ｃｒ与Ｍｏ（－Ａｌ）复合对钢的耐海水腐蚀性的影响与Ｃｒ的影响没有左别大于２％Ｃｒ与Ｍｏ（－Ａｌ）复合大幅度提高钢在海水中短期浸泡的耐蚀性,并使耐蚀性逆转时间明显推迟.小于1%Cr与Mn-Cu、Cu-Si-V、Ni-Cu-Si、Ni-Mn等复合对钢的耐海水腐蚀性有害。     

Economy in Metal Finishing

The effect of chromium and of nickel plating on the fatigue strength of steel was investigated. In the work on chromium a variety of steels of different compositions and ultimate tensile strengths was plated and, for unbaked deposits, a linear relationship between the percentage change in fatigue strength on chromium plating and the fatigue limit of the steel substrate was established. It is thus possible to predict the percentage change in fatigue strength for deposits of known internal stress from a knowledge of the fatigue limit, the ultimate tensile strength, or hardness of the steel, irrespective of its composition and a simple formula has been derived for this purpose.

The mode of failure of chromium plated components under alternating stress is discussed and there is evidence to suggest that for steels of low strengths (less than approximately 18 tons/in.² fatigue limit) failure initiates in the steel at the interface. With steels exceeding this strength the chromium fails first when the applied stress plus the internal stress of the deposit reaches the inherent fatigue limit of the chromium (20–22 tons/in.²). Propagation of the crack into the steel and consequent failure of the component does not appear to occur, however, until the stress concentration at the root of the crack approaches the fatigue limit of the substrate.

The effect of nickel deposits from two dull and three bright baths was studied and there is evidence to suggest that, apart from the effect of thickness, the broad conclusions arrived at in connection with chromium deposits apply for nickel.