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.

ToF-SIMS characterization of a bare-spot defect in a hot-dip galvanized boron-added steel sheet

To determine the root cause of a bare-spot defect in a hot-dip galvanized boron-added steel sheet,we performed metallurgical characterizations using time-of-flight secondary ion mass spectrometry(ToF-SIMS)in addition to glow discharge optical emission spectrometry,field-emission scanning electron microscopy(FE-SEM),and energy dispersive spectroscopy.Mn and B enrichments on the steel surface in the bare-spot area were detected through various methods.FE-SEM revealed external oxide nodules and zinc droplets,which indicated poor wettability.ToF-SIMS further revealed considerably more detailed lateral and depth distributions of Mn,B,and Al.The formation of external Mn-B compound oxides on the steel surface prior to hot dipping,which substantially deteriorated the wettability and prevented the formation of a Fe_(2)Al_(5)inhibition layer,resulted in the formation of a bare-spot defect.ToF-SIMS mapping of Al ion proved that a slight reaction still occurred between the dissolved Al in the molten zinc bath and steel substrate,although no evident Fe_(2)Al_(5)inhibition layer formed in the bare-spot area.

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.

Corrosion behavior and mechanism of the automotive hot-dip galvanized steel with alkaline mud adhesion

The corrosion behavior and mechanism of hot-dip galvanized steel and interstitial-free （IF） substrate with alkaline mud adhesion were investigated by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, electrochemical impedance spectroscopy （EIS）, and linear polarization. The results show that non-uniform corrosion occurs on the galvanized steel and IF substrate during 250 h with the mud adhesion. The corrosion products on the galvanized steel are very loose and porous, which are mainly ZnO, Zn5（OH）8C12·H2O and Zn（OH）2, and Fe-Zn alloy layer with a lower corrosion rate is exposed on the galvanized steel surface; however, the corrosion products on IF substrate are considerably harder and denser, whose compositions of rust are mainly FeOOH and Fe3O4, and several pits appear on their surface. The results of continuous EIS and linear polarization measurements exhibit a corrosion mechanism, that is, under activation control, the charge transfer resistances present different tendencies between the galvanized steel and IF substrate; in addition, the evolution of linear polarization resistances is similar to that of charge transfer resistances. The higher contents of dissolved oxygen and Cl^- ions in the mud play an important role in accelerating the corrosion.

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.

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.

Anticorrosive Properties of Hot-Dip Galvanized Weathering Steel in Atmospheric Exposure

Hot-dip galvanized steel is one of the most used materials in equipment and metallic structures of the Brazilian electric sector. Although carbon steel is the main substrate in the galvanizing hot-dip process, recently, weathering steel has been used as an alternative material to be galvanized. In the transmission line segment of the Brazilian electric sector, for instance, compact towers made of galvanized weathering steel have been installed to conduct energy through urban sites. It is well known that weathering steel, depending on wet and dry cycles and on the pollutants present in the atmosphere, develops a protective patina made of its corrosion products. The patina is dense and strongly adhered to the substrate, blocking the active surface and, thus, reducing the corrosion rate of the base metal. However, when the weathering steel is galvanized, the substrate surface has a layer of zinc and zinc-iron intermetallic alloys. When the sacrificial layer is consumed by atmospheric corrosion, critical questions remain to be answered regarding the underlying substrate. Will the patina of weathering steel be formed? In what condition? Does the hot-dip galvanizing process modify the weathering steel microstructure? The present work carried out an experimental research to shed light on the anticorrosive behavior of hot-dip galvanized weathering steel, after the zinc layer is corroded. This was done by a controlled pickling process, where the zinc layer was removed simulating its consumption during real corrosion processes. The results, obtained through electrochemical techniques and different accelerated corrosion tests, showed that galvanizing weathering steel is a promising technology to enhance the lifetime of structures used in the Brazilian electric sector.

