粉末冶金锰钢研究新进展

铁基粉末冶金产业在继续开发与扩大使用非传统粉末冶金合金化元素.Mo、Ni与Cu的价格、环境与可回收性一直在推动这种扩大使用.Mn是铸锻钢的价格比较低廉且有效的合金化元素;不过,过去氧的敏感性限制了Mn在粉末冶金钢中的应用,现在氧分压低的氮-氢烧结气氛可允许使用Mn.Mn与适量Mo的组合可使粉末冶金钢合金的力学性能接近F...     

Reactions between ferrous powder compacts and atmospheres during sintering – an overview

ABSTRACT

This overview paper describes the interaction of powder metallurgical iron-base alloys with the atmosphere during sintering. The methods of thermal analysis serve to clarify the processes that take place especially during the heating stage of the sintering cycle. After a discussion of the physical and chemical fundamentals of the sintering process, the methods of thermal analysis are explained. The differences between plain iron and alloyed systems are discussed in detail. Classical PM low alloy steels with alloying elements, such as Cu, Ni and Mo, react in a similar way as unalloyed carbon steels. The situation changes dramatically, when oxygen sensitive elements as chromium, manganese and even more silicon come into play. The removal of the surface oxygen is much more crucial, and there are several competing reactions, which have to be considered when these systems should be sintered in industrial scale to reach the desired mechanical and dimensional properties.     

EFFECT OF ADDITIONAL ALLOYING ELEMENTS ON THE PROPERTIES OF SINTERED MANGANESE STEELS

Abstract

Sintered alloys based on the Fe-Mn system have been investigated by using single-pressing and double-pressing techniques. Fe-Mn (Mn up to 8 wt.-%) and Fe-Mn-C (C up to 1·4 wt.-%) alloys were prepared both with manganese as an electrolytic powder and with a Fe-Mn master alloy. The influence of sintering temperature and sintering time on mechanical properties and homogenization is discussed. The effect of the additional alloying elements Cr, Mo, eu, and of their combinations on mechanical properties has been determined. Further investigations were carried out with a Fe-Mn-Cr-Mo-C master alloy. The optimum single-pressed and double-pressed alloy (Fe with Mn 0·8, Cr 0·8, Mo 0·8, and total C 0·6%) has a tensile strength (σ_B) of >700 N/mm². Optimum alloys of all investigated systems were hot-forged and their mechanical properties are compared with those of single- and double-pressing techniques. The alloys were heat-treated and their tempering behaviour determined. Jominy standard tests were carried out to determine hardenability of the porous sintered materials.     

Structure and mechanical properties of sintered Ni free structural parts

Abstract

Ni, Cu and in some cases Mo are the alloying elements which have traditionally been used in sintered steels. High performance of powder metallurgy (PM) structural parts from Fe powders is reached mainly by alloying of Ni. The use of Mn in Fe base PM structural parts has been avoided because of its high affinity to oxygen. It is difficult to sinter Mn steel, without oxidation, in industrial atmospheres. However, the PM industry follows also possibilities in order to develop Ni free sintered steels which render as high mechanical properties as diffusion alloyed Ni containing sintered steels and further fulfil the requirements of health protection. In recent years Mn have been introduced as alloying element in Fe based structural parts, on laboratory scale and also for pilot scale production. In this paper the factors that contribute to the structure and mechanical properties of sintered Mn steels are summarised.     

Microstructural changes in Mo steels during sintering and effect on electrical conductivity

Abstract

An electrical conductivity measurement method was used for studying the sintering mechanism and microstructural changes of low alloyed PM Mo steels in a temperature range between 600-1300°C. The influences of alloying method (elemental or prealloyed), Mo content (1·5 and 3·5 wt-%), and sintering temperature were investigated. The results show that the effects of, for example, formation of Mo carbide(s), ferrite-austenite phase transformation, as well as liquid phase formation during heating of the steel compacts can be detected by the technique cited. Mo dissolution during sintering of compacts from mixed powders results in a decrease of the conductivity with increasing sintering temperature while compacts from Fe-Mo prealloyed powders exhibit the standard behaviour of higher conductivity after sintering at higher temperature. Moreover, the relationship between Mo dissolution, formation of sintered contacts, and mechanical properties was demonstrated to assess the viability of the conductivity measurement method for studying the sintering behaviour of PM materials and its influence on physical and mechanical properties. An approach was also demonstrated for relating the conductivity to the microstructural parameters, e.g. total porosity and contiguity between solid phase, that would be useful for predicting relative changes in mechanical properties dependent on porosity and pore morphology.     

