Thermal treatment improving creep properties of nitrogen-added Mod.9Cr-1Mo steels

Generation IV reactors are being developed to produce a reliable energy safely and with an economic benefit, because nuclear energy is being seriously considered to meet the increasing demand for a world-wide energy supply without environmental effects. Ferritic/martensitic steels are attracting attention as candidate materials for the Gen-IV reactors due to their high strength and thermal conductivity, low thermal expansion, and good resistance to corrosion. In recent years, new ferritic/martensitic steels have been developed for ultra supercritical fossil power plants through advanced technologies for steel fabrication. The microstructural stability of these materials for the pressure vessel, cladding and core structure of the VHTR and SFR is very important. Nitrogen is a precipitation hardening element, and the thermal stability of nitrides is superior to that of carbides. So the formation of nitrides may improve the thermal stability of the microstructure and eventually increase the creep rupture strength of high Cr steels. The effect of nitrogen on the creep rupture strength and microstructure evolution of nitrogen-added Mod.9Cr-1Mo steels has been studied. Creep testing was carried out at 873 and 923 K under constant load conditions. The optimum controlled Cr₂X precipitates were developed by special heat treatment, and they were not dissolved after a creep deformation. These fine and stable Cr₂X precipitates contributed to the increase of the creep rupture strength. The prior austenite grain size and martensite lath width were decreased by the resultant stable nitrides.     

Prospects for 12Cr martensitic creep resistant steels for 650℃steam power plant

In the last three decades new stronger modified 9%Cr steels have been introduced in new power plants with steam parameters up to 300 bar(1 bar =10~5 Pa) and 600℃. In order to further increase the steam parameters of steel based power plants up to a target value of 650℃/ 325 bar it is necessary to double the creep strength compared with todays strongest 9%Cr steels,and at the same time the resistance against steam oxidation must be improved by adding 12%Cr to the steel. However,so far all attempts to make stronger 12%Cr steels have been unsuccessful because the high chromium content introduced severe microstructure instabilities in the tested steels.Recently,it was found that the microstructure instabilities in 11%- 12%Cr steels can be explained by the precipitation of coarse Cr(V,Nb)N Z-phases, which dissolve fine(V,Nb)N nitrides. A new possibility to use the Z-phase for strengthening of 12%Cr steels has been identified,and the development of stable strong martensitic 12%Cr steels based on this concept is expected to allow the construction of 325 bar/ 650℃steam power plants all based on steel.     

Surface hardening of Ti alloys by gas-phase nitridation: Kinetic control of the nitrogen surface activity

A new concept for surface hardening of titanium alloys has been developed and successfully applied to Ti-6Al-4V alloys: gas-phase nitridation under kinetic control of the nitrogen activity. This method avoids the formation of detrimental second-phase nitrides by nitriding under a very low nitrogen activity, combined with rapid diffusion of nitrogen into the specimen. The surface hardness of the Ti-6Al-4V alloy was increased by a factor of 2 to ≈ 12 GPa, with only modest attenuation of ductility. We have realized conditions for generating case depths of ≈ 25 μm in reasonable nitridation times. The nitrogen activity in the gas phase is generated by heating a powder pack of Cr and Cr₂N. A closed two-zone system allows the powder pack and the specimen to be at different temperatures, optimizing both the nitrogen partial pressure and the nitrogen diffusion into the specimen. This low-cost, conformal nitridation process generates a smoothly graded nitrogen concentration profile and can be applied to finished Ti alloy components.     

The microstructure of chromium-tungsten steels

Chromium-tungsten steels are being developed to replace the Cr-Mo steels for fusion-reactor applications. Eight experimental steels were produced and examined by optical and electron microscopy. Chromium concentrations of 2.25, 5, 9 and 12 pct were used. Steels with these chromium compositions and with 2 pct W and 0.25 pct V were produced. To determine the effect of tungsten and vanadium, three other 2.25Cr steels were produced as follows: an alloy with 2 pct W and 0 pct V and alloys with 0 and 1 pct W and 0.25 pct V. A 9Cr steel containing 2 pct W, 0.25 pct V, and 0.07 pct Ta also was studied. For all alloys, carbon was maintained at 0.1 pct. Two pct tungsten was required in the 2.25Cr steels to produce 100 pct bainite (no polygonal ferrite). The 5Cr and 9Cr steels were 100 pct martensite, but the 12Cr steel contained about 25 pct delta-ferrite. Precipitate morphology and precipitate types varied, depending on the chromium content. For the 2.25Cr steels, M₃C and M₇C₃ were the primary precipitates; for the 9Cr and 12Cr steels, M₂₃C₆ was the primary precipitate. The 5Cr steel contained M₇C₃ and M₂₃C₆. All of the steels with vanadium also contained MC.     

