Investigation and improvement of tiny spot defects on hot-dip galvanized automotive steel sheets

The causes of tiny spot defects on the surface of hot-dip galvanized automotive steel sheets were studied using scanning electron microscopy(SEM)and energy dispersive spectrometer(EDS),and effective control measures were introduced.The results show that rubbing against the top roller after galvanizing is easy due to the local thickness of tiny spot defect location coating;therefore,the surface morphology is different from the normal part.Three kinds of defects,namely zinc slag,small slivers,and pitting,are likely to cause local thickening of the coating after galvanizing,leading to the formation of tiny spots.Therefore,resolving the three types of defects can effectively control the generation of tiny spot defects.Among them,due to the hereditary nature of the small sliver defect,focusing on its control and supervision is necessary.

Change Rules of Γ_2 Particles in Hot-dipped Zn-Ti Coating

Hot-dip Zn-Ti galvanizing can restrain the excess growth of the coating which has better corrosion resist- ances than hot-dip pure Zn. The change rules of Г2 intermetallic compound in hot-dip Zn-Ti galvanizing is investiga ted by immersion time, titanium content and the slag test using scanning electron microscopy （SEM）, energy dis- persive spectroscopy （EDS） and X-ray diffraction （XRD）. And the mechanism of nucleation and growth of Г2 inter- metallic compound is analysed. The results show that, when adding 0. 05mass% titanium to the zinc bath, the Г2 particles form in the η layer, which nucleate by obtaining Ti atoms from the phase and Fe atoms from the dissol- ving ζ phase layer. Moreover, the more titanium is added into the bath, the more and bigger Гz particles appear. The Fz particles in the coatings grow up noticeably with prolonging the immersion time.

Recent development of UHSS and its hot-dip galvanizing processes in Baosteel

Baosteel has excelled in automotive steel sheets in the past three decades.It has made a significant contribution to the development of China’s automotive industry by producing a wide range of high-quality steel products.Some milestones achieved by Baosteel automotive steel sheet were briefly reviewed.The current challenges in producing ultra-high strength steel(UHSS),especially hot-dip galvanized UHSS,were summarized.The most current advancements in UHSS and the corresponding hot-dip galvanizing processes were discussed.The galvanizability of Si-Mn-added QP steel and DP steel, Mn-added TWIP steel, and Al-added low-density steel has been improved by different techniques in Baosteel.

Effect of hot-dip galvanizing processes on the microstructure and mechanical properties of 600-MPa hot-dip galvanized dual-phase steel

A C–Mn dual-phase steel was soaked at 800°C for 90 s and then either rapidly cooled to 450°C and held for 30 s(process A) or rapidly cooled to 350°C and then reheated to 450°C(process B) to simulate the hot-dip galvanizing process. The influence of the hot-dip galvanizing process on the microstructure and mechanical properties of 600-MPa hot-dip galvanized dual-phase steel(DP600) was investigated using optical microscopy, scanning electron microscopy(SEM), transmission electron microscopy(TEM), and tensile tests. The results showed that, in the case of process A, the microstructure of DP600 was composed of ferrite, martensite, and a small amount of bainite. The granular bainite was formed in the hot-dip galvanizing stage, and martensite islands were formed in the final cooling stage after hot-dip galvanizing. By contrast, in the case of process B, the microstructure of the DP600 was composed of ferrite, martensite, bainite, and cementite. In addition, compared with the yield strength(YS) of the DP600 annealed by process A, that for the DP600 annealed by process B increased by approximately 50 MPa because of the tempering of the martensite formed during rapid cooling. The work-hardening coefficient(n value) of the DP600 steel annealed by process B clearly decreased because the increase of the YS affected the computation result for the n value. However, the ultimate tensile strength(UTS) and elongation(A80) of the DP600 annealed by process B exhibited less variation compared with those of the DP600 annealed by process A. Therefore, DP600 with excellent comprehensive mechanical properties(YS = 362 MPa, UTS = 638 MPa, A_(80) = 24.3%, n = 0.17) was obtained via process A.

