Graphite nucleation control in grey cast iron

Abstract

A research programme has been undertaken to achieve a more detailed understanding of graphite nucleation control in grey cast irons, at different sulphur (0˙02–0˙1%), residual aluminium (0˙001–0˙010%) and zirconium (0˙001–0˙015%) levels in iron melts. It was found that three groups of elements are important to sustain a three stage model for the nucleation of graphite in grey irons:

(i) strong deoxidising elements (Al, Zr) to promote early formed very small microinclusions, oxide based, which will act as nucleation sites for later formed complex (Mn,X)S compounds

(ii) Mn and S to sustain MnS type sulphide formation

(iii) inoculating elements (Ca, Sr, etc.) which act in the first stage or/and in the second one of graphite formation, to improve the capability of (Mn,X)S compounds to nucleate graphite.

It was confirmed that 0˙07%S level is beneficial for graphite nucleation in grey irons with a lower incidence of carbides and undercooled graphite, compared to 0˙023%S cast irons. Low residual Al level (0˙001–0˙003%) results in higher chill and more undercooled graphite and lower eutectic cell count, in inoculated irons. A 0˙007–0˙010%Al content in the melt is important to sustain type A graphite nucleation and reduced chill. Not only inoculation but also the preconditioning (Al or/and Zr) of the base iron has a strong beneficial effect on the solidification pattern of cast irons. Both Al and Zr sustain the type A graphite formation with a lower degree of undercooling and free carbides. These elements were associated in a complex alloy (FeSi based), very efficient in preconditioning of grey irons for thin wall castings, at a low addition rate.     

Complex（Mn, X）S compounds - major sites for graphite nucleation in grey cast iron

Despite the cubic system, the ability of sulphides to nucleate graphite can be enhanced by inoculating elements which transform them in complex compounds with a better lattice matching to graphite, a low coagulation capacity, good stability and adequate interracial energy. (Mn,X)S compounds, usually less than 5.0 μm in size, with an average 0.4-2.0 μm well defined core (nucleus), were found to be important sites for graphite nucleation in grey irons. A three-stage model for the nucleation of graphite in grey irons is proposed: (1) Very small micro-inclusions based on strong deoxidizing elements (Mn, Si, Al, Ti, Zr) are formed in the melt; (2) Nucleation of complex (Mn,X)S compounds at these previously formed micro-inclusions; (3) Graphite nucleates on the sides of the (Mn,X)S compounds with lower crystallographic misfit. Al appears to have a key role in this process, as Al contributes to the formation of oxides in the first stage and favors the presence of Sr and Ca in the sulphides, in the second stage. The 0.005-0.010% Al range was found to be beneficial for lower undercooling solidification, type-A graphite formation and carbides avoidance.     

高强度D型石墨铸铁的研究进展

综述了灰铸铁中产生D型石墨的原因，D型石墨对灰铸铁性能的影响以及D型石墨灰铸铁的应用。国内外的研究表明：深过冷，在灰铸铁中加入提高过冷度的合金元素（钛，铝，锑，碲，稀土元素等）或者二者的结合都会促进生成D型石墨；D型石墨灰铸铁具有较高的强度，较好的抗氧化性，抗生长性，抗热疲劳性和耐磨性；D型石墨灰铸铁已经广泛用于生产玻璃模具，压缩机缸体，压缩机曲轴等铸件。笔者还介绍了采用钒钛生铁生产的D型石墨合金铸铁凸轮轴的性能特点及其应用情况。     

Inoculated Slightly Hypereutectic Gray Cast Irons

The current experimental investigation in this article was designed to characterize the structure of mold (M) and ladle (L) inoculated, low-S (0.025 wt.% S), low-Al (0.003 wt.% Al), slightly hypereutectic (CE = 4.4-4.5 wt.%) electric melted gray irons, typical for high performance thin-wall castings. It describes the effect of a Ca, Al, Zr-FeSi inoculant addition of 0-0.25 wt.% on structure characteristics, and compares to similar treatments with hypoeutectic irons (3.5-3.6 wt.% CE, 0.025 wt.% S, and 0.003 wt.% Al). A complex structure including primary graphite, austenite dendrites, and eutectic cells is obtained in hypereutectic irons, as the result of nonequilibrium solidification following the concept of a coexisting region. Dendrites appear to be distributed between eutectic cells at higher eutectic undercooling, while in inoculated irons and for lower undercooling, the eutectic cells are “reinforced” by eutectic austenite dendrites. A Zr, Ca, Al-FeSi alloy appears to be an effective inoculant in low S, low Al, gray cast irons, especially for a late inoculation technique, with beneficial effects on both graphite and austenite phases. First, inoculation influenced the nucleation of graphite/eutectic cell, and then their characteristics. A further role of these active elements directly contributed to form nucleation sites for austenite, as complex (Mn,X)S particles.     

