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 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.     

合金元素对双相钢形变及退火织构的影响

分析了双相钢冷变形过程中形变织构的演变规律以及合金元素对双相钢形变织构的影响规律。分析结果表明,虽然存在有少量珠光体,但双相钢冷变形织构与体心立方金属相近;非碳化物形成元素Si的加入对形变织构没有明显的影响;碳化物形成元素Cr和Nb导致形变织构在α取向线的{112}<110>取向位置上的取向密度增强。测试分析了双相退火过程中钢的织构演变规律。结果表明,退火时晶粒的取向将沿着α取向线向γ取向线位置转变,Si或Cr对晶粒取向改变的阻碍作用不明显,微合金元素Nb明显阻碍晶粒取向改变,退火织构仍保持很高的α取向线织构组分。对上述的实验结果进行了理论分析。     

Influence of Gas Atmosphere Dew Point on the Galvannealing of CMnSi TRIP Steel

The Fe-Zn reaction occurring during the galvannealing of a Si-bearing transformation-induced plasticity (TRIP) steel was investigated by field-emission electron probe microanalysis and field-emission transmission electron microscopy. The galvannealing was simulated after hot dipping in a Zn bath containing 0.13 mass pct Al at 733 K (460 °C). The galvannealing temperature was in the range of 813 K to 843 K (540 °C to 570 °C). The kinetics and mechanism of the galvannealing reaction were strongly influenced by the gas atmosphere dew point (DP). After the galvannealing of a panel annealed in a N₂+10 pct H₂ gas atmosphere with low DPs [213 K and 243 K (?60 °C and ?30 °C)], the coating layer consisted of δ (FeZn₁₀) and η (Zn) phase crystals. The Mn-Si compound oxides formed during intercritical annealing were present mostly at the steel/coating interface after the galvannealing. Galvannealing of a panel annealed in higher DP [263 K and 273 K, and 278 K (?10 °C, 0 °C, and +5 °C)] gas atmospheres resulted in a coating layer consisting of δ and Г (Fe₃Zn₁₀) phase crystals, and a thin layer of Г ₁ (Fe₁₁Zn₄₀) phase crystals at the steel/coating interface. The Mn-Si oxides were distributed homogeneously throughout the galvannealed (GA) coating layer. When the surface oxide layer thickness on panels annealed in a high DP gas atmosphere was reduced, the Fe content at the GA coating surface increased. Annealing in a higher DP gas atmosphere improved the coating quality of the GA panels because a thinner layer of oxides was formed. A high DP atmosphere can therefore significantly contribute to the suppression of Zn-alloy coating defects on CMnSi TRIP steel processed in hot dip galvanizing lines.     

热处理过程中纯锌镀层的组织转变和表面氧化

采用FE-SEM,EPMA和XRD等分析了纯锌镀层在加热过程中的组织转变和表面氧化。试验结果表明:GI镀层在较低温度加热后,厚度相对原始镀层没有改变,镀层与基板界面明显,高于800℃加热后,镀层厚度大幅增加,镀层/基体界面并不清晰;500℃加热后镀层组织为ζ相和δ相;随着加热温度升高,镀层组织转变为含铁量更高的Γ1相、Γ相和α-Fe(Zn);900℃加热后镀层几乎全为α-Fe(Zn),只在表面存在少量的Γ相;镀层中的铝随着加热温度升高逐渐向镀层表面迁移,900℃加热后铝完全迁移至镀层表面,形成连续的氧化铝层;低温加热后镀层表面只有很少的Fe-Zn相和氧化物。随着加热温度升高,表面的氧和铝含量增加,锌含量降低。900℃加热后,镀层表面存在Γ相、Al2O3和ZnO。     

