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WO2010012235A1 - 热镀锌钢板及其生产方法 - Google Patents

热镀锌钢板及其生产方法 Download PDF

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Publication number
WO2010012235A1
WO2010012235A1 PCT/CN2009/073004 CN2009073004W WO2010012235A1 WO 2010012235 A1 WO2010012235 A1 WO 2010012235A1 CN 2009073004 W CN2009073004 W CN 2009073004W WO 2010012235 A1 WO2010012235 A1 WO 2010012235A1
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WO
WIPO (PCT)
Prior art keywords
hot
steel sheet
plating bath
temperature
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2009/073004
Other languages
English (en)
French (fr)
Inventor
李炜
徐权
郭太雄
郑之旺
于丹
周一林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pangang Group Research Institute Co Ltd
Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
Panzhihua New Steel and Vanadium Co Ltd
Original Assignee
Pangang Group Research Institute Co Ltd
Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
Panzhihua New Steel and Vanadium Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN200810303233A external-priority patent/CN100591793C/zh
Priority claimed from CN200810303272A external-priority patent/CN100591794C/zh
Priority claimed from CN2008103032579A external-priority patent/CN101323942B/zh
Priority claimed from CN200810303258A external-priority patent/CN100596311C/zh
Application filed by Pangang Group Research Institute Co Ltd, Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd, Panzhihua New Steel and Vanadium Co Ltd filed Critical Pangang Group Research Institute Co Ltd
Priority to US13/003,619 priority Critical patent/US20110256420A1/en
Priority to JP2011520310A priority patent/JP5520297B2/ja
Priority to DE112009001879.3T priority patent/DE112009001879B4/de
Publication of WO2010012235A1 publication Critical patent/WO2010012235A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the invention belongs to the field of manufacturing hot-dip galvanized steel sheets, and particularly relates to a hot-dip galvanized steel sheet with good adhesion of plating and a production method thereof.
  • Hot-dip galvanized steel sheets have been widely used in manufacturing industries such as household appliances and automobile body panels due to their good corrosion resistance, excellent coating properties and clean appearance.
  • the requirement for the coating of hot-dip galvanized steel sheet is that the coating has strong adhesion to the substrate, does not fall off during stamping deformation, and has good welding performance, corrosion resistance and phosphating performance to ensure the adhesion of the paint film and after painting. Corrosion resistance.
  • hot-dip galvanized steel sheets have problems such as pulverization and peeling of the plating layer in the actual press working process, which causes damage of the plating layer and further affects the corrosion resistance and coating property of the plating layer.
  • a method for improving the roughness a method of controlling the conditions of the smoothing roll, rolling conditions, and the like may be mentioned.
  • zinc is liable to accumulate on the roll, so that it is difficult to stably
  • the specified roughness is formed on the surface of the hot-dip galvanized steel sheet.
  • this method does not necessarily increase the adhesion of the coating film.
  • the base material is a steel which is obtained by using C: 0.05-0.25 mass% of low carbon steel and adding a high strength residual austenitic steel of Si and A1 in an appropriate amount.
  • a moderate amount of fixed grain boundary C such as Ti or Nb is added to increase the plating interface strength.
  • this is a technique relating to retained austenitic steel, and it is not necessarily a problem that sufficient performance is obtained for a high-strength steel sheet having no retained austenite phase.
  • the adhesion of the galvanized steel sheet is mainly affected by the composition and structure of the coating.
  • the pulverization and peeling are related to the chemical composition and phase structure of the coating, and the amount of coating pulverization increases as the iron content in the coating increases.
  • the steel plate and the zinc layer are in the order of 1 ⁇ ⁇ , ⁇ and ⁇ phases, and the ⁇ phase is 13 ⁇ 4 ⁇ 1 21
  • the basic intermediate metal phase, the ⁇ phase is an intermediate metal phase based on FeZn 7 , and the ⁇ phase is?
  • the intermediate metal phase based on 1 13 , the ⁇ phase is a solid solution containing a trace amount of iron composed of pure zinc.
  • the pulverization of the plating layer forms microcracks at the interfaces on both sides of the ⁇ phase, and is formed throughout the entire plating layer after expansion.
  • the thickness of the ⁇ phase exceeds ⁇ . ⁇
  • the amount of pulverization increases with the thickness of the ⁇ phase, and the iron content in the plating layer is controlled to about 11%, which can hinder the formation of a thick ⁇ phase, so the main influence of the anti-pulverization performance
  • the factors are the ⁇ phase (fine grain structure) and the ⁇ phase (columnar structure).
  • the ⁇ phase is hard and brittle, which is unfavorable for formability.
  • the hardness of the ⁇ phase is comparable to that of the base steel plate.
  • the plating layer has good formability only when the ⁇ phase and the ⁇ phase in the plating layer have an appropriate ratio.
  • the coating structure when the ⁇ phase of the coating surface disappears and the dense ⁇ phase does not appear is the optimum coating structure.
