Selective Oxidation and Surface Segregation in High Strength Steels during Short Term Annealing in H2‐N2 ‐ Influence of B on Surface Chemistry

In order to achieve appropriate mechanical properties, new high strength steels aimed for the car industry have to be alloyed with solution strengthening elements. The annealing treatment undergone on cold rolled sheets induces the selective oxidation of alloying elements such as Al, Mn, Si and Cr. The formed oxides exhibit a poor wetting by the Zn bath during hot dip galvanising, thus deteriorating the properties of the zinc coating. While surface‐segregating elements get oxidised, they interact with each other through the formation of spinels and/or mixed oxides during annealing and oxides which have a deleterious effect on wetting can be formed. The formation of (Mn, B) oxide was observed on alloys containing even very small amounts of B and this oxide is almost not wetted at all by Zn. Boron is added to interstitial‐free steels to improve the cold work embrittlement, by replacing phosphorus at the grain boundaries. In this paper, the selective oxidation of steels with and without B, in 5 vol. % H₂‐N₂ atmosphere at 820°C and different dew points was investigated. We found a very strong effect of segregation and oxidation of B on Si and S segregation and oxidation behaviour.     

Influence of Minor Alloying Elements on Selective Oxidation and Reactive Wetting of CMnSi TRIP Steel during Hot Dip Galvanizing

The influence of the addition of minor alloying elements on the selective oxidation and the reactive wetting of CMnSi transformation-induced plasticity (TRIP) steels was studied by means of galvanizing simulator tests. Five TRIP steels containing small alloying additions of Cr, Ni, Ti, Cu, and Sn were investigated. After intercritical annealing (IA) at 1093 K (820 °C) in a N₂ + 5 pct H₂ gas atmosphere with a dew point of 213 K (?60 °C), two types of oxides were formed on the strip surface: Mn-rich xMnO·SiO₂ (x > 1.5) and Si-rich xMnO·SiO₂ (x < 0.3) oxides. The addition of the minor alloying elements changed the morphology of the Si-rich oxides from a continuous film to discrete islands and this improved the wettability by molten Zn. The improved wetting effect of the minor alloying elements was attributed to an increased area fraction of the surface where the oxides were thinner, enabling a direct unhindered reaction between Fe and the Al in the liquid Zn and the formation of the inhibition layer during the hot dip galvanizing. The addition of a small amount of Sn is shown to significantly decrease the density of Zn-coating defects on CMnSi TRIP steels.     

Galvanizability of Complex Phase High Strength Steel

Complex phase (CP) steels have very high ultimate tensile strengths, resulting from the use of specific alloying elements, which improve the hardenability but cause difficulties when applying a zinc coating by means of continuous hot‐dip galvanizing. The galvanizability of a cold rolled 1000MPa complex phase steel was investigated by monitoring the surface chemistry before dipping and evaluating the quality of the zinc coatings applied by a laboratory hot‐dipping simulator. Two steel compositions with different Cr levels were used. The influence of the most important production parameters, the annealing temperature and the dew point of the annealing atmosphere, was investigated. Both steel compositions were galvanizable, but both the surface appearance and zinc coating adhesion were improved when low Cr contents were used. At a low dew point of ‐30°C, Cr, Mn and Si segregated to the surface and the presence of Mn₂SiO₄ could be demonstrated. At high dew point of +10°C, less oxides were present at the steel surface. There was no effect of the annealing temperature on the coatability.     

Microstructure and properties of a C–Mn–Si–dual-phase steel

A study has been carried out on an Fe–0.11% C–1.58% Si–0.4% Mn-dual phase steel. The dual-phase microstructures and properties are significantly affected by both the intercritical temperature and cooling rate from (α + γ) field. Upon rapid cooling (water or oil quench) from the temperature range 735–820°C, the structure comprises ferrite + martensite. On the other hand, slow cooling (air cooling) from the temperature range 735–820°C produces microstructures containing ferrite + martensite + pearlite/bainite and more favourable mechanical properties as: σ_0,2 = 281–296 MPa, σ_UTS = 632–690 MPa, TE = 26–30% and continuous yielding behaviour.     