Phase transformation behaviour in two C–Mn–Si based steels under different cooling rates

Abstract

The continuous cooling transformation (CCT) behaviour of two C–Mn–Si based steels was investigated. The effects of chemical composition and cooling rate on γ→α transformation were studied using dilatometric measurements. Quantitative phase analysis was carried out in order to determine the effect of cooling rate on the precise phase distribution after transformation. Presence of Cr and Mo in the experimental steels appears to retard pearlitic transformation and promotes formation of acicular products (combination of acicular ferrite, Widmanstatten ferrite and bainite). Martensitic transformation also starts at a perceptibly lower cooling rate in the Mo containing alloy as compared with the one without any Mo.     

Leaner alloys for the PM industry

Abstract

Numerous lean alloy systems are now available to the PM parts manufacturer as potential lower cost solutions without sacrificing part performance. More recently, steels containing 0·3 and 0·5% prealloyed molybdenum have been introduced which can be tailored with reduced Ni and/or Cu additions to meet specific properties for use in press and sinter applications or as quench and temper grades. These reduced Mo prealloys complement the already familiar 0·85 and 1·5%Mo grades to provide a full range of prealloyed molybdenum steels. Another method to reduce susceptibility to market pricing has been through incorporating manganese, which is historically inexpensive yet highly beneficial to steel properties. Combining Mn with moderate levels of Mo in specially designed alloy grades provides a lean alternative to Ni and Cu containing hybrid alloy steels. This study will examine these lean alloys and explore where there may be opportunity to use them in place of traditional PM grades.     

Processing and properties of sinter hardened Fe–Cr–Mo steels with admixed extra-fine nickel

Abstract

The processing and properties of chromium–molybdenum, powder metallurgy steels with admixed extra-fine nickel (XF Ni) were investigated. Prealloyed Fe–1·5Cr–0·2Mo powder was blended with different quantities of XF Ni, while a hybrid steel with lower Cr content was prepared by blending Fe–1·5Cr–0·2Mo and Fe–0·5Mo prealloyed powders, with additions of XF Ni and copper powders. These steels were compacted into different part shapes in order to evaluate the effect of part thickness on sinterhardening behaviour. These parts were also subjected to different cooling rates after sintering. This study showed that additions of XF Ni improve the compressibility, densification behaviour and mechanical properties of Cr–Mo steels. Furthermore, the properties of the hybrid steel were shown to be either equal to or greater than those of the reference material. Hardenability of all steels was sufficiently high such that part thickness was seen to have negligible impact. Higher cooling rates generally resulted in improved mechanical properties.     

Fatigue crack growth in some PM low alloy steels consolidated by rotary forging and sintering

Abstract

Fatigue crack propagation rates under plane strain conditions have been investigated for three PM low alloy steels consolidated to high densities by rotary compaction followed by sintering and heat treatment. It is shown that the densities and properties are intermediate between those of pressed and sintered materials and of powder forged materials. Threshold stress intensities compare satisfactorily with those for wrought counterparts, but resistances to crack growth are inferior to those of wrought steels. Possible reasons for the properties of the rotary compacted materials are considered in the light of their microstructures and the behaviour of other PM materials.     

Microstructure and properties of hot‐rolled high strength multiphase steels for automotive application

Effects of alloying with combinations of the elements Mo, Cr and B on the bainite transformation behaviour and microstructure of hot‐rolled high strength sheet steels microalloyed with mass contents of Ti and Nb, 0.05 or 0.15 % C and 1.5 % Mn have been studied. The relationships between microstructures formed in the steels coiled at various temperatures and their mechanical properties have been investigated. The 0.15 % C microalloyed steel alloyed with Mo,Cr and B with a complex bainitic microstructure was found to have distinctive high performance behaviour combining continuous yielding, high tensile strength and plasticity after coiling in a wide temperature region. The strain hardening of the micro‐constituents typical for the investigated steels has been analysed to have a better understanding of the mechanical properties of complex phase microstructures in low alloy ferrous alloys. It was found that bainitic ferrite with austenitemartensite islands as a second phase leads to high strength and adequate elongation. The features of the bainite formation in the Mo, Cr and B alloyed CMn steel microalloyed with Ti and Nb during slow cooling from temperatures between 650 and 550 °C was studied by dilatometry.     