The Influence of Al on the Surface Properties of the Hot-dip Galvanized Melt

Wettability of Zn-Al alloy melt on the pure iron substrate at 450℃was studied.The effect of Al content(Zn,Zn-1Al,Zn-2Al,Zn-3Al,Zn-4Al,and Zn-5Al)on the wetting behavior and interfacial reaction was investigated by high-temperature contact angle measuring device and scanning electron microscope(SEM).The results show that,with the increase of Al content,the initial contact angle of the molten alloy on the substrate decreases gradually and the wettability increases gradually.Compared with the initial contact angle,the final contact angle is slightly reduced,because the Fe-Al inhibition layer is preferentially formed at the interface when adding Al to the alloy.The presence of Al will promote the occurrence of the reactive wetting,leading to an insignificant wetting spreading process,and the final contact angle negligibly differs from the initial contact angle.The adhesion work and charge density distributions of interface systems were calculated based on the first-principles.The results show that the adhesion work of the Fe/Zn and Fe/(Zn-Al)interface model is 2.0171 J/m^(2)and 13.7944 J/m^(2),respectively.The addition of Al greatly increases the adhesion work between alloy melt and iron substrate.Compared with the Zn-Fe and Al-Fe interface models,it can be seen that a significant charge migration phenomenon occurs between the interfaces.The amount of charge migration in the Al-Fe interface model is much larger than that in the Zn-Fe interface model,indicating that the bonding between Al-Fe atoms can occur more easily and the interaction between Al-Fe interfaces is stronger.This is also the reason why the addition of Al increases the adhesion work between interfaces.

Surface modification of die casting mold steel by a composite technique of hot-dipping and plasma electrolytic oxidation

The hot dipping process of pure aluminum on H13 steel substrates followed by plasma electrolytic oxidation(PEO) was studied to form alumina ceramic coatings for protective purpose.H13 steel bars were first dipped in pure aluminum melts,and then,a reactive iron-aluminum intermetallic layer grew at the interface between the melt and the steel substrate.The reactive layer was mainly composed of intermetallic Fe-Al(Fe_2Al_5);the thickness of aluminum layer and Fe-Al intermetallic layer were mainly influenced by dipping time(1.5～12.0 min) and dipping temperature(710～760 ℃).After PEO process,uniform Al_2O_3 ceramic coatings were deposited on the surface of aluminized steel.The element distribution,phase composition and morphology of the aluminized layer,and the ceramic coatings were characterized by SEM/EDS and XRD.The distribution of hardness across the composite coating is demonstrated,and the maximum value reaches 1864 HV.The thermal shock resistance of the coated sample is also well improved.

Preparation and hot-dip galvanizing application of CeO_2/Zn nanocomposite

CeO2/Zn nanocomposite was fabricated by high-energy ball milling and subsequent hot-press sintering under vacuum. The produced nanocomposite powders and bulks were characterized using X-ray diffraction （XRD）, transmission electron microscopy （TEM） and scanning electron microscopy （SEM） with an energy dispersive X-ray spectrum （EDS）. The as-fabricated nanocomposite bulks were added successfully into the hot-dip galvanizing bath to improve the corrosion resistance of coatings. The results show that after milling for 120min, nano-sized CeO2 particles are distributed homogeneously on the surface of fine Zn particles to form spherical-like nanocomposite powder with narrow grain size distribution. The subsequent sintering does not lead to a dramatic grain growth, and the distribution of CeO2 nanoparticles in the composite bulk is also homogeneous. With the addition of as-prepared bulks, the corrosion resistance of the galvanized coatings is improved obviously. It provides a feasible route for adding CeO2 nanoparticles into the hot-dip galvanized coating.

Hot-Dip Coating of Lead-free Aluminum on Steel Substrates with Ultrasonic Vibration

Hot-dip coating has been practically employed in manufacturing zinc alloy coated steel sheets.However,it is difficult to coat aluminum alloy on a bulky steel substrate without sufficient preheating,because a rapidly solidified layer containing gas babbles is formed on a substrate surface.A variety of iron-aluminides are also formed at the interface of a steel and aluminum hot-dip coating system,which is the main difficulty in joining of steel with aluminum.Ultrasonic vibration was applied to a steel substrate during hot-dip coating of aluminum alloy to control a rapidly solidified layer and a brittle reaction layer.Hot dipping of columnar steel substrates into molten aluminum alloy （Al-2.7 mass fraction Si-4.6 mass fraction Sn） was carried out through the use of a Langevin oscillator with resonant frequency of 19.5 kHz.The application of ultrasonic vibration is quite effective to control a rapidly solidified layer and a surface oxide layer from a substrate surface by the sonocapillary effect based on a cavitation phenomenon,so that the intimate contact is achieved at the beginning of hot-dip coating.The application of ultrasonic vibration to hot-dipping is effective to control a reaction layer with less than 5 #m in thickness.An impact test exhibits that the good adhesive strength is approved in hot-dipped aluminum coatings with a thin reaction layer of approximately 5μm.