热镀锌技术的最新进展

介绍了近10余年钢材热镀锌工艺和装备的技术进展，内容包括：汽车用IF钢合金化镀锌板，高耐蚀合金镀层，含硅钢热镀锌工艺，美钢联法热镀锌生产线，高温退火炉，高耐蚀耐磨沉没辊，气刀，高频感应加热合金化炉及内加热式锌锅等。     

Simulation of the Soaking and Gas Jet Cooling in a Continuous Annealing Line using Dilatometry

The present study concerns the simulation of a continuous annealing line (CAL), using dilatometry. Simulations of CAL have been performed on four commercial steel grades with different chemical compositions in order to investigate how the alloying elements C, Mn, Si and B affect the microstructure and hardness of dual phase (DP) and martensitic steels. Three annealing cycles corresponding to those used in a CAL have been applied. When annealing intercritically, as is the case in DP‐steel production, the materials do not reach equilibrium during soaking. Mn and C increase the austenite content and consequently the hardness of the materials. Higher levels of Si (0.4 wt %) are required to retard the formation of new ferrite during cooling in the gas jet section, prior to quenching. B increases hardenability effectively when annealing in the austenite region but is not as efficient during intercritical annealing, which implies that boron restrains ferrite nucleation rather than impeding ferrite growth. Results from DICTRA calculations show that it is possible to simulate the phase transformations during soaking, gasjet cooling and quenching.     

The Impact of Selective Oxidation on the Phase Transformation in the Sub‐Surface of Advanced High Strength Steels

The present paper contributes in the discussion of heterogeneous gas/metal reactions by discussing the influence of the dew point (dp) during intercritical annealing on the sub‐surface constitution. Annealing trials with different Advanced High Strength Steels (AHSS) were carried out and the element distribution within the sub‐surface was analysed by glow discharge optical emission spectrometer (GD‐OES). For modelling purpose the gained element distribution data were adjusted in a way that the selective oxidation products were considered within the sub‐surface element profiles. Several transformation temperatures along the depth profiles according to the adjusted GD‐OES data have been computed for the dp ?30 °C and +5 °C. In all cases the according models have been implemented in Matlab. The thermodynamic data have been obtained via the Matlab‐ThermoCalc interface. Empirical equations have been applied for the determination of the bainite and martensite start temperatures. It is shown that the sub‐surface constitution and the transformation temperature differ significantly. In most cases the change of the transformation temperature within the surface and sub‐surface reaches up to 100 °C compared to the bulk. For a Dual‐Phase (DP) Steel with C(0.15%)Mn(1.7%)Al(1.7%)Cr(0.5%), the change of the A_e1‐temperature is with 300 °C significantly higher. However one has to keep in mind that the 2‐phase composition can not be assumed to be constant during intercritical annealing. It is therefore concluded that for the purpose of simulating the selective oxidation processes during intercritical annealing of AHSS the continuous change of the sub‐surface constitution must be incorporated in the future work.     

Hot Dip Galvanizing Simulation of Interstitial Free Steel by Liquid Zinc Spin Coater: Influence of Dew Point on Surface Chemistry and Wettability

In order to establish the relationship between surface chemistry and wettability as a function of dew point, an attempt has been made to simulate the hot‐dip galvanizing process with an ‘in‐house’ built Liquid Zinc Spin Coater. Interstitial free (IF) steel was annealed at 820°C in N₂‐5%H₂ gas atmospheres with dew points of ‐79°C, ‐29°C and 0°C, respectively. The wettability tests were conducted at 470°C at low dew point of ‐79°C. Surface analyses prior to wetting were carried out by using X‐ray photoelectron spectroscopy (XPS) and Field Emission Scanning Electron Microscopy (FE‐SEM). As expected, external oxidation of Al was observed only at the low dew point. With increasing dew point the oxidation of Cr and Si becomes internal. The formation of manganese silicates was observed at all dew points. While sulphur was detected on the specimen surface after all annealing conditions, the segregation of P starts to be significant at dew point 0°C by forming Mn‐phosphates. Despite the surface oxides, specimens annealed at all dew points are in the wetting regime by liquid zinc. Investigations on the steel/zinc interface of IF steel by using the liquid zinc spin coater were successful.     

