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.     

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.     

Surface Oxidation of the High-Strength Steels Electrodeposited with Cu or Fe and the Resultant Defect Formation in Their Coating during the Following Galvanizing and Galvannealing Processes

This study examined the surface oxidation of high-strength steels electrodeposited with Cu or Fe and the resultant defect formation in their coating during the following galvanizing and galvannealing processes. The high-strength steels were coated with an Cu or Fe layer by the electroplating method. Then, the coated steels were annealed in a reducing atmosphere, dipped in a molten zinc, and finally transformed into galvannealed steels through the galvannealing process. The formation of Si and Mn oxides on the surface of the high-strength steel was effectively suppressed, and the density of surface defects on the galvanized steel was significantly reduced by the pre-electrodeposition of Cu and Fe. This effect was more prominent for the steels electrodeposited at higher cathodic current densities. The finer electrodeposit layer formed at higher cathodic current density on the steels enabled the suppression of partial surface oxidation by Mn or Si and better wetting of Zn on the surface of the steels in the following galvanizing process. Furthermore, the pre-electrodeposited steels exhibited a smoother surface without surface cracks after the galvannealing process compared with the untreated steel. The diffusion of Fe and Zn in the Zn coating layer in the pre-electrodeposited steels appears to occur more uniformly during the galvannealing process due to the low density of surface defects induced by 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.     

Initial Oxidation of a 9%CrMo‐ and a 12%CrMoV‐Steel

For the oxidation and high temperature corrosion resistance of 9‐12% Cr steels, the rapid formation of a dense protective Cr‐rich oxide scale is important. The initial oxidation processes were investigated on a 9%CrMo‐steel and a 12%CrMoV‐steel. Auger spectroscopic studies in the first hours showed a non‐uniform oxidation and effects of surface segregation and microstructure. Grain boundaries and martensite laths provide sufficient Cr to the surface for chromia formation, in other areas formation of SiO₂ may prevent Fe‐oxide growth. For up to 100 hours the oxidation kinetics is largely controlled by diffusion of the selectively oxidized elements Cr, Mn and Si in the steel, only gradually the transition to control by diffusion in the oxide occurs. Thickness and composition of the scale, and also the diffusion profiles in the steel were determined after 10 and 100 hours oxidation by SNMS, revealing important effects of surface treatments, such as electropolishing, polishing, grinding or sandblasting. Strong surface deformation favours the formation of Cr‐rich scales and of flat Cr‐depletion minima. Also the effects of different oxidation atmospheres, H₂‐H₂0, N₂‐H₂‐H₂0 and N₂‐O₂ were investigated and described. The kinetics of the oxide growth and the possibilities to obtain protective scales by pre‐oxidation are discussed.     

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.     

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.     

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.     

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.     

Pickling of Process‐Oxidised Austenitic Stainless Steels in HNO3‐HF Mixed Acid

Oxide formation during production annealing and the subsequent pickling response in mixed acid have been studied. The aims were to characterise the oxides formed and to understand how the pickling mechanism and kinetics are affected by the nature of the oxide. Totally, eight different versions of the austenitic stainless steel grades AISI 301, 304L and 309L were studied, all annealed in production lines. Cold rolled oxides (formed during annealing) are thin (< 1 µm), dense and formed in a multilayered manner. Hot rolled oxides (formed during reheating, hot rolling and annealing) are thicker (>1 µm) and more heterogeneous in thickness and composition. The dissolution rate of the chromium depleted layer (CDL) under the oxide is the most important factor for the overall pickling rate. The permeability of acid through the oxide and the tendency of the oxide to spall are also important factors affecting the pickling kinetics. The dense oxide formed on cold rolled materials can to some extent hinder the acid to reach the CDL. The oxides on hot rolled materials are porous and do not provide such a barrier but they are thicker and thereby more difficult to remove. Shot‐blasting prior to pickling of the hot rolled materials improves the pickling performance because it thins the oxide, improves the permeability and increases the tendency of the oxide to spall during the pickling step.     

Oxidation of Fe–18%Mn–0.6%C Steels in Air and a N2–CO2–O2 Mixed Gas Atmosphere at 1273–1473 K

Austenitic Fe–18 wt% Mn–0.6 wt% C steels were oxidized at 1273, 1373, and 1473 K for up to 2 h in either atmospheric air or an 85%N₂–10%CO₂–5%O₂ gas mixture. The alloys oxidized faster in air than in the mixed gas, but the morphology and composition of the oxide scale formed were similar in both atmospheres. The scales that consisted primarily of FeO, Fe₂O₃, and MnFe₂O₄ were highly susceptible to cracking and spallation due to the severe oxidation condition. Since Mn was consumed to form MnFe₂O₄, the original γ‐matrix changed to an α‐matrix in the subscale area, in which Mn‐rich internal oxide precipitates formed locally.     