Alloying Elements in High Speed Steels

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The Role of Alloy Composition on the Stability of Nitrides in Ti-Microalloyed Steels during Weld Thermal Cycles

The effect of weld thermal cycling on titanium nitride stability in a range of normalized Timicroalloyed steels containing various alloying additions of V, Al, and N has been investigated. Nitride dispersions and the chemical analysis of individual particles are studied using transmission electron microscopy and a quantitative 200 kV STEM-EDX-EELS microanalysis system. It is found that whereas the normalized material contains various nitrides of mixed compositions, only nitrides based on TiN survive high energy simulated weld cycles. Grain growth in weld cycled material is highly dependent upon the stability of nitrides during the weld cycle, and this stability depends on the original composition of the nitrides and hence of the steel itself. The presence of aluminum in the particles is particularly detrimental in this respect. The best grain growth control and highest toughness are found in steels based on optimum ratios of Ti/V/N and on low Al levels. The possible way in which the steel’s composition affects particle stability and hence grain growth during weld thermal cycles is discussed.     

Some Highlights on New Steel Products for Automotive Use

This paper is a short review on some recent developments regarding steels for automotive use. A new precoated steel suitable for to hot stamping processing has been developed, which is most appropriate for producing anti‐intrusion parts. Another evolution of precoated steels is a new inorganic treatment (NIT), which has proved to be efficient in increasing the stamping productivity of precoated steels. In the field of corrosion protection, a new generation of thin organic coatings has been implemented and in the future Zn‐Mg metallic coatings will help to save auxiliary anticorrosion measures such as wax and mastics. To offer steels with high stiffness but low weight, Arcelor has developed a new multimaterial sandwich which shows a good potential for large panels due to its high stiffness. Finally, some breakthrough steel products are discussed as possible candidates for mid/long term applications.     

Titanium Containing High Strength Sulfuric Acid Corrosion Resistant Steel

Ti containing low alloy steel free of Sb is found to have higher strength than and equivalent sulfuric acid corrosion (SAC) resistance to traditional SAC resistant steels in Cu? Cr? Sb system. SAC resistance of the Ti containing steel was investigated with potentiodynamic polarization, linear polarization resistance, electrochemical impedance spectroscopy, and weight loss measurements in a solution of 20 wt% H₂SO₄ at 20°C. All measurements confirm that Ti addition is suitable for designing high strength SAC resistant steels.     

Development and Application of a Stainless CrNbMoC Tool Steel

Steels with 15 mass% Cr, 2 mass% Mo and varying contents of C, V, Nb and Ti were investigated by thermodynamic calculations to find a stainless grade promising a wear resistance equal to that of the standard cold work tool steel X153CrMoV12. It was shown that Nb is most suited to form MC carbides for wear resistance thus reducing the content of M₇C₃, which in turn raised the Cr content dissolved in the matrix to a passivating level. Small melts in the vicinity of steel X140CrNbMoTi15‐5‐2 confirmed this concept in respect to hardenability, wear resistance and corrosion resistance. Industrial manufacturing and application of the new grade RN15X® will be discussed.     

Microstructure and thermal stability of coated Si3N4 and SiC

Microstructure of coatings obtained by treating Si₃N₄ and SiC in Cr powders at 1273–1623 K has been studied employing XRD, SEM, AES and TEM. In accordance with thermodynamic calculations and kinetic consideration, the coatings have layered structures and contain metal-rich silicides and metal-rich nitrides or carbides. The microstructure of the coatings has been found to depend on the treatment conditions. The kinetics of the coatings growth obeys a parabolic growth law, the activation energies being close to the activation energies for self-diffusion of the corresponding metals. Thermal stability of the coated and uncoated Si₃N₄ and SiC in Fe-, Ni- and Co-based matrices has been studied and the coatings have been found to considerably improve the stability of Si₃N₄- and SiC-metal interfaces.     

