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.     

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.     

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.     

Adhesion and Thermal Shock Resistance of Al2O3 Thin Films Deposited by PACVD for Die Protection in Semi‐solid Processing of Steel

In this work thin Al₂O₃ films were deposited on hot working steel AISI H11 by plasma assisted chemical vapour deposition (PACVD). The effect of the AlCl₃/O₂ ratio in the gas mixture and the substrate temperature on the film hardness and constitution of the deposited films was investigated by nanoindentation and X‐ray diffraction, respectively. Within the investigated process parameter window thin films containing either the γ‐Al₂O₃ or the α‐Al₂O₃ phase were grown. The performance of these Al₂O₃ coatings for the semi‐solid processing of steel was studied with respect to hardness, adhesion and resistance to thermal shock. The maximum critical load of 50 N as determined by scratch testing was achieved after plasma nitriding of the substrate. No cohesive or adhesive coating failure could be detected after 1000 thermal shock cycles at a contact temperature of 1170±30 °C. Based on the here presented adhesion and thermal shock data it can be concluded that the Al₂O₃ thin films are suitable candidates for the die protection during semi‐solid processing of steel.     

Analysis of the influence of the hot-rolling material on galvanized product

Hot-rolled galvanized steel sheet is made from hot-rolled pickled sheet by continuous hot-dip galvanizing process.Without the cold-rolling process,it greatly reduces the operating costs and saves investment for shorter process and lower energy consumption.The economic advantage is obvious.The characteristics of high-yield and low cost will greatly enhance the competitiveness of enterprises in the market.There are big differences between the substrates of hot-rolled galvanized steel sheet and cold-rolled galvanized steel sheet in surface roughness,chemical elements,and surface defects.These factors directly affect on the quality of galvanized sheet.Pickling process is used to remove the oxide layer which is formed on the surfaces of hot-rolled steel sheet.The surfaces must be thoroughly cleaned for the oxide layer will seriously affect the adhesion of galvanized coating.Residual impurities,Carbon concentrating and other problems must not be caused during pickling as well.Therefore,the quality of galvanizing depends on the quality of pickled sheet surfaces.Experimental methods such as AES,XPS,SEM,OM are employed during the research for detailed analysis on the effects of hot-rolled plates and hot pickling plates on the quality of hot-rolled galvanized products.     

Comparison of the Activation Energies of the Formation of Chromium Carbide Coating on Carburized and Uncarburized AISI 1020 Steel

Chromium carbide coatings deposited by the salt bath method have a lot of technologically interesting characteristics. This method produces hard, wear–resistant, oxidation and corrosion–resistant coating layers on steel substrates. In the present study, the kinetics of chromium carbide formation on carburized and uncarburized AISI 1020 steel substrates has been compared. The presence of the Cr₇C₃ phase on the surface of steel substrates was confirmed by X‐ray diffraction. Cross–sectional observation of optical and SEM images showed that chromium carbide layers formed on the steel substrates were rather compact and smooth. The kinetics of chromium carbide coating by salt bath immersion indicated a parabolic relationship between carbide layer thickness and treatment time. The activation energy of the formation of carbide on the surface of carburized and uncarburized steel was calculated to be 87.9 and 225.6 kJ/mol, respectively. Moreover, an attempt was made to present contour diagrams for predicting the thickness of the chromium carbide layer. In addition, the possibility of establishing and using some mathematical relationships between process parameters and chromium carbide layer thickness was investigated.     

Microstructural study of galvanized coatings formed in pure as well as commercial grade zinc baths

This investigation is an effort to have a better understanding of the growth kinetics and morphology of the coating formed during the galvanizing process in pure as well as commercial grade zinc baths. The protective coating that is formed during hot dip galvanizing, normally between 450 and 480°C, consists of a series of Fe-Zn intermetallic layers, which have been identified as gamma (Γ), delta (δ), zeta (ξ) and an outer eta (η) layer, highly rich in zinc. There is apparently no delay in the formation of ξ or δ phases in both pure as well as the commercial grade zinc baths. The gamma (Γ) phase is formed after an incubation time of about 30 s at a bath temperature of 470°C in the pure zinc bath. Its formation is further delayed in the commercial grade zinc bath. The last morphological feature is the formation of a second ξ layer at the ξ/δ interface in the pure zinc bath. In the commercial grade zinc bath two different morphologies of ξ phase are seen starting from the lowest dipping time, and also the overall coating is considerably thicker due to formation of several iron-zinc intermetallics which degrade its ductility and outward appearance. Commercial grade zinc also enhances the dross formation in the bath and deteriorates the quality of the coating. Presence of transverse cracks as well as entrapment of dross particles in the coating is attributed to the less compact coating that is formed in the commercial grade zinc bath.     