On the Processing of Martensitic Steels in Continuous Galvanizing Lines: Part II

The conventional continuous hot-dip galvanizing (GI) and galvannealing (GA) processes can be applied to untransformed austenite to produce Zn and Zn-alloy coated low-carbon ultra-high-strength martensitic steel provided specific alloying additions are made. The most suitable austenite decomposition behavior results from the combined addition of boron, Cr, and Mo, which results in a pronounced transformation bay during isothermal transformation. The occurrence of this transformation bay implies a considerable retardation of the austenite decomposition in the temperature range below the bay, which is close to the stages in the continuous galvanizing line (CGL) thermal cycle related to the GI and GA processes. After the GI and GA processes, a small amount of granular bainite, which consists of bainitic ferrite and discrete islands of martensite/austenite (M/A) constituents embedded in martensite matrix, is present in the microstructure. The ultimate tensile strength (UTS) of the steel after the GI and GA cycle was over 1300 MPa, and the stress-strain curve was continuous without any yielding phenomena.     

An instability in Fe-C-M alloys

Some aspects of phase transformations controlled by carbon diffusion in Fe-C-M alloys, M being a substitutional alloying element, are discussed. The rapid carbon controlled reaction comes to an end when the carbon activity has become uniform all over the material. It is found that this state may be unstable if the alloying element M is nonuniformly distributed. A portion of the interface may then move farther into the region of untransformed material. It is proposed that the ferrite formed inside austenite grains during cooling of intercritically annealed dual-phase steels is formed by this mechanism.     

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.     

Influences of Alloying Elements on Oxidation Behavior of Steels and Microstructure of Oxide Scales

In order to figure out the oxidation behavior of steels during heating,five micro-alloyed steels were subjected to continuous and isothermal oxidation using the thermo gravimetric analyzer and the Gleeble-3500thermo-mechanical simulator.The microstructure of oxide scales,especially the thickness fractions of Fe2O3,Fe3O4 and FeO layers,was analyzed using the scanning electron microscope(SEM),electron probe microanalyzer(EPMA)and electron backscattered diffraction(EBSD)techniques.The micro-alloyed steels containing alloying elements(Si,Cr,Ni and Cu)show a higher oxidation resistance compared with the low carbon steel.It is found that alloying elements accumulated at scale/substrate interface during high temperature oxidation.Alloying elements function in two ways in the oxidation of steels:one is enhancing the scale/substrate interface and consequently suppressing the blister of scales;and the other is impeding the outward diffusion of iron cations from substrate to scales,resulting in the decrease of oxidation rate.As the diffusion of iron cations is impeded,the thickness fractions of Fe2O3 and Fe3O4of micro-alloyed steels are more than those of low carbon steels.     

Application of solute drag theory to model ferrite formation in multiphase steels

In novel multiphase steels for automotive applications, alloying elements are usually employed to control the austenite-ferrite transformation, in order to produce microstructures with an excellent combination of strength and formability. A revised austenite-to-ferrite transformation model for low-carbon steels is proposed which is applicable to industrial heat-treatment conditions of commercial steels. In the model, the effect of alloying elements on the transformation kinetics is described from a fundamental point of view. In the framework of the mixed-mode model in which carbon diffusion in the remaining austenite is coupled to the interface reaction, the partitioning and drag effect of the solute elements are explicitly accounted for. The thermodynamic driving pressure is calculated assuming paraequilibrium conditions, and the solute drag theory of Purdy and Brechet has been modified to remove the artifact of residual solute drag at zero interface velocity. This rather complex model employs, similarly to the semiempirical Johnson-Mehl-Avrami-Kolmogorov (JMAK) approach, four adjustable parameters. However, these parameters are now clearly defined in terms of their physics; i.e., they are pertinent to the interface mobility and solute-interface interaction. The model has been validated with experimental data for a C-Mn steel and two multiphase steels containing either Mo or Si as an additional alloying element. The physical relevance of the resulting solute drag parameters and the inherent challenges regarding their selection are discussed.     

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。     

Morphological stability of γ/α interface formed by carburization in Fe-C-X alloys

Effect of alloying elements on the morphological stability of austenite/ferrite interface formed by carburization of Fe-X alloys at 850 °C and 800 °C was investigated. Planar interfaces were found when the alloying elements added were from among the following: Ti, V, Nb, Ta, Cr, Mo, W, Co, and Cu. Nonplanar interfaces with Widmanstätten-like structures and/or an isolated phase were observed when the alloying elements were from the following group: P, Al, Sb, Ni, Mn, Si, and Ge. The degree of supersaturation of C in the α phase adjacent to the γ phase front was analyzed using the concept of local equilibrium. It was confirmed that there was indeed a close correlation between the morphological stability and the degree of C supersaturation, which in itself depended on whether the alloying element added was an α or γ stabilizer and how strongly it bonded with C in the ferrite phase.     