连退板浅表层的富集元素表征

为了研究连退板表层元素富集行为及相互作用,借助扫描电镜、辉光放电光谱仪、光电子能谱仪和透射电镜等技术手段对铝镇静钢和双相钢连退板表层中的富集元素进行了详细地表征与分析。结果表明,铝镇静钢连退板表面的主要富集元素有O、Mn和Al;而双相钢连退板表面的主要富集元素有O、Mn和Si。沿着浅表层深度分析可知,对于合金元素含量较高的双相钢,沿浅表层富集更深,富集深度约为50 nm;而合金元素含量较低的铝镇静钢,富集深度仅约为25 nm。综合分析不难发现,相对于铝镇静钢,双相钢添加了Si元素以后在其表面优先富集Si元素并同时形成了Si的氧化物,从而导致Al元素的富集及氧化物的形成受到了抑制。     

连退板浅表层的富集元素表征

为了研究连退板表层元素富集行为及相互作用,借助扫描电镜、辉光放电光谱仪、光电子能谱仪和透射电镜等技术手段对铝镇静钢和双相钢连退板表层中的富集元素进行了详细地表征与分析。结果表明,铝镇静钢连退板表面的主要富集元素有O、Mn和Al;而双相钢连退板表面的主要富集元素有O、Mn和Si。沿着浅表层深度分析可知,对于合金元素含量较高的双相钢,沿浅表层富集更深,富集深度约为50 nm;而合金元素含量较低的铝镇静钢,富集深度仅约为25 nm。综合分析不难发现,相对于铝镇静钢,双相钢添加了Si元素以后在其表面优先富集Si元素并同时形成了Si的氧化物,从而导致Al元素的富集及氧化物的形成受到了抑制。     

Galvannealing of (High‐)Manganese‐Alloyed TRIP‐ and X‐IP®‐Steel

In this study the influence of Mn on galvannealed coatings of 1.7% Mn‐1.5% Al TRIP‐ and 23% Mn X‐IP®‐steels was investigated. It is shown that the external selective oxides like Mn, Al and Si of the TRIP steel which occur after annealing at 800 °C for 60 s at a dew point (DP) of ‐25 °C (5% H₂) hamper the Fe/Zn‐reaction during subsequent galvannealing. Preoxidation was beneficially utilized to increase the surface‐reactivity of the TRIP steel under the same dew point conditions. The influence of Mn on the steel alloy was investigated by using a 23% Mn containing X‐IP®‐steel which was bright annealed at 1100 °C for 60 s at DP ‐50 °C (5% H₂) to obtain a mainly oxide free surface prior to hot dip galvanizing (hdg) and subsequent galvannealing. As well known from the literature Mn alloyed to the liquid zinc melt stabilizes δ‐phase at lower temperatures by participating in the Fe‐Zn‐phase reactions, it was expected that the metallic Mn of the X‐IP®‐steel increases the Fe/Zn‐reactivity in the same manner. The approximation of the effective diffusion coefficient (D_eff(Fe)) during galvannealing was found to be higher than compared to a low alloyed steel reference. Contrary to the expectation no increased Fe/Zn‐reaction was found by microscopic investigations. Residual η‐ and ζ‐phase fractions prove a hampered Fe/Zn‐reaction. As explanation for the observed hampered Fe/Zn‐reaction the lower Fe‐content of the high‐Mn‐alloyed X‐IP®‐steel was suggested as the dominating factor for galvannealing.     