高耐蚀深冲用不锈钢00Cr17MoTiCu的开发

本文采用电化学、盐雾试验、酸溶液中的耐蚀性试验等腐蚀试验方法,评价了Cr、Mo、Ti、Cu等元素的作用,同时采用力学试验和各种成型试验方法探讨了上述元素的影响。根据试验结果成功地开发了既具有可以和1Cr18Ni9Tj相媲美的不锈耐蚀性能;又具有Cr17型不锈钢美观、价廉等特征的新型深冲用不锈钢00Cr17MoTiCu。该新型不锈钢可广泛应用于食品加工、厨房设备、轻工纺织、建筑五金等行业。     

Nitride Formation and Excess Nitrogen Uptake After Nitriding Ferritic Fe-Ti-Cr Alloys

The microstructure of the nitrided zone of Fe-Ti-Cr alloys, containing a total of 0.30 at. pct (Ti + Cr) alloying elements, with varying Ti/Cr atomic ratio (0.45, 0.87, and 1.90), was investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The stable TiN and CrN nitrides did not precipitate after nitriding. Instead, ultrafine, metastable, mixed Ti_1–x Cr _x N nitride precipitates developed in the nitrided zone: The precipitates were of platelet morphology (length ≤30 nm and thickness ≤3 nm) and of cubic, rock-salt, crystal-structure type. The misfit strain around the nitride platelets in the ferrite matrix increases with increasing Ti/Cr atomic ratio. As a consequence, most pronouncedly for the highest Ti/Cr atomic ratio, a tetragonally distorted ferrite matrix surrounds the precipitates, as evidenced both by XRD and TEM. The amount of nitrogen taken up was determined quantitatively by measuring the so-called nitrogen-absorption isotherms. It follows that the absorbed amount of so-called excess nitrogen dissolved in the matrix and adsorbed at the nitride-platelet faces increases distinctly with increasing Ti/Cr atomic ratio. The results were discussed in terms of the dependence of misfit strain on the Ti/Cr atomic ratio and the higher chemical affinity of Ti for N than of Cr for N.     

Effect of carbon concentration on precipitation behavior of M<Subscript>23</Subscript>C<Subscript>6</Subscript> carbides and MX carbonitrides in martensitic 9Cr steel during heat treatment

The distributions and precipitated amounts of M₂₃C₆ carbides and MX-type carbonitrides with decreasing carbon content from 0.16 to 0.002 mass pct in 9Cr-3W steel, which is used as a heat-resistant steel, has been investigated. The microstructures of the steels are observed to be martensite. Distributions of precipitates differ greatly among the steels depending on carbon concentration. In the steels containing carbon at levels above 0.05 pct, M₂₃C₆ carbides precipitate along boundaries and fine MX carbonitrides precipitate mainly in the matrix after tempering. In 0.002 pct C steel, there are no M₂₃C₆ carbide precipitates, and instead, fine MX with sizes of 2 to 20 nm precipitate densely along boundaries. In 0.02 pct C steel, a small amount of M₂₃C₆ carbides precipitate, but the sizes are quite large and the main precipitates along boundaries are MX, as with 0.002 pct C steel. A combination of the removal of any carbide whose size is much larger than that of MX-type nitrides, and the fine distributions of MX-type nitrides along boundaries, is significantly effective for the stabilization of a variety of boundaries in the martensitic 9Cr steel.     

Influence of titanium microalloying on the properties of low-alloy Cr–Mo–V steel

The influence of titanium, which readily forms nitrides, on the structure and the long- and short-term mechanical properties of Cr–Mo–V steel is investigated. Increase in the Ti content to 0.075% increases the thermal stability of the steel. With increase in Ti content to 0.13%, the thermal stability of the steel declines sharply, on account of structural changes.     

Application of coatings of some transition metal borides by plasma-deposition

Conclusions During plasma-deposition chromium, zirconium, titanium, and tungsten borides experience thermal dissociation and react with nitrogen in the working gas and with oxygen in the ambient atmosphere. This leads to the formation in coatings of nitrides and oxides of the metals and of boron. The amount of such inclusions depends on the coating deposition conditions. Optimum conditions for the plasma-deposition of CrB₂ and ZrB₂ have been chosen. CrB₂ and ZrB₂ coatings adhere to Kh18N10T steel with strengths of 0.153±0.01 and 0.144±0.04 kgf/mm², respectively. A nickel aluminide undercoat more than trebles the adhesional strength of boride coatings on Kh18N10T steel. The processes developed for the manufacture of transition metal borides and its optimum conditions and methods for their deposition on Kh18N10T steel by the plasma process may be recommended for adoption in industry.Translated from Poroshkovaya Metallurgiya, No. 5(209), pp. 73–76, May, 1980.     