  • the aluminum content in the Fe-Al intermediate transition layer between the steel base and the zinc layer of the hot-dip galvanized steel sheet is a measure of the adhesion strength of the coating.
  • the high amount of aluminum in the Fe-Al intermediate transition layer is only a necessary condition for obtaining good coating adhesion, and not a sufficient condition. This is because only when zinc is dissolved in the Fe-Al intermediate transition layer and forms a zinc-depleted solid solution, this layer can act as an adhesion and prevent the diffusion of Fe and Zn, and form a small amount of ⁇ and ⁇ phase.
  • the adhesion of the plating layer is good at this time. If the solubility of Zn in the Fe-Al intermediate transition layer is supersaturated and a zinc-rich solid solution is formed, the absolute content of A1 in the intermediate layer is not reduced, but the percentage of A1 is significantly decreased, and because of zinc Supersaturation destroys the homogeneity of the Fe-Al intermediate transition layer, thereby losing the adhesion of the intermediate layer and preventing the diffusion of Fe and Zn elements, and forming a thicker Fe-containing more ⁇ and ⁇ phases.
  • the Zn alloy layer causes the adhesion of the zinc layer to deteriorate at the same time.
  • the adhesion of the coating to the steel substrate is improved by changing the composition of the steel sheet or by controlling the surface roughness of the hot-dip galvanized steel sheet to form a coating film technology, but no good effect has been obtained, and no control coating has been performed yet.
  • the composition and structure of the structure to improve the adhesion of the coating to the steel base is improved by changing the composition of the steel sheet or by controlling the surface roughness of the hot-dip galvanized steel sheet to form a coating film technology, but no good effect has been obtained, and no control coating has been performed yet.
  • the first technical problem to be solved by the present invention is to provide a hot-dip galvanized steel sheet having high adhesion between a plating layer and a steel base.
  • the technical solution adopted to solve the technical problem is that the atomic concentration Al/Zn ratio of A1 and Zn in the Fe-Al intermediate transition layer between the steel sheet substrate of the hot-dip galvanized steel sheet and the zinc plating layer is 0.9 to 1.2.
  • the present invention further provides a hot-dip galvanized steel sheet having high adhesion between the plating layer and the steel base, and at the same time, the Fe-Al intermediate transition between the steel sheet substrate and the zinc plating layer of the hot-dip galvanized steel sheet.
  • the original of A1 and Zn in the layer The sub-concentration Al/Zn ratio is 0.9 to 1.2, and the zinc-plated grain orientation Zn (002) peak intensity is 25000 to 35000 cts.
  • the second technical problem to be solved by the present invention is to provide a method for producing a hot-dip galvanized steel sheet, wherein the atomic concentration of A1 and Zn in the Fe-Al intermediate transition layer between the steel sheet substrate and the zinc plating layer obtained by the method is Al/ The Zn ratio is 0.9 to 1.2.
  • the technical solution adopted to solve the above technical problems is as follows:
  • the steel plate is subjected to hot-dip galvanizing operation after pickling and annealing, and during the hot-dip galvanizing operation, the temperature of the steel plate into the plating bath is 455 to 485 ° C, and the temperature of the plating bath in the zinc pot is 450 ⁇ 460°C, the content of Fe in the plating bath is ⁇ 0.03%, the content of A1 in the plating bath is 0.16 ⁇ 0.25%, the unit speed is 100 ⁇ 120m/min, the high span temperature of the cooling section is 210 ⁇ 245°C, steel plate The cooling rate is 0 to 90%.
  • the temperature of the steel sheet entering the plating bath is 455 to 465 ° C, and the plating bath in the zinc pot
  • the temperature is 450 ⁇ 460°C
  • the content of Fe in the plating bath is ⁇ 0.03%
  • the weight percentage of A1 in the plating bath is 0.16 ⁇ 0.18%
  • the unit speed is 100 ⁇ 110m/min
  • the high span temperature of the cooling section is 210 ⁇ 220.
  • the steel plate cooling rate is 0%.
  • the second preferred embodiment is a method for producing a hot-dip galvanized steel sheet.
  • the steel sheet is subjected to hot-dip galvanizing after pickling and annealing.
  • the temperature of the steel sheet entering the plating bath is 475 to 485 ° C, and the plating bath is used in the zinc pot.
  • the temperature is 450 ⁇ 460°C
  • the weight percentage of Fe in the plating bath is ⁇ 0.03%
  • the cooling rate of the steel plate is 0%
  • the cooling section high span temperature: 235 ⁇ 245°C plating bath
  • the content of A1 in the weight percentage is 0.16% A1 0.18%.
  • the third preferred embodiment is a method for producing a hot-dip galvanized steel sheet.
  • the steel sheet is subjected to hot-dip galvanizing after pickling and annealing.