Secondary hardening and fracture behavior in alloy steels containing Mo, W, and Cr

In 4Mo, 6W, 2Mo3W, 2Mo2Cr, and 3W2Cr alloy steels, which cointain alloying elements, such as Mo, W and Cr, contributing to the secondary hardening by forming M₂C type carbide, the secondary hardening and fracture behavior were studied. Molybdenum had a strong effect on secondary hardening, while W had a very weak effect on it but delayed the overaging. The MoW steel exhibited both moderately strong hardening and considerable resistance to overaging. On the other hand, the secondary hardening effect was diminished by the Cr addition, because the cementite of M₃C type was stabilized at higher temperatures and the formation of M₂C carbides was thus inhibited. Although the Cr addition had no merit in the secondary hardening itself, it eliminated the secondary hardening embrittlement (SHE). This was observed as a severe intergranular embrittlement due to the impurity segregation for the Mo and MoW steels and as a decrease in upper shelf energy for W steel, even in the overaged condition.     

Secondary hardening and fracture behavior in alloy steels containing Mo, W, and Cr

In 4Mo, 6W, 2Mo3W, 2Mo2Cr, and 3W2Cr alloy steels, which contain alloying elements, such as Mo, W and Cr, contributing to the secondary hardening by forming M₂C-type carbide, the secondary hardening and fracture behavior were studied. Molybdenum had a strong effect on secondary hardening, while W had a very weak effect on it but delayed the overaging. The MoW steel exhibited both moderately strong hardening and considerable resistance to overaging. On the other hand, the secondary hardening effect was diminished by the Cr addition, because the cementite of M₃C type was stabilized at higher temperatures and the formation of M₂C carbides was thus inhibited. Although the Cr addition had no merit in the secondary hardening itself, it eliminated the secondary hardening embrittlement (SHE). This was observed as a severe intergranular embrittlement due to the impurity segregation for the Mo and MoW steels and as a decrease in upper shelf energy for W steel, even in the overaged condition.     

Electrochemical behaviour of sintered,yttria reinforced ferritic stainless steels

Abstract

The electrochemical behaviour of 434L ferritic stainless steels produced by the powder metallurgy (PM) route has been studied. The effects of sintering temperature (1250 and 1400°C) and dispersoid addition (10%Y₂O₃) have been investigated by potent iodynamic polarisation and electrochemical impedance studies in 0·05 M H₂SO₄ solution. All the alloys exhibited active-passive behaviour in the electrolyte. The critical current density for passivation was lower in the case of the PM samples when compared with 430, which has been attributed to the presence of Mo in the samples. The passive current density of the PM samples correlated with the sintered porosities. All the other passivation parameters were similar for the materials. The nature of passive film was investigated using electrochemical impedance spectroscopy. A lower capacitance (i.e. more corrosion resistant) surface film was obtained after sintering at the higher temperature. Yttria dispersoids in ferritic stainless steel decreased the corrosion resistance of the surface film after sintering at the higher temperature, whereas they did not significantly affect the surface film behaviour after lower sintering temperature. The results have been correlated to microstructural parameters of the PM materials.     

The founding of EPMA

Abstract

Liquid phase sintering is commonly used in powder metallurgy to improve physical properties through densification enhancement. With the aim of combining the advantages of liquid phase sintering and the use of promising alloying elements such as Mn and Si, liquid promoters with complex compositions were designed to provide a low melting point to form a liquid phase below the common sintering temperatures. The properties of these liquid phases were characterised in terms of contact angle, spreading evolution and infiltration. Using a Krüss drop shape analysis system, both wetting angle experiments and infiltration experiments were performed by changing the substrate characteristics from sintered to green iron specimens respectively. The discussion is based on the different features found for these liquids compared with copper, which is a well known liquid phase former used for improving the properties of low alloy steels. Simulations of the thermodynamic and kinetic processes taking place were performed by combining ThermoCalc and DICTRA software analysis.     

Quasi‐in‐situ observations of the sintering behaviour of molybdenum‐alloyed sintered steels

The sintering behaviour of molybdenum pre‐alloyed sintered steels was investigated. A scanning electron microscope with a hot stage attachment was used, enabling quasi‐in‐situ observations of the sintering process. The material MSP 1.5Mo (Fe‐1.5% Mo) sinters in the austenitic phase, while MSP 3.5Mo (Fe‐3.5% Mo) sinters completely in the ferritic phase, due to the increased molybdenum mass content. The significantly higher self‐diffusion coefficient of iron in the ferritic phase leads to the accelerated sintering of MSP 3.5Mo, compared to MSP 1.5Mo. The effect on the sintering behaviour by adding the alloying elements chromium and phosphorus was also studied. While phosphorus accelerates sintering processes, chromium decreases the sintering rate. A pronounced shrinkage during non‐isothermal heating, due to cooperative particle movement, was detected for both sintered steels.     

