真空低压渗碳对304与316L奥氏体不锈钢组织和性能的影响

采用真空低压渗碳技术对304和316L奥氏体不锈钢进行表面强化,利用光学显微镜、扫描电镜、Thermo-Calc热力学软件、X射线衍射仪和显微硬度计等对渗碳层显微组织、相组成及硬度分布进行分析表征,计算了奥氏体不锈钢渗碳层中不同衍射峰的偏移量及渗碳前后晶格常数的变化量。结合钼对奥氏体不锈钢渗碳过程的影响,对比研究了304和316L奥氏体不锈钢渗碳后,在渗碳层深度、表面硬度及碳化物的析出规律等方面的差异。结果表明,经750 ℃真空渗碳2.6 h后,304和316L奥氏体不锈钢晶格常数分别增加了1.33%和1.14%,形成了由膨胀奥氏体和Cr₂₃C₆组成的渗碳层,Cr₂₃C₆在渗碳层中主要以条状沿膨胀奥氏体晶界析出,表面硬度较基体硬度均提升了两倍以上。     

Microstructure and mechanical properties of austenitic stainless steels after cold rolling

The effect of austenite stability on the evolution of microstructure and mechanical properties of three austenitic stainless steels during cold rolling has been studied. Samples of different grain sizes have been used to characterize the microstructures during deformation. In the case of 304/8% Ni and 304/10% Ni stainless steels, the transformation microstructures consist of mechanical twins: ε-martensite and α′-martensite. No hexagonal close-packed (hcp) ε-martensite was detected in 316 stainless steel. The volume fraction of α′-martensite formed increases with increasing strain in 304 and 316 stainless steels for a given grain size. The amount of α′ phase increases with a decrease in grain size in 304 stainless steel, while the formation of this phase has been found to be grain size insensitive in 316 stainless steel. The strain-hardening behavior exhibited by the three stainless steels used in this study indicates the contribution of both α′-martensite and grain size strengthening in the case of both 304 stainless steels, while only grain size contribution was found in the case of 316 stainless steel.     

On the stress corrosion cracking and hydrogen embrittlement of sensitized austenitic stainless steels in boiling saturated magnesium chloride solutions: Effect of applied stress

Stress corrosion cracking (SCC) and hydrogen embrittlement (HE) of sensitized stainless steels of types 304, 310 and 316 were investigated as a function of applied stress at different test temperatures in boiling saturated magnesium chloride (MgCl₂) solutions under a constant applied stress condition. The stress dependence of fracture appearance and three parameters of time to failure (t_f), steady-state elongation rate (l_ss) and transition time to time to failure ratio suggests that types 304 and 310 suffered SCC, while type 316 suffered only HE. It was also found that the applied stress dependence of three parameters for the sensitized types 304 and 310 was almost similar to that of the solution-annealed stainless steels, whereas that of type 316 showed a clear difference between sensitized and solution-annealed specimens. The relationships between the logarithms of the time to failure and the steady-state elongation rate became a straight line for all stainless steels. However, its slope depended upon the fracture mode: −2.0 for SCC and −1.5 for HE. This showed that the steady-state elongation rate was a good parameter for predicting the time to failure for the stainless steels in the MgCl₂ solutions. The results obtained were explained in terms of martensite transformation, hydrogen entry site, and sensitization.     

Studies of the tensile and corrosion fatigue behaviour of austenitic stainless steels

Corrosion fatigue behaviour of four types of austenitic stainless steels were investigated in boiling 45% magnesium chloride solution at a stress ratio of 0.25 and a frequency of 0.1 Hz. Type 316LN stainless steel possessed the best resistance and type 304 stainless steel had the lowest resistance to corrosion fatigue. XPS studies on the fracture surface indicated that the presence of nitrogen as ion in the surface film of type 316LN stainless steel gave it the highest resistance to corrosion fatigue. Fractographic examination showed wholly transgranular cracking in all cases.     

Oxidation resistance of sintered stainless steels: effect of yttria additions

The porosity of sintered stainless steels modifies their oxidation behavior, as compared to that of wrought stainless steels. This work studies the oxidation behavior of three sintered stainless steels: one ferritic (AISI 434L) and two austenitic (AISI 316L and 304L). 304L with yttria additions is also been studied to explore the possibility of reducing the oxidation rate of austenitic stainless steels by using this reactive element. The results demonstrate the influence of the formation of NiFe₂O₄ on the high-temperature behavior of sintered austenitic stainless steels and the effectiveness of yttria additions in increasing the oxidation resistance at 800 °C.     

