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.     

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.     

Effect of the presence of alloying elements in interstitial-free and low-carbon steels on their surface composition after annealing in reducing atmospheres (dew point=−30 °C)

The X-ray photoelectron spectroscopy (XPS) method is used to study the outer surfaces of interstitial-free (IF) and low-carbon (LC) steels with different alloying element contents (P, Ti, Nb, and Mn) after annealing at temperatures of 805 °C and 705 °C, respectively, for 40 seconds in reducing atmospheres (dew point=−30 °C). The work discussed seeks to establish possible relationships between the bulk composition of the IF and LC steels and the contents of segregated alloying element observed by XPS on the surface of the annealed steels, as well as to establish the influence of the presence of a thin iron oxide film on the steel surface on the segregation and oxidation of the alloying elements. Despite the low Mn and Si bulk steel contents and the shortness of the annealing cycle, considerable enrichment of these elements on the surface is seen, mainly as manganese and silicon oxides. The formation of a MnO layer on the annealed steel surface seems to be related to the reduction of iron oxides and the increase in the metallic Fe content. Despite its low content in LC steels, carbon also seems to diffuse towards the annealed steel surface to reduce iron oxides.     

Selective Oxidation and Sub‐Surface Phase Transformation of TWIP Steel during Continuous Annealing

The selective oxidation of Twinning Induced Plasticity (TWIP) steel during annealing at 800 °C in a N₂ + 10%H₂ gas atmosphere with a dew point of ?17 °C and ?3 °C was investigated by means of high resolution transmission electron microscopy of cross‐sectional samples. The annealing resulted in the selective oxidation of Mn and Si and the austenite‐to‐ferrite phase transformation of the sub‐surface region. In the low dew point atmosphere, the annealing resulted in the formation of a MnO layer at the surface. Crystalline c –xMnO · SiO₂ (x ≥ 2) particles and amorphous a –xMnO · SiO₂ (x < 0.9) particles were found at the interface between the MnO layer and the steel matrix. In a narrow zone of the sub‐surface, the Mn depletion resulted in the transformation of the initial austenite. In the high dew point atmosphere, a thicker MnO layer was formed on the surface and no mixed manganese‐silicon oxides particles were observed at the MnO/steel matrix interface. In the sub‐surface, Mn was significantly depleted in the range of 2–3 µm below the surface and the initial austenite in this zone was transformed to ferrite. MnO particles were found at the grain boundaries and in the interior of grains.     

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 annealing conditions on the galvanizability and galvannealing properties of TiNb interstitial-free steels, strengthened with phosphorous and manganese

A high-strength interstitial-free (HS IF) steel, solution strengthened with P and Mn, was hot-dip galvanized and galvannealed in a laboratory hot-dip simulator. The dew point of the N₂-H₂ annealing atmosphere during recrystallization was varied, and the effect of the dew-point changes on the galvannealing kinetics was studied. Annealing in a high-dew-point N₂-H₂ atmosphere improved the wettability by the zinc and the galvannealing reactivity of the Mn-P-added IF steels considerably. Scanning electron microscopy (SEM) analysis and glow discharge optical emission spectroscopy (GDOES) depth profiles of the surface of the steel sheet and the subsurface region revealed clear differences in oxidation mode after recrystallization annealing. Plane-view SEM and transmission electron microscopy (TEM) analyses were done on the inhibition layer of the as-galvanized samples. Differences in the Mn and P contents were found. By analyzing the Mn and P contents in the coatings during galvannealing, a mechanism was proposed to explain the higher galvannealing reactivity which is observed when the dew point during recrystallization annealing is increased.     