  • the temperature of the steel sheet entering the plating bath is 475 to 485 ° C, and the plating bath in the zinc pot The temperature is 450 ⁇ 460°C, the weight percentage of Fe in the plating bath is ⁇ 0.03%, the weight percentage of A1 in the plating bath is 0.18% ⁇ A1 0.21%, the unit speed: 100 ⁇ 110m/min, the cooling rate of the steel plate is 0. %, cooling section high span temperature: 235 ⁇ 245 °C.
  • the fourth preferred embodiment is a method for producing a hot-dip galvanized steel sheet.
  • the steel sheet is subjected to hot-dip galvanizing after pickling and annealing.
  • the temperature of the steel sheet entering the plating bath is 455 to 465 ° C, and the plating bath is used in the zinc pot.
  • the temperature is 450 ⁇ 460°C
  • the content of Fe in the plating bath is ⁇ 0.03%
  • the weight percentage of A1 in the plating bath is 0.16 ⁇ 0.18%
  • the unit speed is 110 ⁇ 120m/min
  • the steel plate is cooled by air cooling. Forced cooling, cooling rate 70 ⁇ 90% (relative to the cold cooling nozzle, the cooling rate is 0% natural cooling, the cold air nozzle opening ratio is 70 ⁇ 90%).
  • the fifth preferred embodiment is a method for producing a hot-dip galvanized steel sheet.
  • the steel sheet is subjected to hot-dip galvanizing after pickling and annealing.
  • the temperature of the steel sheet entering the plating bath is 455 to 465 ° C, and the plating bath is used in the zinc pot.
  • the temperature is 450 ⁇ 460 °C
  • the weight percentage of A1 in the plating bath 0.21 ⁇ 0.25%
  • the weight percentage of Fe in the plating bath is ⁇ 0.03%
  • the unit speed 100 ⁇ 110m/min
  • the cooling rate of the steel plate is 0%
  • composition of the steel sheet to be galvanized includes C: 0.03 to 0.07%, Mm 0.01-0.03%, Si: 0.19 to 0.30%, P: 0.006 to 0.019%, S: 0.009 to 0.020% by weight percent. , A1: 0.02 ⁇ 0.07%, and the rest is Fe.
  • the thickness of the steel plate to be galvanized is 0.8 mm, the weight of the zinc layer after galvanizing is 180 to 195 g/m 2 , and the surface of the zinc layer is passivated by SiO 2 .
  • the hot-dip galvanizing process condition of the present invention enables the Fe-Al intermediate transition layer between the steel sheet substrate and the zinc plating layer to prevent interdiffusion between Fe and Zn, and to reduce the formation of the Fe-Zn alloy layer, which is not in the plating layer.
  • the ⁇ phase will be formed, the ⁇ phase is thinner, the ⁇ phase is few, and the coating layer is mostly composed of ⁇ phase, which improves the adhesion of the hot-dip galvanized steel plate coating, and the phenomenon that the coating zinc powder falls off and peels off;
  • the hot-dip galvanizing process condition of the present invention optimizes the grain orientation of the hot-dip galvanized steel sheet, and the scratch resistance, wear resistance and adhesion performance of the plating layer are significantly improved;
  • Fig. 1 is a spectroscopic scanning spectrum of a plating profile electron probe (EPMA1600 type) of Experimental Example 1.
  • 2 is a scanning electron microscope (SEM) cross-sectional morphology of Experimental Example 1 and Comparative Example 6, 11 plating, (a) Experimental Example 1; (b) Comparative Example 6; (c) Comparative Example 11.
  • Fig. 3 is a photograph of a metallographic microscope with a magnification of 100x in an optical metallographic microscope (OLYMPUS Model BX51), (a) is an experimental example 1, and (b) is a comparative example 6.
  • Fig. 4 is a graph showing the atomic percentage change of the elemental transition layer A1 and Zn of the Fe-Al intermediate layer of Experimental Example 1 and Comparative Example 6,11.
  • Fig. 5 is a graph showing changes in the average atomic percentage of Al and Zn at positions 2 to 4 in Experimental Examples 1 to 5 and Comparative Examples 6 to 10 and 11 to 15 in a Fe-Al intermediate transition layer (shown in Fig. 1).
  • Figure 6 is a graph showing the change in mass percentage of Fe, Zn and A1 elements at various positions on the surface of the steel substrate to the zinc layer (shown in Figure 1) in the coatings of Experimental Example 1 and Comparative Examples 6, 11 and the metallographic structure in the plating layer, ( a) Experimental Example 1; (b) Comparative Example 6; (c) Comparative Example 11.
  • Fig. 7 is a typical XRD diffraction pattern of Experimental Example 1 and Comparative Examples 6 and 11 (a) Experimental Example 1, (b) Comparative Example 6, and (c) Comparative Example 11.
  • Figure 8 is a schematic view of the shape of a U-shaped curved specimen: 1 bending tester fixture, 2 bending specimen.
  • Fig. 9 is a graph showing the mean value and variance of the amount of zinc powder falling off in the samples of Experimental Examples 1 to 5 and Comparative Examples 6 to 10 and 11 to 15.