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.     

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。     

Prediction of Continuous Cooling Transformation Diagrams for Dual-Phase Steels from the Intercritical Region

The purpose of the present work is the implementation and validation of a model able to predict the microstructure changes and the mechanical properties in the modern high-strength dual-phase steels after the continuous annealing process line (CAPL) and galvanizing (Galv) process. Experimental continuous cooling transformation (CCT) diagrams for 13 differently alloying dual-phase steels were measured by dilatometry from the intercritical range and were used to tune the parameters of the microstructural prediction module of the model. Mechanical properties and microstructural features were measured for more than 400 dual-phase steels simulating the CAPL and Galv industrial process, and the results were used to construct the mechanical model that predicts mechanical properties from microstructural features, chemistry, and process parameters. The model was validated and proved its efficiency in reproducing the transformation kinetic and mechanical properties of dual-phase steels produced by typical industrial process. Although it is limited to the dual-phase grades and chemical compositions explored, this model will constitute a useful tool for the steel industry.     

Effect of substrate grain size on iron-zinc reaction kinetics during hot-dip galvanizing

In the galvanizing process, it has been proposed that the grain size of the substrate steel influences the Fe-Zn alloy phase reaction kinetics and growth rate during immersion in the liquid Zn bath. Two grain sizes (nominally 15 and 85 μm) were developed in a decarburized low-carbon (0.005) steel and hot-dipped galvanized in 0.00 wt pct Al-Zn and 0.20 wt pct Al-Zn baths to study the effect of substrate grain size on Fe-Zn phase formation. Uniform attack of the substrate steel occurred in the 0.00 wt pct Al-Zn bath, since an Fe₂Al₅ inhibition layer did not form. No barrier to nucleation of the Fe-Zn phases exists in this Zn bath, and therefore, the substrate steel grain size had no significant effect on the kinetics of phase growth for the gamma, delta, and zeta phase layers. In the 0.20 wt pct Al-Zn bath, discontinuous Fe-Zn phase growth (outburst formation) occurred due to the initial formation of the Fe-Al inhibition layer. The nucleation of the Fe-Zn phases was significantly retarded in this bath for the large (85 μm) substrate grain size. Whereas outbursts were found in the 15-μm grain size substrate after 10 seconds of immersion time, it required 1200 seconds to nucleate just a few outbursts in the 85-μm substrate. These results support the mechanism that Fe-Al inhibition layer breakdown occurs along fast diffusion paths for Zn in the inhibition layer that correspond to the location of substrate steel grain boundaries where reaction with Fe can occur.     

The Development of a Processing Window for the Continuous Galvanizing of a Mn–Cr–Si Martensitic Steel

Martensitic or complex phase steels are leading candidates for automotive impact management applications. However, achieving high strengths while obtaining high quality coatings via continuous galvanizing is a challenge due to cooling rate limitations of the processing equipment and selective oxidation of alloying elements such as Cr, Mn, and Si adversely affecting reactive wetting. The galvanizability of a Cr? Mn? Si steel with a target tensile strength above 1250 MPa was investigated within the context of the continuous galvanizing line. The continuous cooling transformation behavior of the candidate alloy was determined, from which intercritical and austenitic annealing thermal cycles were developed. The evolution of substrate surface chemistry and oxide morphology during these treatments and their subsequent effect on reactive wetting during galvanizing were characterized. The target strength of 1250 MPa was achieved and high quality coatings produced using both intercritical (75% γ) and austenitic (100% γ) annealing using a conventional 95%N₂–5%H₂, ?30°C dew point process atmosphere and 0.20 wt% dissolved (effective) Al bath, despite the presence of significant Mn and Cr oxides on the substrate surfaces. It is proposed that complete reactive wetting by the Zn(Al, Fe) bath was promoted by in situ aluminothermic reduction of the Mn and Cr‐oxides by the dissolved bath Al.     