Analysis of Coating Microstructure of Hot-Dip Aluminum of Deformed Low-Carbon Steel Containing Rare Earth

The coating microstructure of hot-dip aluminum (HDA) of deformed low-carbon steel containing RE was analyzed by metallography microscopy, TEM and XRD, and the forming mechanism was also discussed. The results show that, the Fe_2Al_5 phase, on whose subcrystal boundaries, Al particles with the size of 7～30 μm existing on parallel linear are, grows a strong orientation. And the spread activation energy of Al is 155.22 kJ·mol -1. In addition, the effects of deformation on coating microstructure of hot-dip aluminum and the function of RE were preliminarily analyzed.

Hot-Dip Galvanized Sheet Production and Application

Hot-dip galvanized sheet is wildly used in construction,household appliances,ship,vehicle and vessel building and machinery,etc.In last ten years,with the development of automobile industry,the anti-eorrosion requirements for car body are increasingly strict,by which the rapid development in technology has been promoted.The application of hot-dip galvanized sheet,technological progress in production and some Chinese large units were introduced.

Analysis of causes and influence factors of small black spot defects in hot-dip galvanized pure Zn products

In this study,the factors affecting the formation of small black spot defects on the surface of a hot-dip galvanized pure zinc strip are analyzed. These defects are primarily formed w hen the iron-aluminum inhibition layer is incompletely formed or fails to form or when foreign matter adheres to the surface or embeds in the zinc layer.The defects can be reduced by controlling the cleanliness and activity of the strip base before coating,regulating the zinc pot process parameters,and ensuring the cleanliness of the passline and workshop.

Formation of microstructural features in hot-dip aluminized AISI 321 stainless steel

Hot-dip aluminizing（HDA） is a proven surface coating technique for improving the oxidation and corrosion resistance of ferrous substrates. Although extensive studies on the HDA of plain carbon steels have been reported, studies on the HDA of stainless steels are limited. Because of the technological importance of stainless steels in high-temperature applications, studies of their microstructural development during HDA are needed. In the present investigation, the HDA of AISI 321 stainless steel was carried out in a pure Al bath. The microstructural features of the coating were studied using scanning electron microscopy and transmission electron microscopy. These studies revealed that the coating consists of two regions： an Al top coat and an aluminide layer at the interface between the steel and Al. The Al top coat was found to consist of intermetallic phases such as Al_7Cr and Al_3Fe dispersed in an Al matrix. Twinning was observed in both the Al_7Cr and the Al_3Fe phases. Furthermore, the aluminide layer comprised a mixture of nanocrystalline Fe_2Al_5, Al_7Cr, and Al. Details of the microstructural features are presented, and their formation mechanisms are discussed.

Influence of Si content on interface reaction of iron-based hot-dip aluminizing on Fe sheet

Based on the diffusion channel,the influence of Si content on the microstructure evolution of iron-based hot-dip Al-χSi coating was analyzed(χ=0,1.5 wt%,3.0 wt% and 7.0 wt%).The results show that the introduction of Si makes the reaction interface change from the lingual-tooth interface of hot-dip Al to the flat interface of hot-dip Al-Si.It also reduces the thickness of the alloy layer in the coating,especially the Fe_(2)Al_(5) layer.When the Si content is 1.5 wt%or 3.0 wt%,the diffusion channel crosses the conjugate line of the two-phase region(FeAl_(3)+liquid phase)into the FeAl_(3) single-phase region,and then moves to the region with higher Si content.Next,the diffusion channel cuts off the conjugate line of FeAl_(3)phase,τ_(1)/τ_(9) phase,and Fe_(2)Al_(5)phase,which promotes the form ofτ_(1)/τ_(9) phase.The formedτ_(1)/τ_(9) phase inhibits the diffusion between Fe and Al atoms.When the Si content is 7.0 wt%,the diffusion channel passes through the two-phase region(liquid phase+τ_(5))and enters theτ_(5) single-phase region.The form ofτ_(5) single-phase region has a strong inhibitory effect on the interatomic diffusion of Fe and Al,thereby reducing the thickness of the coating,especially the Fe_(2)Al_(5)layer.