  • Fig. 10 is a typical profile measurement chart at the intermediate positions of the coating layers of Experimental Example 1 and Comparative Examples 6 and 11: 1 is Experimental Example 1, 2 is Comparative Example 6, and 3 is Comparative Example 11.
  • Fig. 11 is a view showing the entire wear scar observed under SEM after the reciprocating sliding wear test of Experimental Example 1 and Comparative Examples 6 and 11.
  • Fig. 12 is a graph showing the atomic percentage change of Al and Zn elements in the Fe-Al intermediate transition layer in the coating layers of Experimental Example 16 and Comparative Example 21.
  • Fig. 13 is an average atomic percentage of Al and Zn elements of the Fe-Al intermediate transition layer in the coating layers of Experimental Examples 16 to 20 and Comparative Examples 21 to 25.
  • Fig. 14 is a graph showing changes in mass percentage and metallographic structure of Fe, Zn and A1 elements in the coating layers of Experimental Example 16 and Comparative Example 21, (a) Experimental Example 16, (b) Comparative Example 21.
  • Fig. 15 is a typical XRD diffraction pattern of Experimental Example 16 and Comparative Example 21 (a) Experimental Example 16 (b) Comparative Example
  • Fig. 16 is a graph showing the mean value and variance of the amount of zinc powder shedding in Experimental Examples 16 to 20 and Comparative Examples 21 to 25.
  • Fig. 17 is a result of profile measurement at the intermediate position of the scratches of the plating layers of Experimental Example 16 and Comparative Example 21, 1 Comparative Example 21, 2 Experimental Example 16.
  • Fig. 19 is a graph showing the mean values and variances of the zinc powder dropping amounts in Experimental Examples 21 to 30, Comparative Examples 26 to 30, and Comparative Examples 31 to 35.
  • Fig. 20 is a result of profile measurement at the intermediate positions of the scratches of the experimental examples 21 and 26 and the comparative examples 26 and 30, 1 Experimental Example 21, 2 Experimental Example 26, 3 Comparative Example 26, 4 Comparative Example 30.
  • Fig. 21 is a graph showing the atomic percentage change of Al and Zn elements in the Fe-Al intermediate transition layer in the plating layers of Experimental Example 31 and Comparative Example 36.
  • Fig. 22 is an average atomic percentage of Al and Zn elements of the Fe-Al intermediate transition layer in the experimental examples 31 to 35 and the comparative examples 36 to 40.
  • Fig. 23 is a graph showing the mass percentage change of Fe, Zn and A1 elements in the plating layers of Experimental Example 31 and Comparative Example 36, and the metallographic structure, (a) Experimental Example 31, (b) Comparative Example 36.
  • Fig. 24 is a typical XRD diffraction pattern of Experimental Example 31 and Comparative Example 36
  • (a) Experimental Example 31, (b) Comparative Example Fig. 25 is a graph showing the mean values and variances of the amount of zinc powder shedding in Experimental Examples 31 to 35 and Comparative Examples 36 to 40.
  • Fig. 26 is a result of profile measurement at the intermediate position of the scratches of the plating layers of Experimental Example 31 and Comparative Example 36, and Comparative Example 36, 2 Experimental Example 31.
  • Fig. 27 is a graph showing the atomic percentage change of Al and Zn elements in the Fe-Al intermediate transition layer in the coating layers of Experimental Example 36 and Comparative Example 41.
  • Figure 28 is an average atomic percentage of Al and Zn elements of the Fe-Al intermediate transition layer in the coatings of Experimental Examples 36 to 42 and Comparative Examples 41 to 47.
  • Figure 29 is a graph showing the mass percentage change of Fe, Zn and A1 elements in the coating layers of Experimental Example 36 and Comparative Example 41, and the metallographic structure, (a) the mass percentage change of Experimental Example 36, (b) the metallographic structure of Experimental Example 36, (c) Comparative Example 41 mass percent change, (d) Comparative Example 41 metallographic structure.
  • Fig. 30 is a graph showing the mean values and variances of zinc powder shedding amounts in Experimental Examples 36 to 42 and Comparative Examples 41 to 47.
  • Fig. 31 is a result of profile measurement at the intermediate position of the scratches of the experimental example 36 and the comparative example 41, 1 : Experimental Example 36; 2: Comparative Example 41.
  • the atomic concentration of A1 and Zn in the Fe-Al intermediate transition layer between the steel sheet substrate of the hot-dip galvanized steel sheet and the zinc plating layer of the present invention has an Al/Zn ratio of 0.9 to 1.2. Further, the zinc plating grain orientation Zn(002) peak intensity is 25000 to 35000 cts.
  • the specific production method of hot-dip galvanized steel is as follows:
  • the steel plate is pickled and annealed and then hot-dip galvanized. During the hot-dip galvanizing operation, the temperature of the steel plate is
  • the bath temperature in the zinc pot is 450 ⁇ 460°C
  • the content of Fe in the plating bath is ⁇ 0.03%
  • the content of A1 in the plating bath is 0.16 ⁇ 0.25%
  • the unit speed is 100 ⁇ 120m/min.