双相钢表面山峰纹问题分析与控制

在生产过程中,热镀锌双相钢表面出现明显的山峰纹缺陷,严重影响热镀锌双相钢产品的表面质量。缺陷处有漏镀、锌层不均和抑制层形成不良等特征,基板表层有脱碳及微裂纹、表层毛刺突起等现象。通过分析认为,基板表层微裂纹是造成热镀锌双相钢表面山峰纹的根本原因。采用低温快烧的加热制度,适当降低轧制温度,合理控制除鳞及酸洗工艺,降低热卷厚度以降低冷轧压下率,可有效控制冷轧板浅表层微裂纹的形成,从而有效解决热镀锌双相钢表面山峰纹问题。     

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.     

高强度热镀锌双相钢的可镀性问题研究

 高强度热镀锌双相钢的可镀性问题是当前热镀锌技术的主要热点之一。生产高强热镀锌双相钢的主要难点在于得到理想的组织与可镀性之间的矛盾。国内外研究机构深入研究了高强度双相钢中的合金元素的选择性氧化行为、氧化物的生长规律,以及在退火炉气氛下气相-金属反应。在工业实践上应用这些基本的理论与规律,开发出了多种可提高高强度热镀锌双相钢可镀性的工艺,包括预氧化-还原法、反应退火法、闪镀法等。     

热浸镀锌铝镁镀层微观组织试验

 研究了热浸镀工艺对于镀层的微观结构的影响,利用扫描电镜（SEM）及能谱分析（EDX）观察了Zn-Al-Mg镀层表面以及截面的微观结构、合金层的形貌、镀层中各相的成分组成,利用辉光放电发射光谱仪(GDS)分析了镀层中各元素沿深度方向的分布,利用电子探针（EPMA）分析了镀层中各元素的分布,利用X射线光电子能谱（XPS）分析了镀层表面元素,利用X射线衍射(XRD)分析了镀层的相组成。结果表明,镀层中各元素沿镀层的深度方向的分布并不均匀,Mg在镀层表面富集,镀层组织呈现多相混合结构,以Zn晶粒、MgZn2与Zn组成的共晶为主,同时存在块状富铝相以及一层较薄的合金层。     

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.     

Phase and Microstructural Analysis of Hot Rolled FeNi42 Sheet,its Response in Magnetic and Mechanical Properties

Inclusions unavoidably existing in steels and consequently also in final products obtained by e.g. rolling markedly affects the physical properties. This paper is devoted to investigation of FeNi42 steel hot rolled into a sheet form. The structural and phase analysis is done by scanning electron microscopy, X‐ray diffraction, and Mössbauer spectroscopy completed by magnetic and hardness measurements. The results yield an inhomogeneous nickel distribution in the sheet resulting in a formation of the intermetallic Ni₃Fe phase. A depletion of sheet surface by nickel leads to an intensive surface oxidation; its thickness increases in the direction of sheet edges. The non‐metallic oxide inclusions are concentrated predominantly at grain boundaries, which contribute to an easier cracking. The formation of Ni₃Fe affects a small increase in saturation magnetization. The oxides and consequently cracks formation cause magnetic hardening as can be seen on an increase of the structurally sensitive remnant magnetization. The hard oxide inclusions evoke also the hardening of material, rise brittleness and crack liability.     

Effect of Titanium Addition on As Cast Structure and Macrosegregation of High‐Carbon High‐Chromium Steel

In casting heavy ingots of high‐chromium high‐carbon cold work steels, macrosegregation develops in the center of the ingot, causing difficulties during subsequent hot working. Heat transfer and solidification of an industrial scale high‐carbon high‐chromium steel ingot was simulated and thereafter a laboratory scale representative ingot was designed to model the solidification of the industrial scale ingot. Titanium in the range of 0.3–1% was added to the high‐chromium high‐carbon (12%Cr–2%C) steel during melting process. Microstructures, macrosegregation and phase formations were studied using optical microscopy, scanning electron microscopy, energy dispersive X‐ray spectrometry, wave dispersive X‐ray spectrometry, optical emission spectroscopy, and X‐ray diffraction. Addition of 0.3% titanium was sufficient to diminish the macrosegregation; however it did not have a significant effect on the grain size. Addition of 0.7 and 1% titanium had a substantial effect on grain size in the longitudinal direction and refined the primary carbides structure. The formation of small TiC carbides that precipitated before solidification of liquid iron acted as nuclei for primary pro‐eutectic austenite grains.     