Evolution of appearance profile of hot-dip galvanized car-body steel sheet during deformation process

In recent years, the waterborne free intermediate coating process has been widely used in the automotive industry. Because the baking times and coating thickness are decreased, the surface covering capability of the painting process is reduced, which directly affects the appearance quality（ long-and short-wave values） of the body paint. Thus, there are correspondingly higher requirements for the white body surface profile prior to painting. The surface profile of the white body is mainly affected by the plate material, the surface profile, and the deformation process. So,the change rule for the surface profile during deformation of the steel plate is a key factor in coating appearance optimization. In this paper, we first analyze the typical deformation of the outer cover of a car body. Then ,we examine the change tendency of the surface profile of steel plates with respect to different deformation rates, specifically for a steel plate comprising a hot-dip galvanized bake-hardened steel sheet. Based on our analysis of the influence of the deformation on the coating appearance,we selected 3% ,5% ,and 8% deformation rates in this research. We found the roughness （Ra） value in the typical deformation range （3% -8% ） of the car body to exhibit a decreasing trend at first and then an increasing trend. The Ra value of the 8% deformation is not more than the original plate test value. When the Pc value of the original plate is in the lower range （ about 60）, it exhibits a slight increasing trend in the deformation process （3 % -8 % ）. And when the Pc value of the original plate is in the higher range （ about 120 ）, it exhibits no increasing trend in the deformation process （ 3% -8% ）. In contrast,the waviness （WCA） value in the car body＇s typical deformation range （3%-8%） shows a significant growth trend.

Development of Cr-free anti-fingerprint hot-dip galvanized sheet for household appliances

China has become the maximum household appliances manufacturing base worldwide.It is a new challenge facing the steel industry to develop the low-cost and environment-friendly sheet for household appliance industry,so Cr-free anti-fingerprint hot-dip galvanized sheet for household appliances is the upgraded product which satisfies the requirement of China household appliance industry' s nuisanceless treatment.The paper discusses the technical key points of development on Cr-free anti-fingerprint galvanized sheet for household appliances,including the development of the Cr-free anti-fingerprint chemical and the production technology of Cr-free anti-fingerprint galvanized sheet for household appliances.The paper elaborates the main compositions,physical features and properties of the Cr-free anti-fingerprint chemical, surface quality control technology,anti-fingerprint coating quality control technology,influence of anti-fingerprint film weight on corrosion resistance,conductibility,high-temperature discolouration resistance,acid resistance,alkaline resistance and solvent resistance of Cr-free anti-fingerprint hot-dip galvanized sheet, influence of anti-fingerprint coating uniformity on paintability of the sheet,influence of strip surface roughness on corrosion resistance and conductivity of the sheet and influence of strip surface quality on corrosion resistance of the sheet.Adopting the suitable Cr-free anti-fingerprint chemical and the reasonable production process parameters,the properties of the Cr-free anti-fingerprint hot-dip galvanized sheet conform to the delivery technical norms and the Cr-free anti-fingerprint hot-dip galvanized sheet becomes the new material for household appliances such as computer case.

Application of WC cermet sprayed composite coating in hot-dip galvanizing lines

With the rapid development of the automobile industry, the use of galvannealed and galvanized steel sheets in automobiles is on the rise. These sheets must meet very high surface quality requirements. The surface treatment of line rolls is known to have a great impact on strip quality. To prevent dusts such as zinc ash from pressing into the strip surface, we used a composite thermal spray surface treatment technique to treat rolls. The successfully developed tungsten carbide （WC） ＋ Ni-P composite plating technology improved the quality of the tungsten carbide thermally sprayed WC roll surface. This technique is also helpful to control defects such as adhered foreign materials in hot-dip galvanized automobile outer panel surfaces.

Lead and Cadmium Distribution in Tubes of Galvanized Steel by Hot-Dip Used for Drinking Water Supply

The main objective of this work was to evaluate the presence of lead and cadmium in galvanized steel tubes by hot-dip used exclusively for drinking water supply.In this research,samples of galvanized tubes were removed from walls of residential buildings with 30 years of use.In the process of hot galvanizing,the manufacturing standards allow or for low cost conveniences,and the use of primary zinc ingot with 1.6%metallic impurities,such as lead and cadmium,is allowed,enabling the incorporation of these metals into the zinc coating deposited on the carbon steel.The associated corrosion of these tubes can release these toxic metals,contaminating the drinking water used by residents.The samples taken from the tubes were evaluated by a square-wave anodic stripping voltammetry technique,and the results for lead and cadmium suggested randomly distributed levels,indicating that the contents of these contaminants depend mainly on the quality of the added primary zinc and the operational conditions of the immersion bath.The metallographic evaluations performed on the samples of the galvanized tubes showed irregularities in thickness and even a lack of the zinc layer deposited on the carbon steel surface.These facts suggest that galvanized tubes should not be used for drinking water.