Transformations

Hot-dip galvanized drawing quality special killed (DQSK) steel and titanium stabilized interstitial free (IF) steel substrates were annealed under varying temperature and time conditions in order to characterize the coating structure development which occurs during the annealing portion of the galvannealing process. Through the use of light optical microscopy, the coating morphology development (Fe-Zn alloy layer growth) observed in cross section on both substrates was defined in three distinct stages. The three characteristic microstructures were classified as type 0 (underalloyed), type 1 (marginally alloyed), and type 2 (overalloyed) morphologies. The morphology transitions were quantitatively defined by total iron content in the coating and by the thickness of an interfacial Fe-Zn gamma phase layer. The DQSK steel coating type 1 to type 2 morphology transition occurred at an iron content of 9 to 10 wt Pct. For the titanium IF material, the same type 1 to type 2 morphology transition occurred at an iron content of 10.5 to 11.5 wt Pct and at an interfacial layer thickness of approximately 1.0 μm. An increased amount of aluminum in the galvanizing bath delayed the alloying reaction during galvannealing for both substrates. The overall inhibition effect of aluminum was less pronounced on the titanium stabilized IF material, indicating that its coating alloying kinetics were not as significantly influenced by bath aluminum content.     

Impact of Martensite Spatial Distribution on Quasi-Static and Dynamic Deformation Behavior of Dual-Phase Steel

The effects of microstructure parameters of dual-phase steels on tensile high strain dynamic deformation characteristic were examined in this study. Cold-rolled steel sheets were annealed using three different annealing process parameters to obtain three different dual-phase microstructures of varied ferrite and martensite phase fraction. The volume fraction of martensite obtained in two of the steels was near identical (~ 19 pct) with a subtle difference in its spatial distribution. In the first microstructure variant, martensite was mostly found to be situated at ferrite grain boundaries and in the second variant, in addition to at grain boundaries, in-grain martensite was also observed. The third microstructure was very different from the above two with respect to martensite volume fraction (~ 67 pct) and its morphology. In this case, martensite packets were surrounded by a three-dimensional ferrite network giving an appearance of core and shell type microstructure. All the three steels were tensile deformed at strain rates ranging from 2.7 × 10^?4 (quasi-static) to 650 s^?1 (dynamic range). Field-emission scanning electron microscope was used to characterize the starting as well as post-tensile deformed microstructures. Dual-phase steel consisting of small martensite volume fraction (~ 19 pct), irrespective of its spatial distribution, demonstrated high strain rate sensitivity and on the other hand, steel with large martensite volume fraction (~ 67 pct) displayed a very little strain rate sensitivity. Interestingly, total elongation was found to increase with increasing strain rate in the dynamic regime for steel with core–shell type of microstructure containing large martensite volume fraction. The observed enhancement in plasticity in dynamic regime was attributed to adiabatic heating of specimen. To understand the evolving damage mechanism, the fracture surface and the vicinity of fracture ends were studied in all the three dual-phase steels.     

Preparation of nanosized zinc oxide by vacuum oxidation and behaviors of impurity elements

Nanosized zinc oxide with the purity ≥99.98 was prepared with a vacuum oxidation method based on hot-dip galvanizing slag by using air as the oxygen source. The effects of reaction temperature and vacuum degree on the product morphologies were investigated, and the influences of main impurity elements in raw materials on the quality of products were evaluated under different oxidation conditions. Reaction temperature arid vacuum degree dramatically affect the product morphologies. At appropriate temperature and vacuum degree, the main products are wurtzite crystals. The crystal needles are elongated and long in length. Impurity Fe and Pb elements influence the quality of products through various patterns under different oxidation conditions. Fe remains in the products mainly relying on the mechanical entrainment of Zn vapor and the positive deviation of Fe-Zn system, while Pb is retained mainly based on the vapor pressure and the positive deviation of Pb-Zn system.