Reactive wetting of SiO<Subscript>2</Subscript> substrates by molten Al

The reactive wetting behavior of SiO₂ substrates by molten Al was investigated at temperatures between 800 °C to 1250 °C in a purified Ar-3 pct H₂ atmosphere of about 0.11 MPa using an improved sessile drop method. The time dependence of the changes in contact angle and droplet geometry was monitored and the wetting kinetics was identified. The initial equilibrium or quasi-equilibrium contact angles are generally larger than 90 deg and do not significantly vary with temperature. The subsequent remarkable decrease in the contact angle mainly results from the progressive decrease in the droplet volume rather than the advance of the solid-liquid interfacial front. The significant effect of temperature on the wetting kinetics is essentially related to its effect on the reaction and molten Al penetration progress. For systems with a considerable decrease in the droplet volume during reactive wetting, a criterion for evaluation of the true wetting improvement was proposed.     

Influence of intercritical annealing temperature on microstructure and mechanical properties of medium Mn TRIP steel

The transformation, microstructure and mechanical properties of the 0. 2C- 5Mn TRIP steel after intercritical annealing were investigated using dilatometer, scanning electronic microscopy (SEM), transmission electron microscopy(TEM), X- ray diffraction (XRD), and tensile testing machine. The phase transformation thermodynamics of the investigated steel after intercritical annealing was calculated by Factsage software and the characteristics of the transformation were discussed. The results show that the reversed austenite content increases with the increasing of the intercritical annealing temperature, the carbon content in reversed austenite firstly increases and then decreases, manganese content in reversed austenite decreases, which results in the decreasing of the thermal stability of reversed austenite. When the intercritical annealing temperature is 700??, an obvious martensitic transformation occurs during the cooling process. With the increasing of intercritical annealing temperature, cementite is gradually dissolved, but it cannot be completely dissolved due to the short transformation time. When the intercritical annealing temperature is 600-675??, the microstructure after intercritical annealing consists of ferrite, cementite and retained austenite. When the intercritical annealing temperature is 700??, the microstructure after intercritical annealing consists of ferrite, retained austenite, martensite and a small amount of undissolved cementite. The engineering stress and strain curves of the investigated steel are significantly changed with increasing intercritical annealing temperature. At the same time, the optimal mechanical properties with tensile strength of 1138MPa and total elongation of 23% can be obtained after annealed at 675?? for 3min.     

Hot-dip galvanising behaviours of a CMnSiCr DP780 steel

In order to evaluate the galvanisability of a CMnSiCr DP780 steel, which is originally designed for manufacturing continuously annealed bare steel sheet, hot-dip galvanising experiments were conducted on a hot-dip process simulator. The process and galvanising behaviours were investigated. The results indicate that the alloying elements such as Si, Mn and Cr segregate and selectively oxidise at the surface during annealing. Besides external oxidation, internal oxidation of Cr and Mn is observed. Aluminothermic reducing reaction is effective to reduce the negative effect of surface oxides on the galvanisability of this steel and improve the coating quality. According to the measurement results and discussions, it is believed that this CMnSiCr DP780 steel could possibly be used to produce the corresponding hot-dip galvanised or galvannealed product when further increasing the Al content in Zn bath slightly, especially for galvannealed product.     

Influence of Gas Atmosphere Dew Point on the Selective Oxidation and the Reactive Wetting During Hot Dip Galvanizing of CMnSi TRIP Steel

The selective oxidation and reactive wetting of intercritically annealed Si-bearing CMnSi transformation-induced plasticity steels were investigated by high-resolution transmission electron microscopy. In a N₂ + 10 pct H₂ gas atmosphere with a dew point (DP) ranging from 213 K to 278 K (?60 °C to 5 °C), a continuous layer of selective oxides was formed on the surface. Annealing in a higher DP gas atmosphere resulted in a thinner layer of external oxidation and a greater depth of internal oxidation. The hot dipping was carried out in a Zn bath containing 0.22 mass pct Al, and the bath temperature was 733 K (460 °C). Coarse and discontinuous Fe₂Al_5?x Zn _x grains and Fe-Zn intermetallics (?? and ??) were observed at the steel/coating interface after the hot dip galvanizing (HDG) of panels were annealed in a low DP atmosphere 213 K (?60 °C). The Fe-Zn intermetallics were formed both in areas where the Fe₂Al_5?x Zn _x inhibition layer had not been formed and on top of non-stoichiometric Fe-Al-Zn crystals. Poor wetting was observed on panels annealed in a low DP atmosphere because of the formation of thick film-type oxides on the surface. After annealing in higher DP gas atmospheres, i.e., 263 K and 278 K (?10 °C and 5 °C), a continuous and fine-grained Fe₂Al_5?x Zn _x layer was formed. No Fe-Zn intermetallics were formed. The small grain size of the inhibition layer was attributed to the nucleation of the Fe₂Al_5?x Zn _x grains on small ferrite sub-surface grains and the presence of granular surface oxides. A high DP atmosphere can therefore significantly contribute to the decrease of Zn-coating defects on CMnSi TRIP steels processed in HDG lines.     