Interpretation on Sebisty effect of hot-dip galvanized steels

Sebisty effect describes the unusual fact that the thickness of the hot-dip galvanizing coating on the steel containing 0.12%0.25% silicon decreases with increasing temperature of zinc bath. The microstructures of hot-dip galvanized coatings on silicon-containing steels (0.14%Si) immersed in zinc bath at 723K and 753K were analyzed. It is found that the thickness of η and ζ layer decreases with the increase of temperature of zinc bath and Г layer changes from discontinuous layer (at 723K) to relatively continuous layer (at 753K). The improvement of the fluidity of zinc bath due to the rising temperature of zinc bath makes η layer thinner. Moreover, the existence of relatively continuous Г layer and the acceleration of the dissolution of ζ layer to zinc bath co-lead to the decrease of the thickness of ζ layer with increasing temperature.

Rare earth and silane as chromate replacers for corrosion protection on galvanized steel

The present work aimed at using rare earth lanthanum salt and trimethoxy（viny）silance as chromate substitutes for galvanized steel passivation, in contrast to zinc coating samples treated with chromate.The corrosion resistance was assessed by electrochemical impedance spectroscopy（EIS） and neutral salt spray tests（NSS）.Scanning electron microscopy（SEM） was used to characterize the sample surfaces.The organic coating adhesion on the panel was also investigated via varnishes-cross cut tests.The results indicated that rare earth and silane two-step treatment gave more effective anticorrosion performance than Cr, which also provided good paint adhesion.The coating formation mechanism was also discussed.

Post treatment of silane and cerium salt as chromate replacers on galvanized steel

A complex film on hot-dip galvanized steel sheet（HDG） was prepared by immersing the sheet in 0.1wt.% Ce（NO3）3 solution and 5vol.% silane solution in turn.The corrosion protection of the complex film was evaluated by potentiodynamic linear polarization（LPR）, electrochemical impendence spectra（EIS） and natural salt spray（NSS） tests and compared with that of single cerium film and silane film.The results showed that, the presence of these films on the zinc coating hindered corrosion reaction by reducing the rate of both anodic and cathodic reaction in the corrosion process, and the corrosion protection of the complex film was much better than that of single cerium film or silane film and closed to that of chromate film, because the polarization resistance Rp and electrochemical impendence were increased markedly.Microstructure and chemical composition of these pretreated films were also investigated by scanning electron microscopy（SEM） and AES.

Cerium-tannic acid passivation treatment on galvanized steel

A novel cerium-tannic acid passivation treatment was performed on galvanized steel. The corrosion resistance of cerium-tannic passivated samples was tested by dropping test with 0.5 wt.% CuSO4 aqueous solution. The mass loss per unit area of passivated samples was measured after the corrosion in 0.5 mol/L NaCl ＋ 0.005 mol/L H2SO4 at room temperature for 96 h. The electrochemical behaviors of cerium, tannic acid, and cerium-tannic acid passivated samples on galvanized steel in 0.5 mol/L NaCl solution were investigated by polarization curves and electrochemical impendence spectra. The corrosion equivalent circuit was established according to the impedance characteristics. The results show that cerium-tannic acid treated samples exhibit better corrosion resistance than the sole cerium or tannic acid treated samples under the same condition. The mechanism of synergistic effect for cerium-tannic acid passivation on galvanized steel was discussed.

Investigation of Surface Damage in Forming of High Strength and Galvanized Steel Sheets

Powdering/exfoliating of coatings and scratching galvanized steels and high strength steels （HSS）, are the main forms of surface damage in the forming of which result in increased die maintenance cost and scrap rate. In this study, a special rectangular box was developed to investigate the behavior and characteristics of surface damage in sheet metal forming （SMF） processes. U-channel forming tests were conducted to study the effect of tool hardness on surface damage in the forming of high strength steels and galvanized steels （hot-dip galvanized and galvannealed steels）. Experimental results indicate that sheet deformation mode influences the severity of surface damage in SMF and surface damage occurs easily at the regions where sheet specimen deforms under the action of compressive stress. Die corner is the position where surface damage initiates. For HSS sheet, surface damage is of major interest due to high forming pressure. The HSS and hot-dip galvanized steels show improved ability of damage-resistance with increased hardness of the forming tool. However, for galvannealed steel it is not the forming tool with the highest hardness value that performs best.