Hot-dip Galvanizing of Carbon Steel after Cold Rolling with Oxide Scale and Hydrogen Descaling简

A new processing method for producing hot dip galvanized steel is designed and tested, in which pickling is skipped. Hot-rolled low carbon steel sheets are roiled with oxide scale in an experimental mill at room temperature, prior to annealing under a 20% hydrogen reducing atmosphere and galvanizing on a hot-dip galvanizing simulator. Micro-cracks formed in the oxide scale during cold rolling roughen the steel surface and enlarge the specific surface. Through-thickness cracks provide transport channels for hydrogen, and hence the reduction of oxide scale is en- hanced. When the sheet is dipped in the zinc bath, cracks are submerged by liquated zinc and the defects are not dis- tinct after hot-dip galvanizing. The overlay coating occludes with rough surface of the sheet, whereby a superior coat- ing adherence is realized.     

先进高强钢选择性氧化及抗粉化性能

介绍了生产先进高强钢热浸镀锌板的重要性,论述了生产过程中出现选择性氧化的原因及合金化板产生粉化的原因.具体分析了保护气氛的露点、保护气氛的组成、退火温度及时间、合金元素的种类和含量对高强钢选择氧化的影响.并分析了合金化工艺及锌液成分对合金化镀层相结构及抗粉化性能的影响.     

Thermal Fatigue Testing of Plasma Transfer Arc Stellite Coatings on Hot Work Tool Steels under Steel Thixoforming Conditions

The thermal fatigue performance of Stellite 12 coating deposited on X32CrMoV33 hot work tool steel via the plasma transfer arc (PTA) process was investigated under steel thixoforming conditions. Stellite 12 coating has made a favorable impact on the thermal fatigue performance of the X32CrMoV33 hot work tool steel. The latter survived steel thixoforming conditions lasting much longer, for a total of 5000 cycles, when coated with a PTA Stellite 12 layer. This marked improvement is attributed to the higher resistance to oxidation and to temper softening of the Stellite 12 alloy. The Cr-rich oxides, which form during thermal cycling, provide adequate protection to high-temperature oxidation. In contrast to hot work tool steel, Stellite 12 alloy enjoys hardening upon thermal exposure under steel thixoforming conditions. This increase in the strength of the coating is produced by the formation of carbides and contributes to the superior thermal fatigue resistance of the Stellite 12 alloy. When the crack finally initiates, it propagates via the fracture of hard interdendritic carbides. The transformation of M₇C₃ to M₂₃C₆, which is more voluminous than M₇C₃, promotes crack propagation.     

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.     

热镀锌双相钢表面粗糙问题分析与控制

 目前强度级别较高的双相钢产品已经可以普遍采用热镀锌工艺生产,热镀锌双相钢在生产过程中,表面出现明显的粗糙缺陷,形成边部与中部的色差,严重影响热镀锌双相钢产品表面质量。粗糙缺陷伴随粗糙度异常升高、锌层不均、抑制层形成不良、基板表面微裂纹等现象。分析认为,基板表面微裂纹是造成热镀锌双相钢表面粗糙的主要原因。热轧态组织和冷轧压下率是决定冷硬板浅表层微裂纹形成的关键因素。通过优化卷取温度及热轧卷厚度,改善热轧态组织及降低冷轧压下率,可有效控制冷轧板表面浅表层微裂纹的形成,从而良好解决热镀锌双相钢表面粗糙问题。     

热镀锌锌层粘附性影响因素及控制

分析了镀锌原板状态、加热炉工艺、锌液化学成分、镀锌温度等因素对改良森吉米尔法热镀锌锌层粘附性的影响;通过提高对原板的要求、优化加热炉工艺条件、严格控制锌液中各元素含量、优化镀锌温度等措施,得到锌层粘附性良好的热镀锌板。