生长条件对灰口铸铁共晶凝固过程石墨形态的作用

灰铸铁、蠕铁、球铁被统称为灰口铸铁,在现代工业中应用广泛.在主要成分相近情况下,由于微量元素等条件的不同引起石墨生长形态各异,从而同属灰口铸铁的三类铸铁性能迥异.懂得其基本规律及相关原理,有益于铸造工程技术人员在灰铁、蠕铁、球铁的生产实际中理性而有效地控制产品质量.本文基于灰口铸铁的奥氏体-石墨共晶凝固方式,从基本概念及原理、G形成过程、实际组织观察与分析的全新视角,主要针对灰铁和球铁概述了石墨形态的形成规律和机理.文中诸多图片等实例是以往国内教科书及专业书籍中未见的,文章内容也体现了对相关现象描述及观点上新的发展,有助于读者对该方面有关问题获得更为清晰的理解和认识.     

Casting of Iron Aluminides

Iron aluminides form an interesting class of materials which combine excellent corrosion and oxidation resistance with good mechanical properties at moderate to high temperature (up to 500 °C). These materials, however, suffer from low room-temperature ductility (under 5% elongation in tension), which is mostly due to environmental effects. Casting is a processing route traditionally applied to brittle alloys (e.g., gray cast irons), but to cast a part without defects, several thermochemical properties are needed, as well as information on the tendency of the alloy to form foundry defects (e.g., shrinkage voids, pores). The present work aims to provide this information using parts produced on laboratory scale. In particular, the solidification contraction and the efficiency of TiB₂ as inoculant are investigated. Three alloys with nominal composition (in at.%) Fe28Al, Fe28Al6Cr, and Fe28Al6Cr1Ti (about 1.5 kg for each melt) were melted in an induction furnace under argon flux protection using conventional raw materials (carbon steel, commercial aluminum, metallic chromium, and commercial ferrotitanium). The resulting melts were treated by adding Al-TiB₂ master alloy used in the aluminum industry and poured into “staircase” molds, designed to investigate feeding distance effects in complex parts. Characterization of the microstructure of the alloys revealed that alloys Fe28Al and Fe28Al6Cr showed κ-carbide precipitation, while alloy Fe28Al6Cr additionally showed chromium carbides at dendritic boundaries. Addition of 1 wt.% Ti in alloy Fe28Al6Cr1Ti changed the solidification microstructure, refining the dendrite morphology and forming TiC-containing eutectic in interdendritic spaces.     

In Situ fracture observation and fracture toughness analysis of pearlitic graphite cast irons with different nodularity

Effects of microstructural modification and microfracture mechanisms on fracture toughness of pearlitic graphite cast irons with different nodularity were investigated by in situ observation of microfracture process. Six pearlitic graphite cast irons were fabricated by adding a small amount of Mg as a nodularizing element for graphite, and their microstructures including pearlite, ferrite, graphite, and eutectic carbide were analyzed. Most of ferrites were observed in a layer shape around graphites because of carbon-depleted zones formed near graphites. As the nodularity and nodule count increased, fracture toughness linearly increased in the cast irons except the iron containing many fine graphites. According to in situ observation of microfracture process, cracks initiated at nodular graphites and carbides even at a small load, and then propagated readily through the adjacent graphites or carbides, thereby resulting in the lowest fracture toughness. The cast iron having widely spaced graphites and ferrite layers thickly formed around graphites showed the highest fracture toughness because of the blocking of crack propagation by ductile ferrite layers and the crack blunting and deflection by graphites, which was also confirmed by the R-curve analysis.     