  • the high-span temperature of the cooling section is 210 ⁇ 245 °C
  • the cooling rate of the steel plate is 0 ⁇ 90%.
  • a row of cold air nozzles is installed, and forced cooling is performed by blowing cold air; the horizontal cooling section of the strip steel entering the cooling tower through the first deflection roller is called a high span section, and the high span section is provided with four sets of bellows to adjust the temperature.
  • the high span temperature is the temperature at which the transmitted steel sheet enters the high span.
  • the temperature of the steel sheet entering the plating bath is 455-465 ° C
  • the plating bath in the zinc pot Temperature is 450 ⁇ 460 °C
  • plating The weight percentage of Fe in the bath is ⁇ 0.03%
  • the weight percentage of A1 in the plating bath is 0.16 ⁇ 0.18%
  • the unit speed is 100 ⁇ 110m/min
  • the high span temperature of the cooling section is 210 ⁇ 220°C
  • the cooling rate of the steel plate is 0%.
  • the method for producing the hot-dip galvanized steel sheet controls the Al/Zn ratio in the Fe-Al intermediate transition layer by the high-span temperature of the cooling section in the hot-dip galvanizing process, reduces the formation of the Fe-Zn alloy layer, and improves the adhesion of the plating layer.
  • the cooling rate of the steel plate is 0%, which means that the pre-cooling section completely closes the cold air nozzle, and the natural cooling is performed only by heat radiation and convection.
  • the atomic concentration Al/Zn ratio of A1 and Zn in the Fe-Al intermediate transition layer between the steel sheet substrate obtained by the method and the zinc plating layer is 0.9 to 1.2.
  • the second preferred embodiment is a method for producing a hot-dip galvanized steel sheet.
  • the steel sheet is subjected to hot-dip galvanizing after pickling and annealing.
  • the temperature of the steel sheet entering the plating bath is 475 to 485 ° C, and the plating bath is used in the zinc pot.
  • the temperature is 450 ⁇ 460°C
  • the weight percentage of Fe in the plating bath is ⁇ 0.03%
  • the cooling rate of the steel plate is 0%
  • the cooling section high span temperature: 235 ⁇ 245°C plating bath
  • the content of A1 in the weight percentage is 0.16% A1 0.18%.
  • the atomic concentration Al/Zn ratio of A1 and Zn in the Fe-Al intermediate transition layer between the steel sheet substrate and the zinc plating layer obtained by the method is 0.9 to 1.2, and the zinc coating grain orientation Zn (002) peak intensity is 25000 ⁇ 35,000cts.
  • the third preferred embodiment is a method for producing a hot-dip galvanized steel sheet.
  • the steel sheet is subjected to hot-dip galvanizing after pickling and annealing.
  • the temperature of the steel sheet entering the plating bath is 475 to 485 ° C, and the plating bath in the zinc pot The temperature is 450 ⁇ 460°C, the weight percentage of Fe in the plating bath is ⁇ 0.03%, the weight percentage of A1 in the plating bath is 0.18% ⁇ A1 0.21%, the unit speed: 100 ⁇ 110m/min, the cooling rate of the steel plate is 0. %, cooling section high span temperature: 235 ⁇ 245 °C.
  • the atomic concentration Al/Zn ratio of A1 and Zn in the Fe-Al intermediate transition layer between the steel sheet substrate and the zinc plating layer obtained by the method is 0.9 to 1.2, and the zinc coating grain orientation Zn (002) peak intensity is 25000 ⁇ 35,000cts.
  • the Al/Zn ratio in the Fe-Al intermediate transition layer is controlled by the temperature of the steel sheet entering the plating bath in the hot-dip galvanizing process, the formation of the Fe-Zn alloy layer is reduced, and the most plating layer is adjusted. Excellent grain orientation to improve adhesion of the coating.
  • the fourth preferred embodiment is a method for producing a hot-dip galvanized steel sheet.
  • the steel sheet is subjected to hot-dip galvanizing after pickling and annealing.
  • the temperature of the steel sheet entering the plating bath is 455 to 465 ° C, and the plating bath is used in the zinc pot.
  • the temperature is 450 ⁇ 460°C
  • the content of Fe in the plating bath is ⁇ 0.03%
  • the weight percentage of A1 in the plating bath is 0.16 ⁇ 0.18%
  • the unit speed is 110 ⁇ 120m/min
  • the steel plate is cooled by air cooling.
  • the atomic concentration Al/Zn ratio of A1 and Zn in the Fe-Al intermediate transition layer between the steel sheet substrate and the zinc plating layer obtained by the method is 0.9 to 1.2, and the zinc coating grain orientation Zn (002) peak intensity is 25000 ⁇ 35,000cts.
  • the method for producing the hot-dip galvanized steel sheet controls the Al/Zn ratio in the Fe-Al intermediate transition layer by the cooling rate of the steel plate after the hot-dip galvanizing process For example, the formation of the Fe-Zn alloy layer is reduced, the optimal grain orientation of the plating layer is adjusted, and the adhesion of the plating layer is improved.