0Cr25Ni7Mo4、316与304不锈钢临界点蚀温度研究

采用外加恒定电位下腐蚀电流-温度扫描方法研究了0Cr25Ni7Mo4、304和316不锈钢在1 mol/L NaCl水溶液中的点蚀行为。利用不锈钢临界点蚀温度评价了材料的耐点蚀性能.测得0Cr25Ni7Mo4和316不锈钢的临界点蚀温度分别为79.5 ℃和15 ℃,304不锈钢在0 ℃以下.对0Cr25Ni7Mo4不锈钢材料优良耐点蚀性能的原因进行了分析讨论.     

ATMOSPHERIC CORROSION OF 304AND 316 STAINLESS STEELS

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Cl离子对 304、316不锈钢临界点蚀温度的影响

采用外加恒定电位下腐蚀电流-温度扫描的方法分别研究了304、316不锈钢在不同浓度NaCl水溶液中的临界点蚀温度.得到了材料临界点蚀温度随Cl-浓度变化的关系曲线.在分析温度与Cl-浓度分别对钝化膜影响的基础上阐述了二者对不锈钢点蚀的综合作用机理.     

Depassivation-repassivation behavior of type-312L stainless steel in NaCl solution investigated by the micro-indentation

Repassivation behavior of type-312L stainless steel containing 6% of molybdenum was examined in NaCl solution using in situ micro-indentation technique, together with type-304 and 316L stainless steels. High stability of the passive film formed on the type-312L stainless steel was also examined by depth profiling analysis of passive films using glow discharge optical emission spectroscopy (GDOES). In 0.9 mol dm⁻³ NaCl solution at 296 K the type-304 and 316L stainless steels are passive only up to 0.3 V (SHE), above which pitting corrosion occurs. In contrast, no pitting corrosion occurs on type-312L stainless steel. Despite the significant difference of the pitting corrosion resistance, the repassivation kinetics of the three stainless steels, examined by micro-indentation at 0.3 V (SHE), is similar. The presence of molybdenum in the stainless steel does not influence the repassivation kinetics. The charge required to repassivate the ruptured type-312L stainless steel surface increases approximately linearly with the potential, even though the passivity-maintaining current increased markedly at potentials close to the transpassive region. Repassivation occurs without accompanying significant dissolution of steel, regardless of the stability of passive state. Depth profiling analyses of the passive films on the type-312L stainless steels formed at several potentials revealed that molybdenum species enrich in the outer layer of the passive film, below which chromium-enriched layer is present. The permeation of chloride ions may be impeded by the outer layer containing molybdate, enhancing the resistance against the localized corrosion of the type-312L stainless steel.     

The Role of Silicon in the Reactive-Elements Effect on the Oxidation of Conventional Austenitic Stainless Steel

In this work we evaluate the influence of silicon on the high-temperature oxidation of austenitic stainless steels and propose a mechanism that explains the Reactive-Element Effect (REE) in terms of a synergistic action between the reactive element and the silica layer that forms in the innermost areas of the scale. To do this we have studied the oxidation at 900°C of austenitic commercial alloys (AISI-304, AISI-316 and AISI-310S) and a laboratory-designed high-silicon stainless steel (AISI-304). Lanthanum was selected as the reactive element which was surface deposited by means of ion interchange. Results obtained in this work allowed us to state that the reactive element would enhance the formation of a silica layer that shows diffusion through the scale. The reactive element also changes the expansion coefficient at the scale-alloy interface, increasing the adherence of the oxide layer to the metal.     

Effect of Cold-Rolling on Precipitation Phenomena in Sensitized Type 316L and 340L Austenitic Stainless Steels

Precipitation phenomena in Type 316L and 304L stainless steels were studied mainly by transmission electron microscopic (TEM) observations after cold-rolling ranging from 0% (as solution annealed) to 80% reduction in thickness,and then by sensitization treatment. Precipitates were identified by electron diffraction analysis and EDS analysis.Precipitates observed in sensitized 316L stainless steel were sigma and chi phases, whereas carbide and sigma were observed in sensitized 304L stainless steel. Recrystallized grains were formed in 30% cold-rolled and sensitized 304L.However, the tendency toward recrystallization in sensitized 316L was much lower than in 304L. Precipitation of sigma and chi phases was accelerated by cold-rolling and they were observed at grain boundaries in lower cold-rolling; they were also seen, in grain interiors in higher cold-rolling. Higher deformation induced partially recrystallization combined with precipitation, resulting in the formation of heterogeneous microstructures.     