Einflüsse von Mo,V, Nb,Ti, Zr und deren Karbiden auf die Korrosion und Wasserstoffaufnahme des Eisens in Schwefelsäure

Effects of Mo, V, Nb, Ti, Zr and their carbides on the corrosion and hydrogen uptake of iron in sulphuric acid The effects of Mo, V, Nb, Ti, Zr and their carbides on the corrosion and hydrogen uptake of iron in 1 M H₂SO₄/N₂/25°C were investigated by electrochemical and surface analytical methods using binary and ternary Fe-Me alloys with about 0.2 at.-%Me. Due to the experimental conditions, no protective surface layers formed. The transition metals were enriched at the iron surface only as a carbide or oxicarbide. Mo or Zr were not markedly enriched. The corrosion current density and the hydrogen activity were decreased only by Mo or Zr. Hydrogen permeation measurements were analysed in terms of the trapping theory. The average binding energy of shallow traps for hydrogen increases with increasing atomic radius of the substituted alloying elements in the order V, Mo, Ti, Nb and Zr. Correspondingly, the hydrogen diffusion coefficient (after saturation of the deep traps) decreases and the hydrogen solubility increases. The steadystate hydrogen permeation rate remains almost unaffected. The total hydrogen content is determined by the density of deep traps and thus mostly independent of the external hydrogen activity. The trapping effect of iron is strongly increased by dissolved Zr or Nb or in the presence of fine dispersed carbides as VC_x. The effect of coarse carbide particles at a lower density is small.     

干扰元素对铸铁组织和性能的影响

介绍了来源于铸造生铁中的S、P、Pb和废钢中的Mn、Cr、Ni、Mo等元素在铸铁中形成碳化物,影响球化,增大缩孔缩松倾向,降低灰铸铁强度的情况。提出了消除其有害影响的主要措施:(1)严格管理炉料、控制铁液的化学成分;(2)加入抗干扰元素;(3)采用高纯铸造生铁。认为使用高纯生铁是解决原材料困扰的重要途径之一。     

Saturated Fractional Design of Experiments: Toughness and Graphite Phase Optimizing in Nihard Cast Irons

The aim of the present research is to identify the manufacturing factors that exert an active influence on the graphite phase formation in mottled Nihard cast irons constituting the roll shells of duplex work rolls processed by the double pour method during centrifugal casting. The studied rolls, referred to as alloy indefinite chill, were processed at industrial scale and had a core consisting of spheroidal graphite cast iron with a matrix of ferrite and pearlite. An additional aim of this study was to evaluate the effect and extent of these factors on the dynamic toughness response of the roll shell material. The research methodology employed consisted of the application of a saturated design of experiments with seven factors, eight experiments, and resolution III. The measured responses for graphite were: the volume fraction, count number per unit area, and morphology, determined by quantitative metallography. Impact testing was characterized by Charpy tests on U-notched specimens at 350 °C. The manufacturing factors studied were: the final weight percent of silicon, sulfur, and manganese; the liquidus and the casting temperatures; and, finally, inoculation with SiCaMn and A-type FeSi (with Zr). The statistical experimental method conducted allowed us to confirm the significance of factors such as the %Si, the liquidus temperature and inoculation with SiCaMn on the precipitation of graphite in a white cast iron such as the Nihard irons used in the roll shell, in agreement with the precipitation of graphite in gray cast irons widely reported in the literature. It was also shown that the development of lamellar graphite shapes were favored by an increase in the total equivalent carbon and also by the increase in the amount of A-type FeSi added. Furthermore, the impact toughness was shown to improve with the increase in both the %Si and the liquidus temperature.     

球墨铸铁与灰口铸铁的超声衰减鉴别

为了找到快速准确鉴别球墨铸铁件与灰口铸铁件的现场检测方法，采用不同频率的超声波对不同厚度的球墨铸铁和灰口铸铁试样进行了超声衰减测试，发现灰口铸铁件超声衰减明显，而球墨铸铁件超声衰减微乎其微。分析认为在通常采用的波长范围内，产生超声衰减的主要原因是灰口铸铁中石墨晶体的构造以及石墨组织的形状、大小和分布。利用这一原理可以十分方便地鉴别球墨铸铁件和灰口铸铁件。     