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.     

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.     

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.     

Effects of Alloying Elements on High-Temperature Oxidation and Sticking Occurring During Hot Rolling of Modified Ferritic STS430J1L Stainless Steels

In the present study, mechanisms of sticking that occurs during hot rolling of modified STS430J1L ferritic stainless steels were investigated by using a pilot-plant-scale rolling machine, and the effects of alloying elements on sticking were analyzed by the high-temperature oxidation behavior. The hot-rolling test results indicated that the Cr oxide layer formed in a heating furnace was broken off and infiltrated the steel, thereby forming Cr oxides on the rolled steel surface. Because the surface region without oxides underwent a reduction in hardness rather than the surface region with oxides, the thickness of the surface oxide layer favorably affected the resistance to sticking. The addition of Zr, Cu, and Ni to the ferritic stainless steels worked in favor of the decreased sticking, but the Si addition negatively affected the resistance to sticking. In the Si-rich steel, Si oxides were continuously formed along the interfacial area between the Cr oxide layer and the base steel, and interrupted the formation and growth of the Cr oxide layer. Because the Si addition played a role in increasing sticking, the reduction in Si content was desirable for preventing sticking.     

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.     

Effect of Mn,Si and Mn‐Si Alloying on the Precipitation of Ultra‐fine Oxides in Fe during Solidification

The effect of Mn, Si and Mn‐Si alloying on the precipitation of oxide inclusions in Fe during solidification has been investigated. The results show that the inclusions precipitating during solidification are relatively small and distribute uniformly in Mn, SI and Mn‐Si alloyed steels. Most of the inclusions are nearly spherical. The maximum diameter of inclusions is only 3.3μm in the three types of alloyed steels. The average size of inclusions is 1.3μm, 1.2μm and 1.1μm in Mn, Si and Mn‐Si alloyed steels, respectively. The maximum amount of inclusions is 1.1×10⁵ per unit volume (mm^?3) in Mn alloyed steel and the minimum is 5.8×10⁴ per unit volume in Si alloyed steel. The volume fractions of the inclusions with Mn, Si and Mn‐Si alloying are 0.01%, 0.005% and 0.006%, respectively.     

Effect of steel composition on failure of oxide scales in tension under hot rolling conditions

The differences in failure of oxide scales formed on mild, Si‐Mn, Mn‐Mo and stainless steels were investigated using a high‐temperature tensile test technique over the range of test parameters near to the hot rolling conditions at entry into the roll gap. Temperature, strain and strain rates were 783 – 1200 °C, 2.0 – 5.0 % and 0.2 – 4.0 s^?1 respectively. The scale thickness was maintained within 5 – 250 μm. Mild steel has the highest oxidation rate throughout the temperature range. A slightly thicker scale for the Mn‐Mo steel compared with Si‐Mn steel was observed. The stainless steel has shown the highest resistance to oxidation. Although through‐thickness cracks and sliding were competitive mechanisms for oxide scale failure for the mild steel, the other steel oxides failed only by through‐thickness cracking or were delaminated over the whole temperature range 783 ‐ 1200 °C. Modelling based on the finite‐element method was applied for better understanding of the micro‐events both during uni‐axial tension and just before contact with the rolls. The part of the model related to oxide scale failure has been upgraded taking into account experimental evidence concerning differences in scale failure, due to the steel chemical content, which were observed in the hot tensile tests.     

Surface and Grain Boundary Segregation in Fe‐3%Si Alloy

The surface segregation on the Fe‐3wt.%Si alloy was studied using X‐ray Photoelectron Spectroscopy (XPS) with synchrotron radiation at 150 eV photon beam energy (Si 2p). A silicon oxide layer and also segregation of Si atoms in three clearly resolved phases occurred during heat treatment. A formation of silicides mainly with the Fe₃Si superstructure was observed. A silicon nitride layer was created by nitrogen ion implantation. The structure and atomic ordering in a surface layer of the samples (approx. 300 nm thick) was checked by Conversion Electron Mössbauer Spectroscopy (CEMS). Simultaneously emission Mössbauer spectroscopy was used for the investigation of the Si concentration and atomic ordering at grain boundaries.     

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.