Local Equilibrium and Nodule Formation on Al‐TRIP‐Aided Steel Surfaces During Intercritical Annealing

Several advanced high strength steels were intercritically annealed at a dew point of ?5°C. Afterwards, surface morphology was investigated by scanning and transmission electron microscopy (TEM). In Al alloyed TRIP‐aided steels, nodules of metallic Fe containing traces of Mn could be proven by TEM analysis. To clarify the mechanism of origin, several further annealing trails were done and finally a new component of the occurring heterogeneous gas/metal reaction during intercritical annealing was postulated. It is concluded that neither the diffusion mechanism of the alloying elements nor the stress gradient between stress‐free surface region of the internal oxidation front nor the oxygen partial pressure dominates alone the selective oxidation process. It is suggested that the reactivity of the considered surface, its local surface chemistry and the local thermodynamic equilibrium should be taken into account in greater detail. Preferred dissociation points of absorbed water vapor could lead to a local increased oxygen partial pressure. With this, a nanoscaled oxidation/reduction process could be initiated.     

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.     

Selective Oxidation and Reactive Wetting during Galvanizing of a CMnAl TRIP-Assisted Steel

A transformation induced plasticity (TRIP)-assisted steel with 0.2 pct C, 1.5 pct Mn, and 1.5 pct Al was successfully galvanized using a thermal cycle previously shown to produce an excellent combination of strength and ductility. The steel surface chemistry and oxide morphology were determined as a function of process atmosphere oxygen partial pressure. For the 220 K (–53 °C) dew point (dp) + 20 pct H₂ atmosphere, the oxide morphology was a mixture of films and nodules. For the 243 K (–30 °C) dp + 5 pct H₂ atmosphere, nodules of MnO were found primarily at grain boundaries. For the 278 K (+5 °C) dp + 5 pct H₂ atmosphere, nodules of metallic Fe were found on the surface as a result of alloy element internal oxidation. The steel surface chemistry and oxide morphology were then related to the reactive wetting behavior during continuous hot dip galvanizing. Good wetting was obtained using the two lower oxygen partial pressure process atmospheres [220 K dp and 243 K dp (–53 °C dp and –30 °C dp)]. An increase in the number of bare spots was observed when using the higher oxygen partial pressure process atmosphere (+5 °C dp) due to the increased thickness of localized oxide films.     

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.     

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.     

内氧化对热镀锌高强钢镀层/基板界面的影响

 由于高强钢中添加的Si、Mn等合金元素会在退火时会发生选择性氧化,从而影响镀液与带钢之间的润湿性,因此热镀锌高强钢生产存在可镀性的难题。为了提高热镀锌高强钢的镀层附着性,以不同镀层附着性的连续热镀锌0.2%C-1.8%Si-1.8%Mn高强钢为研究对象,采用GD-OES、SEM、FIB、TEM等研究了镀层/基板界面抑制层与基板次表层内氧化层的特征,同时采用模拟退火试验研究了退火气氛露点对内氧化层形成的影响,揭示了退火气氛露点、内氧化层厚度、抑制层覆盖率与镀层附着性之间的相关性。结果表明,该热镀锌高强钢镀层附着性优劣由镀层/基板界面位置抑制层决定,当抑制层覆盖率达到80%以上时,可获得良好的镀层附着性。内氧化层厚度对抑制层覆盖率的影响存在临界厚度,约为0.58 μm。当内氧化层厚度由0逐渐增加至0.58 μm时,抑制层覆盖率由约10%增加至约80%;当内氧化层厚度由0.58进一步增加至3.85 μm时,抑制层覆盖率略有增加,介于80%~90%之间。提高退火气氛露点可以促进基板次表层形成内氧化,在退火温度分别为800和870 ℃、保温时间为120 s、退火气氛为N₂-5% H₂(体积分数)的试验条件下,当退火气氛露点由-40 ℃提高到+10 ℃时,内氧化层厚度由基本为0提高至3~5 μm。为了获得合适的内氧化层厚度,建议将0.2%C-1.8%Si-1.8%Mn高强钢的退火气氛露点控制在-20~-10 ℃范围内。     

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.     

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.     