Effect of Zr on microstructure and mechanical properties of binary TiAl alloys

Ti43Al and Ti47Al alloys with different contents of zirconium were prepared by non-consumable vacuum arc melting furnace. The microstructure and mechanical properties were investigated. The results showed that Zr had no obvious effect on microstructure morphology of Ti43Al, while that of Ti47Al was modified from dendrites into equiaxed grains. The addition of Zr could refine the grains. Zr promoted the formation of γ phase significantly and the solubility values of Zr in γ phase were 12.0% and 5.0% (molar fraction) in Ti43Al and Ti47Al, respectively. Zr-rich γ phase mainly formed through β→γ in Ti43Al?xZr (molar fraction, %) and β→α→γ in Ti47Al?xZr (molar fraction, %). Fine-grain strengthening and solution strengthening were beneficial to improving the compressive strength while severe micro-segregation was detrimental to compressive properties. Large solubility of Zr was bad for ductility of alloys as well. The maximum compressive strengths of Ti43Al?xZr and Ti47Al?xZr were 1684.82 MPa (x=5.0%) and 2158.03 MPa (x=0.5%), respectively. The compressive strain fluctuated slightly in Ti43Al?xZr and reached the maximum value of 35.24% (x=0.5%) in Ti47Al?xZr. Both alloys showed brittle fracture.     

微量Cr、Mn、Zr、Ti、B元素对铸态AlZnMgCu合金的晶粒细化效果的影响

采用光学显微镜、扫描电镜和能谱分析仪考察了Cr、Mn、Zr、Ti、B的联合加入对AlZnMgCu合金的晶粒细化效果。结果发现在铸态合金中同时加入Cr-Mn-Ti-B时晶粒尺寸由256 μm 降为102 μm。而当联合加入Ti-Zr-B后能产生更加强的细化效果,晶粒平均尺寸降为55 μm。这是因为Cr、Mn原子簇团有利于促进Al3Ti形核并成为其结晶基底。当联合加入Cr、Mn、Zr、Ti、B时则可产生更加明显的晶粒细化效果,平均晶粒尺寸变为22 μm。这是因为富Cr、Mn原子簇团在成为Al3Ti结晶核心后,部分Zr原子置换了其中的Ti原子形成了新的Al3(Tix, Zr1-x)结晶核心。而过渡族金属Cr、Mn还能降低液体金属和Al3Ti和Al3(Tix, Zr1-x)的表面张力,抑制结晶核心的长大。     

A型和D型石墨合金灰铸铁断口形貌对比研究

介绍了D型石墨的合金灰铸铁在国内外的应用情况,以及试验生产A型和D型石墨Cr-Ni-Cu合金灰铸铁的方法,检查结果:A型石墨合金灰铸铁中的石墨较粗大;另外,在化学成分相近的情况下,D型石墨合金灰铸铁具有更高的抗拉强度。分析认为两种合金灰铸铁的断口主要是由于片状石墨解理以及石墨/基体之间的界面分离造成的,其中D型石墨合金灰铸铁断口表面的显微疏松更少,枝晶更发达,这正是其具有更高强度、适于制造液压元件的原因。     

多弧离子镀Ti-Al-Zr-Cr-N系双层膜的结构与力学性能

采用多弧离子镀技术和Ti-Al-Zr合金靶及Cr单质靶,在WC-8%Co硬质合金基体上制备了(Ti,Al,Zr)N/(Ti,Al,Zr,Cr)N和Cr N/(Ti,Al,Zr,Cr)N 2种四元双层氮化物膜。利用扫描电镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)分析2种双层膜的微观组织、成分和结构;利用划痕仪和显微硬度计对比2种双层膜的力学性能。结果表明,获得的2种双层膜均具有B1-NaCl型的TiN面心立方结构;双层膜的组织均是典型的柱状晶结构;沉积偏压为–50~–200 V时,双层膜的力学性能均优于(Ti,Al,Zr,Cr)N单层膜,并与Ti-Al-Zr-Cr-N系梯度膜的力学性能相当,同时(Ti,Al,Zr)N/(Ti,Al,Zr,Cr)N双层膜可获得更高的硬度(HV_(0.01)最高值为41 GPa),而CrN/(Ti,Al,Zr,Cr)N双层膜可获得更强的膜层与基体间结合力(所有值均大于200 N)。     