Effect of Cold-Rolling on Precipitation Phenomena in Sensitized Type 316L and 304L Austenitic Stainless Steels

Precipitation phenomena in Type 316L and 304L stainless steels were studied mainly by transmission electron microscopic (TEM) observations after cold-rolling ranging from 0% (as solution annealed) to 80% reduction in thickness,and then by sensitization treatment. Precipitates were identified by electron diffraction analysis and EDS analysis.Precipitates observed in sensitized 316L stainless steel were sigma and chi phases, whereas carbide and sigma were observed in sensitized 304L stainless steel. Recrystallized grains were formed in 30% cold-rolled and sensitized 304L.However, the tendency toward recrystallization in sensitized 316L was much lower than in 304L. Precipitation of sigma and chi phases was accelerated by cold-rolling and they were observed at grain boundaries in lower cold-rolling; they were also seen, in grain interiors in higher cold-rolling. Higher deformation induced partially recrystallization combined with precipitation, resulting in the formation of heterogeneous microstructures.     

Investigation of the diffusion kinetics of borided stainless steels

In this study, the kinetics of borides formed on AISI 420, AISI 304 and AISI 304L stainless steels was investigated. Boronizing treatment was carried out using Ekabor-II powders at the processing temperatures of 1123, 1173 and 1223 K for 2, 4 and 6 h. The phases of the boride layers of borided AISI 420, AISI 304 and AISI 304L stainless steels were FeB, Fe₂B, CrB and NiB, respectively. The thickness of the boride layer formed on the borided steels ranged from 4.6 to 64 μm depending on the boriding temperature, boriding time and alloying elements of the stainless steels. Depending on the chemical composition, temperature and layer thickness, the activation energies of boron in AISI 420, AISI 304 and AISI 304L stainless steels were found to be 206.161, 234.641 and 222.818 kJ/mol, respectively. The kinetics of growth of the boride layers formed on the AISI 420, AISI 304 and AISI 304L stainless steels and the thickness of the boride layers were investigated.     

不锈钢盐酸露点腐蚀行为的原位研究

利用一种新型的露点腐蚀模拟装置结合原位的电化学阻抗谱,电化学噪声等测试手段评价了304和316L两种不锈钢的盐酸露点腐蚀行为.结果表明,316L不锈钢表现出更优异的耐盐酸露点腐蚀性能,主要原因可归结为两点:一是316L不锈钢钝化膜中含有较高的Cr/(Cr+Fe) 比以及较低含量的Fe;二是316L不锈钢钝化膜中含有能改善抗点蚀性能的Mo.     

Effect of sulfur and oxygen on weld penetration of high-purity austenitic stainless steels

Convective flow during arc welding depends upon the surface tension gradient (dy/dT, Marangoni flow), buoyancy, arc drag force, electromagnetic force, shielding gas, and the viscosity of the melt. The Marangoni and the buoyancy-driven flow are the major factors in controlling weld penetration in ferrous alloys, especially austenitic stainless steels such as 304 and 316. Small variations in the concentration of surfactants, such as sulfur and oxygen, in stainless steels cause significant changes in the weld penetration and depth/width (D/W) ratio of the fusion zone. Gas-tungsten arc (GTA) welds were done on low- and high-sulfur 304 and 316 heats using pure argon and argon/oxygen shielding gases. Also, laser beam (LB) welds were done on the 304 and 316 heats using pure argon as the shielding gas. Increase in the sulfur content decreased the D/W ratio for the GTA 304 welds using pure argon, but for the case of LB 304 welds the results were the opposite. For the GTA 316 welds and LB 316 welds, increase in sulfur increased the D/W ratio of the fusion zone. Oxygen increased the D/W ratio of both the 304 and 316 GTA welds.     