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 Magnetic Field Direction on γ‐fiber Texture Evolution in Cold‐rolled Interstitial‐free Steel Sheet during Annealing

The effects of magnetic field direction on γ‐fiber texture evolution in as‐annealed interstitial‐free (IF) steel sheet were investigated by means of X‐ray diffraction ODF analysis. Specimens cut from cold‐rolled IF steel sheets were placed at the center of a 12‐T magnetic field, tilted by different angles to the magnetic field direction respectively, and annealed at 750 °C for 30 min. The results show that altering the specimen orientation to the magnetic field direction during annealing does not change the final annealing textures. The average intensity of the γ‐fiber texture of specimens annealed under the magnetic field is higher compared to conventionally annealed specimens. The intensity of the main γ‐fiber texture components presents a similar periodic variation with respect to the specimen orientation to the magnetic field, i.e., it is weakened as the tilt angle increases from 0°, and subsequently strengthened to a maximum value at 45°, and then weakened again as the tilt angle continues to increase. When the magnetic field is applied in the direction perpendicular to the specimen's rolling plane, the intensity of the main γ‐fiber texture components of specimens annealed in the magnetic field is close to that of the specimen annealed without field. This phenomenon might be attributed to the demagnetic effect.     

In‐situ investigation on the oxidation behaviour of low alloyed steels annealed under N2‐5%H2 protective atmospheres

The oxidation behaviour of low alloyed steels, Fe‐0.6%Mn and Fe‐1.5%Mn, under different annealing conditions was studied. Due to the crucial importance of the surface state of the sample, the experiments were performed in an in‐situ device to avoid any contact with air after the annealings. The annealing experiments were carried out under different conditions: high vacuum (~10^?6 mbar), N₂/H₂ protective atmospheres with traces of water (dew point ‐30 °C) and temperatures ranging from 873 to 1073 K. Under this variety of heat treatments, the reconstruction of the Fe surface and the formation of different oxides was observed and characterised, paying special attention to the selective oxidation of manganese. The surface structure and composition was investigated by means of the combined use of reflection high‐energy electron diffraction (RHEED) and X‐ray photoelectron spectroscopy (XPS). The analyses show that the use of RHEED is a good alternative for determining the crystallographic structure of the outermost layers of the surface. With this technique the structures of iron and manganese oxides can be distinguished despite the similar structures and lattice parameters. It is also possible to identify the crystallographic textures present on the oxidation products and to give qualitative information about the surface reconstruction of the grains.     

Effect of soaking temperature and annealing atmosphere on magnetic properties of semi-processed nonoriented electrical steel containing 0.4 % silicon

In order to investigate the effect of soaking temperature and annealing atmosphere on magnetic properties of the semi-processed nonoriented electrical steel containing 0.4 % silicon, customer annealing was carried out at a temperature ranging from 730 to 950 and in different annealing atmospheres. As the soaking temperature increases from 730 to 950 in the dry N2 atmosphere, the core loss at 1.5 Tesla decreases continuously, whereas the permeability at 1.5 Tesla increases up to 890 and then decreases significantly at 950 °C. Among DX atmospheres having a dew point of -23 °C, the air to LPG ratio of 19.5 is found to reveal the best magnetic properties due to the lowest carbon content. At a dew point of +5 °C and an air to LPG ratio of 18.5 the best magnetic properties are to be achieved regarding both carbon content and internal oxidation layer.     

Adverse effect of high purity atmosphere on sintering of manganese steels

Abstract

The Fe–(2, 3)Mn and Fe–(2, 3)Mn–0·4C specimens were sintered in the dilatometer tests for 30 min at 1150°C in an H₂–H₂ O atmosphere with a dew point of –30 and –70°C. The Mn addition at sintering of the specimens with a dew point of –30°C resulted in higher swelling with a maximum at 1150°C and processing at a dew point of –70°C resulted in minimal differences in swelling of the specimens in dependence on the Mn addition. Processing in the high purity atmosphere (–70°C) causes a loss of Mn in the form of Mn vapour transported away by the flowing atmosphere needed for alloying of the Fe matrix. On the contrary, at sintering in a low purity atmosphere (–30°C) the reaction of Mn vapour with oxygen of high partial pressure occurs near the surface of the specimens. Sintering of Mn steels requires the low purity atmosphere in contrast to the thermodynamic requirements. The sintering of Mn steels occurred under the effect of Mn vapour formed by sublimation regardless the thermodynamics for Mn–O system.