CSP工艺钛微合金碳钢中的碳氮化钛析出相

 应用透射电镜、高分辨电镜等方法观察分析了薄板坯连铸连轧EAF-CSP工艺生产的微钛低碳钢热轧板的含钛析出相,实验钢的成分为(mass%）：C：0.04~0.07%、Si：0.6%、Mn：0.6%、Ti：0.06~0.14 %。电解萃取及X射线衍射分析结果表明：钢中存在不同碳氮比的碳氮化钛析出相,这些碳氮化物的C/N比值的差异是由各个析出相的形成温度及析出时钛和氮、碳元素在钢中的过饱和度不同而造成的。实验钢萃取粉末（包括各种析出相）的质量分数约占钢的0.305%。其中五分之四左右为渗碳体,另外五分之一主要是钛的碳化物、氮化物和碳氮化物,还有少量的硫化物和氧化物。 在薄板坯连铸连轧工艺的连铸坯及热轧板中均观察到了由相间沉淀方式形成的碳氮化物粒子列。本文讨论了相间沉淀的形成机制。与传统连铸连轧工艺生产的同类钢相比,CSP工艺低碳钢中微量钛的加入明显增加了细小析出相的数量。     

Transformation behaviour of the high temperature martensitic steels with 8 – 14% chromium

Comprehensive development work on martensitic steels belonging to the so-called 12% Cr steel group were performed at the Institute for Materials Research (IMF) of Forschungszentrum Karlsruhe on martensitic steels, the so-called 12% Cr steel group, in order to meet the various requirements in nuclear and conventional energy technology. The transformation characteristics of 29 different grades of steel and 38 heats have been determined and continuous cooling transformation (CCT) diagrams have been prepared. The diagrams are first described by groups of subjects in a chronological order because the change in the chemical composition cannot be correlated in all cases with the change in transformation behaviour. The quenching hardness can be satisfactorily described as a function of the C+N content if, taking into account the Nb, Zr, Ta, Hf fractions, a common effectiveness factor is calculated. This effectiveness factor is also integrated in the calculation of the M_s point by modifying accordingly the equation proposed by Steven and Haynes for low-alloy steels and supplemented by the summands for V and W. An equation is introduced for the calculation of the critical cooling rate for pearlite transformation which takes into account the special influence exerted by elements Cr, V, Mo, W, Ge. The comparison between calculated and measured values for Ms and Vcrit is satisfactory, except for some steels.     

Study of High Temperature Deformation and Recrystallization in W9Mo3Cr4V Steel

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Surface Solidification Behaviour of Micro‐Alloyed Steels under Continuous Casting Conditions

Micro‐alloyed steels are important in steel industry with regard to their unique mechanical properties. Their characterisitcs are mainly caused by the refinement of ferrite grain size by controlled precipitation of nitrides during thermomechanical treatment in hot rolling. Uncontrolled precipitations of titanium nitrides in the surface region during casting and solidification can negatively influence the surface quality of continuously cast steel, particularly when casting, thermal soaking and hot rolling are carried out in a combined process chain. Focus of this work are experimental simulations and mathematical investigations of early solidification in a CC mould, primary precipitation of nitrides, and effects of different influences such as mould contact through casting flux or direct mould contact. A laboratory rig to lead solidification on liquid casting flux was developed. The carbon content of the steel melts was varied.     

Some Thermophysical Properties of Liquid Cr‐Mn‐Ni‐Steels

In the last years new Cr‐Mn‐Ni‐TRIP/TWIP steels have been developed at the Institute of Iron and Steel Technology, Freiberg University of Mining and Technology. Within the Collaborative Research Center SFB 799, the ZrO₂‐ceramic‐TRIP‐steel composite materials are produced using the infiltration of open foam ceramics with liquid steel and using powder metallurgy with small additions of ceramic powder before sintering. The thermophysical properties of liquid steel play an important role in both production routes. They affect the infiltration efficiency in one process and the produced powder size in the other, and therefore finally determine the composite properties. In this work some of these properties were estimated, as they are not available in literature. The investigated steels contain approximately 16% chrome, 7% manganese and 3% to 9% nickel. The surface tension was estimated using two methods: the drop weight method and the maximum bubble pressure method. In the drop weight method similar conditions at the gas/metal interface exist as during the atomization or the infiltration process, where liquid metal is exposed to high volume of inert gas. In all these cases the evaporation of manganese affects the surface tension. For comparison of results and for estimation of the liquid steel density the maximum bubble pressure method was used where the evaporation of manganese is limited. The wettability on partially MgO‐stabilized ZrO₂ ceramic substrates and its change with contact time was determined using the sessile drop method.