Electrochemical and XPS studies of the passive film formed on stainless steels in borate buffer and chloride solutions

The passivity of AISI 304L and AISI 316L stainless steels in a borate buffer solution, with and without the addition of chloride ions, was studied using cyclic voltammetry and potentiodynamic measurements. The passive layers formed by electrochemical oxidation at different passivation potentials on both the stainless steels were studied by X-ray photoelectron spectroscopy, their compositions were analysed as a function of depth, and the cationic fraction of the passive film was determined. The passive films established on the two stainless steels in the borate buffer solution at pH = 9.3 contained the oxides of two main elements, i.e., Fe and Cr. The oxides of the alloying elements Ni and, optionally, Mo, also contribute to the passive layer. In the presence of chloride ions a strong chromium enrichment was observed in the passive layers.     

Pitting Potential of stainless steels in artificial sweat

The pitting potentials of 12/12, 316 PX, AISI 303, 304, 316F and 316L austenitic stainless steels were determined in artificial sweat (perspiration) at room temperature. Two compositions of sweat were used: the BAM composition which contains two malodorous organic acids and the composition proposed in an ISO standard which does not contain them. The quasi-potentiostatic method (10 mV potential steps per min), potentiodynamic technique (1 V/min linear sweep) and scratch test were used on mechanically polished and HNO₃-passivated surfaces. The aggressivity of the two artificial sweats with respect to stainless steels was found to be practically the same. The pitting potentials and the classification of the stainless steels according to their pitting potential values were found to depend on the surface preparation and, to a lesser extent, on the test method. The experimental techniques were often complementary and a combination of two or three methods in conjunction may increase the confidence with which the conclusions can be applied. The lowest pitting corrosion resistance was found for AISI 303 and the highest for AISI 316L. As expected stainless steels with the lowest concentration of nonmetallic inclusions (sulfides and oxides) exhibited the best pitting corrosion resistance.     

Effect of Mo and Mn additions on the corrosion behaviour of AISI 304 and 316 stainless steels in H2SO4

The work addresses the influence of Mn and Mo additions on corrosion resistance of AISI 304 and 316 stainless steels in 30 wt.% H₂SO₄ at 25 and 50 °C. Corrosion mechanism was determined by gravimetric tests, DC polarization measurements and electrochemical impedance spectroscopy (EIS). The morphology and nature of the reaction products formed on the material surface were analysed by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). Reduction of temperature from 50 to 25 °C drastically decreased the corrosion rate of AISI 304 and 316 stainless steels in sulphuric acid solution. Mn additions did not affect significantly the general corrosion resistance due to its low ability to form insoluble compounds in acid medium. Meanwhile, the formation of molybdenum insoluble oxides enhanced the corrosion performance.     

Influence of Cu and Sn content in the corrosion of AISI 304 and 316 stainless steels in H2SO4

This paper addresses the influence of Cu and Sn addition on the corrosion resistance of AISI 304 and 316 stainless steels in 30 wt% H₂SO₄ at 25 and 50 °C. The corrosion process was evaluated by gravimetric tests, DC measurements and electrochemical impedance spectroscopy (EIS). The corrosion products were analysed by SEM, X-ray mapping and XPS before and after accelerated tests. The behaviour of both AISI 304 and 316 stainless steels in sulphuric acid solution was greatly improved by increasing Cu concentration and the synergic effect of Cu and Sn. Addition of Sn increased corrosion resistance, but less than addition of copper.     

Improvement of pitting corrosion resistance of AISI 444 stainless steel to make it a possible substitute for AISI 304L and 316L in hot natural waters

The pitting corrosion resistance of AISI 444, 304L and 316L stainless steels in two tap waters with different chloride concentrations at 80 °C was studied. Cyclic potentiodynamic polarization (CPP) tests were carried out starting from E_corr ? 30 mV until the current density reached 0.1 mA/cm² (scan rate 0.166 mV/s); the scan was then reversed and continued until new passivity conditions were achieved. The corrosion potential was measured before the polarization experiments. From the E‐log i plots, the values of pitting and protection potential were obtained; from these potentials, the perfect and the imperfect passivity regions were defined to compare the corrosion resistance of the studied steels. CPP tests were performed both on as received stainless steel samples and on samples submitted to different cleaning–passivation treatments to improve their corrosion resistance. The results indicate that, for industrial production, AISI 444 stainless steel can substitute the more expensive AISI 304L or 316L after a cleaning–passivation treatment that reduces the presence of inclusions.