  • the fifth preferred embodiment is a method for producing a hot-dip galvanized steel sheet.
  • the steel sheet is subjected to hot-dip galvanizing after pickling and annealing.
  • the temperature of the steel sheet entering the plating bath is 455 to 465 ° C, and the plating bath is used in the zinc pot.
  • the temperature is 450 ⁇ 460°C
  • the weight percentage of A1 in the plating bath 0.21 ⁇ 0.25%
  • the weight percentage of Fe in the plating bath is ⁇ 0.03%
  • the unit speed 100 ⁇ 110m/min
  • the cooling rate of the steel plate is 0%
  • the atomic concentration Al/Zn ratio of A1 and Zn in the Fe-Al intermediate transition layer between the steel sheet substrate and the zinc plating layer obtained by the method is 0.9 to 1.2, and the zinc coating grain orientation Zn (002) peak intensity is 25000 ⁇ 35,000cts.
  • the method for producing the hot-dip galvanized steel sheet controls the Al/Zn ratio in the Fe-Al intermediate transition layer by the aluminum content in the plating bath in the hot-dip galvanizing process, reduces the formation of the Fe-Zn alloy layer, and adjusts the optimal crystal of the plating layer.
  • the grain orientation improves the adhesion of the coating.
  • composition of the steel sheet to be galvanized is C: 0.03-0.07%, Mn: 0.01-0.03 by weight percent.
  • the thickness of the steel plate to be galvanized is 0.8 mm, the weight of the zinc layer after galvanizing is 180 to 195 g/m 2 , and the surface of the zinc layer is passivated by SiO 2 .
  • Example 1 Hot-dip galvanized steel sheet Experimental Example 1 to 5 and Comparative Example 6 to 15 Preparation and performance measurement
  • the thickness is 0.8 mm
  • the composition is C: 0.03 - 0.07%, Mn: 0.01 - 0.03 %, Si: 0.19 - 0.30%, P: 0.006 - 0.019%, S: 0.009 - 0.020%, A1: 0.02 - 0.07%,
  • the remaining DX51D cold-rolled steel sheets with Fe and inevitable impurities are pickled and annealed, and then hot-dip galvanized under the various hot-dip galvanizing conditions listed in Table 1.
  • the initial temperature of the plating bath in the zinc pot is 450 °C.
  • the bath bath Fe content is ⁇ 0.03 %, the A1 content is 0.160 ⁇ 0.180%, the unit speed is 100m/min, the cooling section high span temperature is 240°C, the cooling rate is 0%, and the steel plate temperature is adjusted to 475 ⁇ 485° when entering the plating bath.
  • C performs the hot-dip galvanizing operation to obtain the sample of the sample No. 1 to No. 5; the temperature of the steel plate is adjusted to 455 to 465 ° C and 440 to 450 ° C respectively during the plating bath to obtain the hot-dip galvanizing operation to obtain 6 to 10 and 11 to 15 No. Comparative sample.
  • the weight of the zinc layer is controlled to 180 to 195 g/m 2 , and the surface of the zinc layer is passivated by SiO 2 .
  • the metallographic sample preparation of the invention adopts oblique mounting, and the mounting material is bakelite powder.
  • the mounting material is bakelite powder.
  • Three samples of hot-dip galvanized steel sheets were glued together with 502, placed side by side on a diagonal pad with an inclination angle of 30° from the horizontal plane, and then mounted on a hot mount, polished and polished. The visible range of the entire section is approximately doubled, and the Fe-Al intermediate layer transition layer between each coating and the steel-based interface is clearly displayed.
  • the atomic mass and mass percentage of each element in the Fe-Al intermediate transition layer were determined by electron probe (EPMA1600 type) spectroscopy and point composition analysis.
  • the samples used in EPMA were all slanted and unetched metallographic samples.
  • all the experimental examples and comparative examples have a dark black belt-Fe-Al intermediate transition layer as shown in Fig. 1, and the two sides are respectively a steel base and a zinc layer.
  • the coating profiles were analyzed from the steel base to the surface of the zinc layer at equal distances. The specific position is shown in Figure 1, where 0 is the steel base position and 1 to 5 is the Fe-Al intermediate layer. Position, 6 to 12 for the zinc layer position.
  • the typical metallographic sample of the coating is analyzed by EPMA.
  • the spectrum of the EPMA line is analyzed.
  • the A1 element has the highest content in the middle layer.
  • the Zn element gradually increases from the steel base to the surface of the coating.
  • the Fe element starts from the steel base to the surface of the coating. gradually decreases.
  • FIG. 2 is a cross-sectional morphology of a metallographic sample of Experimental Example 1, Comparative Example 6, and Comparative Example 11 measured by a scanning electron microscope (SEM). Due to the oblique mounting, the Fe-Al intermediate transition layer with a thickness of several tens to several hundreds of nanometers between the zinc layer and the steel-based interface is clearly displayed, showing a fine grain morphology. Due to the oblique mounting, the width of the Fe-Al intermediate layer and the width of the entire coating are not compared.