The site occupancies of alloying elements in TiAl and Ti3Al alloys

The site occupancies of V, Cr, Mn, Fe, Ni, Zr, Nb, Mo, Ta, Ga and Sn (1–5 at.%) in TiAl alloys with different compositions, and in Ti₃Al with the compositions of Ti–26 at.%Al–(1–2 at.%)X, were measured by the atom location channelling enhanced microanalysis (ALCHEMI) method. For TiAl alloys, the results show that Zr, Nb and Ta atoms invariably occupy Ti sites, while Fe, Ni, Ga and Sn atoms occupy Al sites, the alloy composition having no significant influence on their site preference. By contrast, the site preference of V, Cr, and Mn changes considerably with alloy composition (the Ti/Al ratio in particular), the probability of these elements substituting for Ti decreasing in the above order. For quaternary Ti–Al–V–Cr alloys, the site occupancies of V and Cr do not show much mutual influence. In general, with increasing atomic number, elements in the same period show increasing tendency to substitute for Al, as is the tendency to substitute for Ti for elements in the same group of the periodic table. For Ti₃Al alloys, Ga and Sn atoms occupy Al sites, while V, Cr, Mn, Zr, Nb, Mo and Ta atoms occupy Ti sites, the site preference of V, Cr, Mn and Mo in TiAl alloys being different from that in Ti₃Al. The experimental results are interpreted in terms of a Bragg–Williams-type model and bond-order data obtained from electronic structure calculation. Qualitative agreement between the model and measurements is reached.     

复合孕育剂Ti、Zr对2519铝铜合金焊缝组织及性能的影响

采用3种焊丝对2519铝铜合金进行MIG焊,研究了孕育剂Ti、Zr对焊缝组织和性能的影响。结果表明:Ti和Zr的细化作用是相容的,当焊丝中单独添加孕育剂Ti或Zr时,焊缝几乎由粗大的柱状晶组成;焊丝中复合添加少量的孕育剂Ti和Zr时,Ti和Zr在熔池中分别形成Al3Ti和Al3Zr,促进了α(Al)非均质形核;随着焊丝中Ti和Zr含量的增加,焊缝组织逐步细化,当焊丝中Ti和Zr含量较高时,Ti和Zr还在熔池中形成大量的Al3(Ti,Zr)质点,促进α(Al)非均质形核;焊缝组织由细小均匀的等轴晶组成,显著提高了接头强度和塑性。     

Ti对灰铸铁件性能的影响

介绍了不同Ti量对中低CE灰铸铁件组织、力学性能和致密性影响的研究方法。试验结果表明:(1)一定量的Ti增加了铁液的过冷倾向,促进了灰铸铁件D型石墨的形成,湿型砂造型的D型石墨明显多于干型砂。(2)随着铁液中w(Ti)量的增加,中低CE灰铸铁件中D型石墨也不断增加。当D型石墨达到较高比例时,铸件中的厚大热节也大量出现D型石墨,CE较高的铸件力学性能增加;当CE降为3.66%,随着w(Ti)量增加,强度下降幅度较大。(3)随着w(Ti)量的增加,灰铸铁件的致密性下降,缩松几率明显增加。w(Ti)0.17%、w(Al)0.023%时,灰铸件缩松几率为70%。     

Crack Initiation and Propagation in Spheroidal-graphite Cast Iron with Different Micromorphologies

The increasing adoption of spheroidal-graphite (s.-g.) cast irons for use in safety critical parts calls for a study of the materials' fracture mechanics. It is becoming necessary to analyse the reliability criteria of these materials on a more rigorous basis. This paper describes studies based upon qualitative and quantitative analysis of crack initiation and propagation under the action of fatigue and three-point bending loads on s.-g. cast irons with the same graphite nodularisation characteristics, but having matrices exhibiting different quantities of ferrite, pearlite and cellular-contour carbides.     

金属型对灰铸铁和球铁力学性能的影响研究

采用铜合金金属型和铸铁金属型浇注灰铸铁和球铁Y形试块，加入不同量的Mn、Ti、Cu和Sn，研究金属型材料和添加合金对灰铸铁和球铁抗拉强度和疲劳强度的影响。结果发现：与采用铸铁金属型浇注相比，未加合金、采用铜合金金属型浇注的灰铸铁和球铁的力学性能略高。采用铜合金铸型浇注时，由于冷速较快，使石墨和基体组织细化的作用较强，添加合金元素改善力学性能的作用较为明显，而且反复浇注时，铜合金金属型的热应力较小。因此，灰铸铁和球铁采用铜合金金属型铸造比采用铸铁金属型有利。