Microstructure,Mechanical Properties,and Abrasive Wear Behaviour of Si‐Mn‐Cr‐B Cast Steel as a Function of Carbon Concentration

The microstructures, mechanical properties and abrasive wear behaviour of five kinds of Si‐Mn‐Cr‐B cast steels were studied. The steels investigated contained X wt.% C with X= 0.15, 0.25, 0.35, 0.45, 0.55, 2.5 wt.% Si, 2.5 wt.% Mn, 0.5 wt.% Cr, 0.004 wt.%B . The results showed that the A_c1temperatures increased and A_c3 and M_s temperatures decreased with increasing carbon concentration. From the continuous cooling transformation (CCT) curves, it was discovered that the incubation period of pearlitic transformation was prolonged and the transformation curves of pearlite and bainite were separated significantly with rising carbon concentration. At lower carbon concentration, the normalized structure of Si‐Mn‐Cr‐B cast steel consisted mainly of granular bainite and M‐A islands. The normalized microstructures of the cast steel changed from granular bainite gradually to needle‐like bainite, upper bainite, and lower bainite with rising carbon concentration. The tensile strength and hardness of Si‐Mn‐Cr‐B cast steel increased and impact and fracture toughness decreased with increasing carbon content. The wear testing results showed that the wear resistance of Si‐Mn‐Cr‐B cast steel improved with higher carbon content but was obviously unchanged beyond the carbon concentration of 0.45%. The best balance of properties of Si‐Mn‐Cr‐B cast steel is obtained at the carbon concentration range of 0.35 ‐ 0.45%C.     

奥氏体化温度对30Cr3SiMnNiWMo钢组织性能的影响

试验研究了860～980℃奥氏体化处理对30Cr3SiMnNiWMo钢(%:0.28C、0.74Mn、1.04Si、2.70Cr、1.15Ni、0.45Mo、1.04W、0.07V、0.05Al)组织以及260℃回火后钢的力学性能的影响。结果表明,30Cr3SiMnNiWMo钢860～920℃淬火组织中存在大量M6C碳化物,对回火钢的韧性不利;950℃淬火后,钢中M6C碳化物基本溶解,原奥氏体晶粒开始长大,回火后钢的强度降低;30Cr3SiMnNiWMo钢经920℃1h油淬+260℃2h回火可以获得具有少量残余奥氏体和未溶碳化物的板条马氏体组织,并具有优良的强韧性(Rm=1680 MPa, Rp0.2=1330 MPa,A=13%, Z=58.5%, AKU=85 J) 。     