  • Experimental Example 1 has a fine uniform pure zinc dendritic cross-sectional shape; More cracks indicate that a hard and brittle structure is formed between them, and the zinc layer is easily peeled off during processing; Comparative Example 11 Cracks have formed between the intermediate layer and the plating layer, and the plating layer has lost adhesion.
  • Fig. 3 is a metallographic photograph of the experimental example and the comparative example.
  • Figure 3 (a) shows that there is a Fe-Al intermediate transition layer in the coating, a thin ⁇ phase, and a small amount of dispersed ⁇ phase.
  • the coating is mostly composed of a pure zinc layer ⁇ phase.
  • the coating was tested for adhesion properties. This experimental example (1) had good adhesion to the coating.
  • Fig. 4 is a graph showing the atomic percentage change of the elements A1 and Zn of the Fe-Al intermediate transition layer of the experimental example 1 and the comparative examples 6 and 11.
  • Fig. 5 is the average atomic percentage of Al and Zn elements at positions 2 to 4 in the intermediate layer of the Fe-Al intermediate layer of the experimental example 1 and the comparative examples 6 and 11.
  • Table 2 lists the atomic concentration and Al/Zn ratio of A1 and Zn in the Fe-Al intermediate transition layer of each of the plating layers of the examples and the comparative examples. It can be seen from the above results that the atomic percentage of A1 element in the Fe-Al intermediate transition layer is larger than that in the comparative example.
  • the atomic percentage of Zn element is not much different from that of the comparative example, but the Al/Zn ratio of the experimental example is greater than 0.9.
  • the comparative example Al/Zn ratio was between 0.358 and 0.553.
  • each phase element in the plated structure was determined by EPMA spectroscopic point composition analysis. According to the mass percentage of Fe and Zn elements in each phase of the coating, and the metallographic photograph of the comparative coating structure, the ⁇ , ⁇ , ⁇ ⁇ phase existing in the coating can be judged.
  • Figure 6 shows the masses of Fe, Zn and A1 elements in the coatings of Experimental Example 1 ( Figure 6a), and Comparative Example 6 ( Figure 6b) and Comparative Example 11 ( Figure 6c) from the beginning of the steel substrate to the surface of the zinc layer. The percentage change and the metallographic structure in the coating.
  • Table 2 lists the phase structures of the coatings of the experimental and comparative examples based on the phase organization categories measured at six locations of the zinc layers 7 to 12.
  • the ⁇ phase and the ⁇ phase are less, and the pure zinc layer has more ⁇ phase; while the comparative layer has a thicker ⁇ phase and a ⁇ phase, and the pure zinc layer ⁇ phase is thinner.
  • a Fe-Al intermediate transition layer containing a high A1 content is formed between the steel base and the plating layer, and only zinc is unsaturatedly dissolved and forms zinc-depleted in the Fe-Al intermediate transition layer.
  • this layer can act as an adhesion and prevent the diffusion of Fe-Zn, and form a thin Fe-Zn alloy layer, ⁇ phase and ⁇ phase. Reduced, at this time, the adhesion of the coating is good.
  • the surface of the plating layer was left untreated, and a small angle diffraction (grazing angle of 5°) was applied to the X-ray diffractometer (XRD) to measure the diffraction peak intensity of the plating layer.
  • Experimental Example 1 and Comparative Examples 6 and 1 1 The typical diffraction pattern of the surface of the coating at a 5° glancing angle is shown in Fig. 7.
  • Table 2 lists the diffraction intensities of the Zn(002) peaks of each sample.
  • the anti-shedding properties of the coating were examined by a "U" bending test.
  • the bending test is carried out in accordance with the national standard GB/T 232- 1999 (Metal material bending test method), and the sample preparation is referred to GB/T 2975-1998 (sampling position and sample preparation for mechanical properties test of steel and steel products).
  • Figure 8 shows the final shape of the curved specimen.
  • the sample is processed by a wire cutter.
  • the surface of the sample is wiped with ethanol before the test.
  • the same size of the transparent tape is pasted on the inner and outer surfaces of all the bent portions of the sample.
  • the sample is bent together with the tape on the bending test machine, and the curved portion is collected through the tape.
  • the exfoliated zinc powder was measured by the ICP method for the amount of zinc powder peeled off from each plating layer.
  • Figure 9 shows the amount of zinc powder shedding in the experimental and comparative samples. The mean and variance of the experimental examples, the amount of zinc powder shedding was significantly smaller than that of the comparative example.
  • Table 3 Evaluation of the coating peeling resistance of each of the samples of the examples and the comparative examples according to the following criteria: ⁇ particularly good (zinc powder shedding amount: ⁇ 0.0100 mg); o good (zinc powder shedding amount: at 0.0100 to 0.0300 mg) Between) eight bad (zinc powder shedding amount: between 0.0300 ⁇ 0.0360mg); X bad (zinc powder shedding amount: ⁇ 0.0440mg).