UV-LED Curing Cationic Passivation Film for the Surface of Hot-Dip Aluminum-Zinc Coated Steel Plate

The surface treatment technology of hot aluminum-zinc steel plate and UV curing technology may be effectively combined in the present research. According to different light curing mechanisms, different formulations from UV curing surface treatment agents can be applied to the surface treatment of hot aluminum-zinc steel plate, mainly including 3-ethyl-3-benzoxy-methyl oxacyclobutane (TCM 104) and 3,4-epoxy-cyclohexylformic acid -3',4'-epoxy-cyclohexyl methyl ester (UVR 6110) as active diluents, high molecular weight polyfunctional oxacyclobutane as oligomer, triaryl sulfonium salt as a cationic photoinitiator, and an anthracene compound as a sensitizer. 385 nm LED lamp used as a radiation resource, the effects of the proportion of active diluent, the type and amount of photoinitiator, the amount of sensitizer, the curing temperature, and the amount of nano-SiO2 on the photocuring rate were investigated by photoper-scanning differential calorimetry (Photo-DSC). The experimental results show that the system has the fastest photocuring rate under the conditions of 8:2 ratio of TCM 104 to UVR 6110, 2.5% photoinitiator, 0.6% sensitizer, 0.2% nano-SiO2 additive, and 80˚C curing temperature. Based on addition of the appropriate number of various additives, the cationic photocuring surface treatment solution was prepared and further coated on the hot-dip galvalume steel plates. After curing, the passivation films were characterized by neutral salt spray test (NSST), Fourier transform infrared spectroscopy (FT-IR), electrochemical testing and other methods. The results show that the formulations could be cured at an energy of 150 mJ/cm2, and the overall performance of the passivation film could meet with the requirements of the downstream users.

A Carbonation and Chloride Induced Corrosion Model for Hot-dip Galvanised Reinforcement Bar Material in Concrete

This paper focuses on methodological issues relevant to corrosion risk prediction models.A model was developed for the prediction of corrosion rates associated with hot-dip galvanised reinforcement bar material in concrete exposed to carbonation and chlorides in outdoor environment.One-year follow-up experiments,over five years,were conducted at various carbonation depths and chloride contents.The observed dependence of corrosion rate on the depth of carbonation and chloride content is complex indicating that the interaction between the carbonation and chloride influencing the corrosion.A non-linear corrosion model was proposed with statistical analysis to model the relationship between the corrosion rate and the test parameters.The main methodological contributions are(i)the proposed modeling approach able to take into account the uncertain measurement errors including unobserved systematic and random heterogeneity over different measured specimens and correlation for the same specimen across different measuring times,which best suits the measurement data;(ii)the developed model in which an interaction parameter is introduced especially to account for the contribution and the degree of the unobserved carbonation-chloride interaction.The proposed model offers greater flexibility for the modelling of measurement data than traditional models.

Effect of Si on growth kinetics of intermetallic compounds during reaction between solid iron and molten aluminum

The effect of Si on the growth kinetics of intermetallic compounds during the reaction of solid iron and molten aluminum was investigated with a scanning electron microscope coupled with an energy dispersive X-ray spectroscope, and hot-dip aluminized experiments. The results show that the intermetallic layer is composed of major Fe2Al5 and minor FeAl3. The Al-Fe-Si ternary phase, rl/rg, is formed in the Fe2Al5 layer. The tongue-like morphology of the Fe2Als layer becomes less distinct and disappears finally as the content of Si in aluminum bath increases. Si in the bath improves the prohibiting ability to the growth of Fe2Als and FeAl3. When the contents of Si are 0, 0.5%, 1.0%, 1.5%, 2.0% and 3.0%, the activation energies of Fe2Al5 are evaluated to be 207, 186, 169, 168, 167 and 172 kJ/mol, respectively. The reduction of the activation energy might result from the lattice distortion caused by Si atom penetrating into the Fe2Al5 phase. When Si atom occupies the vacancy site, it blocks easy diffusion path and results in the disappearance of tongue-like morphology.