The thermodynamics of interactive co-segregation of phosphorus and alloying elements in iron and temper-brittle steels

The thermodynamics of co-segregation and precipitation of P and alloying elements (transition metals M and carbon) involved in temper embrittlement of steels are studied quantitatively on the basis of the regular solution model for co-segregation. The equations of this model are fitted to the available Auger data for grain boundary segregation in high purity iron-base alloys and commercial steels, allowing the determination of the intrinsic segregation energies ΔG_i ^o and of the binary β_P ^gb, β_c ^gb and ternary β_PC ^gb, ß_MP ^gb interaction coefficients in the grain boundaries. This analysis shows that Ni, Cr, and Mo do not segregateper se in iron whereas Mn does weakly, and that the segregation of these elements is essentially driven by that of P through the strongβ_MP ^gb attractive interaction energyat the boundaries. This energy, which increases in the order Ni, Mn, Cr, Mo, is remarkably close to the bulk values β_MP ^B in the corresponding phosphides as calculated on the basis of solubility data. The scavenging of P by M elements with largebulk M-P interactions is shown to play a determining role in low Mo and high (12 pct) Cr steels. The beneficial role of carbon is complex since it drives Mo to the grain boundaries due to the large Mo-C attraction, but it also strongly opposes P segregation due to the large repulsive P-C interaction.     

无磁钢的研究概况和我国无磁钢的发展思路

奥氏体无磁钢分为无磁高锰结构钢和无磁不锈钢。无磁高锰结构钢主要应用于电力、交通、建筑等民用领域,无磁不锈钢主要应用于国防军工等高技术领域。分析了Fe-Mn系、Fe-Mn-Cr系和Fe-Mn-Al系无磁高锰结构钢以及无磁不锈钢的国内外发展和研究概况。提出我国开发节约Ni、Mo、Cr等金属资源的减量化高锰无磁钢和高端无磁不锈钢的发展思路,既满足民用领域对无磁钢的力学和无磁性能的需要,又满足国防军工用无磁钢的良好力学、焊接和防腐蚀等综合性能要求。     

Spectral interference of polyatomic ions of Cr,Fe, Mn,Mo, Ni,and W in steel using inductively coupled plasma mass spectrometry

Because of the low resolution of quadrupole mass filter, polyatomic ions interfere with analyte ions in inductively coupled plasma mass spectrometry. In order to achieve accurate results it is urgently recommended to know the kind and the amount of ions of the major concentrated elements of the sample. The matrix elements of high purity iron, low, and high alloy steels are Fe, Cr, Ni, Mn, Mo, and W. 175 different polyatomic ions of the matrix elements and those of nitric, hydrochloric, and hydrofluoric acid are experimentally determined in steel sample solutions. Signal intensities higher than a threshold of 30 counts/s have been considered as significant. 100 isotopes of 25 elements show interference at 69 m/z-values.     

Coarsening resistance of M2C carbides in secondary hardening steels: Part II. Alloy design aided by a thermochemical database

In high Co-Ni steels containing the strong carbide-forming elements Mo, Cr, and W, secondary hardening is accomplished by the precipitation of fine-scale M₂C alloy carbides. Thermodynamic stability and coarsening resistance of these carbides depend on the alloy content of these elements. A model for the M₂C coarsening kinetics in multicomponent alloys has been used to identify the optimum alloying addition for maximum coarsening resistance and as a basis for selection of four experimental alloy steels. Necessary information pertaining to the equilibrium in these steels was obtained using the Thermo-Calc software and database developed at the Royal Institute of Technology, Stockholm, Sweden.     

Gigacycle fatigue of ultra high density sintered alloy steels

Abstract

Sintered steel specimens with density levels of up to 7·6 g cm^?3 have been prepared from Cr–Mo and Mo prealloyed powders. The fatigue response has been studied using an ultrasonic resonance testing device that enabled testing up to 10⁹ cycles. It showed that the fatigue endurance strength can be drastically increased by raising the density and that the sintering conditions are effective, though less than the density. The existence of a true fatigue limit was disproved up to 10⁹ cycles for all materials tested, with sintered steels thus being similar to wrought ones. Cr–Mo steels was shown to be superior to Mo alloyed grades due to the markedly finer as sintered microstructure and higher sintering activity. Fatigue crack initiation was found to originate from pores at first at multiple sites, with microstructural orientation being dominant compared to the direction of stress; with progressive loading, some cracks join to form a propagating macrocrack from which the final failure then starts.