Galvanizing and Galvannealing Behavior of CMnSiCr Dual-Phase Steels

Alloying elements, such as Mn, Mo, Si, and Cr, are commonly used to enhance the strength of advanced high-strength steels. Those elements also play an important role in the hot-dip galvanizing (GI) and galvannealing (GA) process. In this study, two kinds of CMnSiCr dual-phase steels were galvanized and galvannealed using a hot-dip simulator to investigate the effect of the alloying elements on the microstructure of the GI and GA coatings. The results showed that the dual-phase steels had good galvanizability because no bare spots were observed and the Fe-Zn phases were readily formed at the interface. However, the alloying reaction during the GA process was significantly hindered. XPS analysis showed that external oxidation occurred under an extremely low dew point [213 K to 203 K (?60 °C to ?70 °C)] atmosphere during the annealing prior to hot dipping. However, most of the oxides were reduced during the GI process. After the GI process, the Al was present as solid solutes in the Fe-Zn phase, suggesting that the Fe-Zn phase was formed from the transformation of the Fe-Al inhibition alloy. Meanwhile, the solubility of Si in the ζ phase was extremely low. With continued GA reaction, the ζ phase transformed into the δ phase, which contained approximately 1.0 at.pct Si. The Si also diffused into the Zn layer during the GA reaction. Hence, the ζ phase did not homogeneously nucleate at the steel substrate/Zn coating interface, but was found at the area away from the interface. Therefore, the Fe-Zn phases on the CMnSiCr dual-phase steels were relatively non-uniform compared to those on interstitial-free steel.     

Selective Oxidation of TWIP Steel During Continuous Annealing

The selective oxidation of Al‐free and Al‐added TWIP steel after full austenitic annealing at 800°C in a N₂ + 10%H₂ gas atmosphere with a dew point of ?17°C was investigated by means of transmission electron microscopy. A thick MnO layer was formed at the surface of Al‐free TWIP steel after the recrystallization annealing. Small crystalline c‐xMnO · SiO₂ (x > 2) particles and amorphous a‐xMnO · SiO₂ (x < 0.9) particles were found at the MnO/steel interface. In the subsurface, the Mn depletion resulted in the formation of a narrow ferrite layer. The annealing of the Al‐added TWIP steel also resulted in the formation of a thick MnO surface layer. At the MnO/steel interface, Kirkendall voids were formed between the amorphous a‐xMnO · SiO₂ (x < 0.9) oxide and crystalline c‐xMnO · Al₂O₃ oxide in the case of Al‐added TWIP steel. In the subsurface, a thin layer was depleted of Mn and the original austenite had transformed into ferrite. Internal oxidation of Al to Al₂O₃ and the formation of crystalline c‐xMnO · Al₂O₃ (x > 1) compound oxide particles were found to occur at the grain boundaries of the Mn‐depleted ferritic zone. The present contribution highlights the implications of the selective oxidation of TWIP steels for their processing in continuous annealing and continuous hot dip galvanizing lines.     

Effects of Solution Treatment and Test Temperature on Tensile Properties of High Mn Austenitic Steels

Tensile properties of high Mn austenitic Fe‐26.5Mn‐3.6Al‐2.2Si‐0.38C‐0.005B (HM1) and Fe‐18.9Mn‐0.62C‐0.02Ti‐0.005B (HM2, in mass%) steels after different solution treatments have been investigated. The results show that the solution treatment has a significant influence on microstructure and mechanical properties of the investigated steels. By appropriate solution treatment the product of tensile strength (R_m) and total elongation (A₅₀) of the hot rolled steel can be improved from ? 40000‐50000 MPa% to ? 55000‐65000 MPa% depending on the steel chemical composition. A solution treatment with a very high temperature, e.g. at 1100 °C for the Fe‐18.9Mn‐0.62C‐0.02Ti‐0.005B steel, results in a significant increase in the ?‐martensite fraction during quenching. This deteriorates the ductility of the steel. A solution treatment at low temperature in the austenitic range, e.g. at 700 °C for the Fe‐18.9Mn‐0.62C‐0.02Ti‐0.005B steel, results in a decrease in the grain size of the steel. This suppresses the ?‐martensite transformation during cooling. EBSD measurements revealed the mechanisms contributing to the overall plasticity of the investigated steels on the microscale. The plasticity of the 26.5Mn‐3.6Al‐2.2Si‐0.38C‐0.005B steel is produced mainly by TWIP mechanism under the examined experimental conditions, whereas for the Fe‐18.9Mn‐0.62C‐0.02Ti‐0.005B steel TWIP and TRIP mechanisms occur with different degrees depending on the test temperature of the tensile test.