Composition and Performance of the Composite Coatings Obtained by Phosphating and Cerium Nitrate Post-Sealing on Galvanized Steel

To improve the corrosion resistance of phosphate coatings, the phosphated hot-dip galvanized (HDG) steel was post-sealed with cerium nitrate solution. The morphology, composition, corrosion resistance of the coatings was investigated by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and neutral salt spray (NSS) tests. The results show that after post-sealing the phosphated HDG samples with cerium nitrate solution, the pores among the zinc phosphate crystals are sealed by the compounds containing phosphorus, oxygen and cerium; the zinc phosphate crystals are covered by the flocculent cerium compounds; and the continuous composite coatings are formed on HDG steel. The corrosion resistance of the composite coatings, which increases with the increase in phosphating time and cerium nitrate post-sealing time, is far higher than that of the single phosphate coatings. The composite coatings with the optimal corrosion resistance are obtained for phosphating 300 s and post-sealing 300 s; and the corrosion resistance is more outstanding than that of the chromate coatings.

CO_2 laser-micro plasma arc hybrid welding for galvanized steel sheets

A laser lap welding process for zinc-coated steel has a well-known unsolved problem-porosity formation. The boiling temperature of coated zinc is lower than the melting temperature of the base metal, which is steel. In the autogenous laser welding, the zinc vapor generates from the lapped surfaces expels the molten pool and the expulsion causes numerous weld defects, such as spatters and blow holes on the weld surface and porosity inside the welds. The laser-arc hybrid welding was suggested as an alternative method for the laser lap welding because the arc can preheat or post-beat the weldment according to the arrangement of the laser beam and the arc. CO2 laser-micro plasma hybrid welding was applied to the lap welding of zinc-coated steel with zero-gap. The relationships among the weld quality and process parameters of the laser-arc arrangement, and the laser-arc interspacing distance and arc current were investigated using a full-factorial experimental design. The effect of laser-arc arrangement is dominant because the leading plasma arc partially melts the upper steel sheets and vaporizes or oxidizes the coated zinc on the lapped surfaces. Compared with the result from the laser-TIG hybrid welding, the heat input from arc can be reduced by 40%.

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.

Study on resistance spot brazing process and joint performance of pure aluminum 1060/galvanized steel

Resistance spot brazing was used to perform the lap test of pure aluminum 1060 and SGCC hot-dip galvanized steel plate,the joint interface structure was studied,and the mechanical properties of the joint were tested.The results show that the aluminum-silicon(Al-Si)alloy solder used in the test has good wetting,and an intermetallic compound with a double-layer structure and uneven thickness is produced at the welded joint interface after welding.The thickness is<10μm.The welding current is at 7.8 kA,the tensile shear load of the joint reaches a peak value of about 4.72 kN.Under the same process parameters,the tensile shear load of the resistance spot brazed joint is significantly higher than that of the spot welded joint.The joint fracture mostly occurs on the aluminum plate side,and mainly at the heat-affected zone and not at the welding point.It indicates that the quality of the spot brazed joint is good,but due to the local"unbrazed"defect on the aluminum side interface of the weld,tensile stress will occur at the weld interface and the stress effect on the intermetallic compound.It is easy to produce cracks.

Laser brazing with filler wire for galvanized steel sheets

The process properties and interface behavior of CO_2 laser brazing with automatic wire feed for galvanized steel sheets were investigated, in which the brazing filler metal was CuSi3 and no flux was used. As to the appearance quality of the brazing seams, the roles of the processing parameters, such as brazing speed, wire feeding rate, inclination and feeding direction of the wire, laser power, spot diameter and heating position, were assessed. The further investigation indicates that the behavior of the active elements Si, Mn and Zn are significantly influenced by energy input. At the interface, the microstructure of the base metal was composed of columnar crystals and the acicular α solid solution was found on the filler metal side.

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.

Chrome free surface treatments for galvanized steels—present and future

As the galvanized steels used for electrical and office appliances has achieved a complete chrome-free production worldwide,surface treatment technologies have entered a new phase of development.Grenter effort will be made in exploring new frontier for future surface treatment technologies.A greater contribution will be made for environmental protection,energy-saving and resource-saving,to prevent globalwarming.

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.