  • the scratch resistance test of the coating was completed on the CETR UMT-2 multi-functional friction and wear tester in the United States.
  • the scratch test device was applied to the scratch resistance test.
  • the indenter of the scratch test was spade diamond, and the radius of curvature of the head was 800 ⁇ m.
  • the scratch test uses a linearly increasing loading method with a loading load increasing from 0.5 ⁇ to 2 ⁇ .
  • the Ambios XP2 profiler was used to measure the contour of the scratch after each coating test.
  • Fig. 10 shows typical profile measurement results at the intermediate positions of the plating scratches in Experimental Example 1 and Comparative Examples 6 and 11. It can be seen that the scratch depth of the plating layer in Experimental Example 1 was significantly smaller than that of Comparative Examples 6 and 11.
  • Table 3 evaluates the scratch resistance of each of the experimental and comparative samples according to the following criteria: o good (scratch depth 7.00 ⁇ ) ; slightly poor (scratch depth between 7.00 and 8.00 ⁇ m ⁇ ); (scratch depth 8.00 ⁇ ).
  • the coating wear resistance test was completed on the US CETR UMT-2 multi-function friction and wear tester reciprocating sliding friction test platform.
  • the upper sample (the grinding sample) is a stainless steel ball having a diameter of 10 mm, and the lower sample is a hot-dip galvanized steel plate.
  • the Ambios XP2 profiler was used to measure the wear profile of each coating after the test.
  • Fig. 11 shows the entire wear scars observed under SEM after the reciprocating sliding wear test of Experimental Example 1 (Fig.
  • Example 2 Hot-dip galvanized steel sheet Experimental Example 16 to 20 and Comparative Example 21 to 25 Preparation and performance measurement
  • DX1 cold-rolled steel plate has a thickness of 0.8mm, a composition of C 0.03 ⁇ 0.07 %, Mn 0.01 ⁇ 0.03%, Si 0.19 ⁇ 0.30%, P 0.006 ⁇ 0.019%, S 0.009-0.020%, A1 0.02-0.07%, and the rest is Fe.
  • hot-dip galvanizing operation is carried out under the hot-dip galvanizing process conditions listed in Table 4, wherein the initial temperature of the plating bath in the zinc pot is 450 ° C, in the plating bath Fe content ⁇ 0.03 %, unit speed: 100 m/min, cooling section high span temperature: 240 ° C, cooling rate 0%.
  • the content was adjusted to 0.18 % ⁇ A1 0.21%.
  • the hot-dip galvanizing operation was carried out to obtain the experimental example No. 16 to No. 20, the temperature of the steel sheet was adjusted to 460 ° C when the plating bath was introduced, and the A1 content in the plating bath was adjusted to 0.16 to 0.17% for hot plating.
  • the zinc operation gave 21 to 25 comparative examples.
  • the weight of the zinc layer is controlled to about 180 to 195 g/m 2 , and the surface of the zinc layer is passivated by SiO 2 .
  • Experimental Example 16 to 20 Electroplating Profile Electron Probe (EPMA1600 Type) The results of the spectral scanning analysis spectrum were the same as in Experimental Example 1 (see Fig. 1).
  • Fig. 12 shows atomic percentage changes of A1 and Zn elements in the typical Fe-Al intermediate transition layers of the experimental examples 16 to 20 and the comparative examples 21 to 25.
  • Fig. 13 shows the average atomic percentages of the A1 and Zn elements at positions 2 to 4 in the intermediate layer of the Fe-Al intermediate layer of the experimental examples 16 to 20 and the comparative examples 21 to 25.
  • Table 5 shows the atomic concentrations and Al/Zn ratios of A1 and Zn in the Fe-Al intermediate transition layers of the coatings of Examples 16 to 20 and Comparative Examples 21 to 25.
  • the atomic percentage of the A1 element in the Fe-Al intermediate transition layer of the experimental examples 16 to 20 is significantly larger than that of the comparative examples 21 to 25.
  • the atomic percentage of the Zn element is increased as compared with the samples of the comparative example.
  • the Fe/Al intermediate transition layer Al/Zn ratio was between 0.963 and 1.134
  • the comparative example 21 to 25 Al/Zn ratio was between 0.421 and 0.499.
  • the experimental examples 16 to 20 Al/Zn ratio were significant. It is larger than Comparative Examples 21 to 25 and larger than the above-mentioned Experimental Examples 1 to 5 Fe-Al intermediate transition layer Al/Zn ratio.
  • Fig. 14 shows the change in the mass percentage of the elements of Fe, Zn and Al in the plating layers of Experimental Examples 16 to 20 and Comparative Example 21 and the metallographic structure in the plating layer.
  • Table 5 lists the phase structures of the respective plating layers of Experimental Examples 16 to 20 and Comparative Examples 21 to 25. It can be seen that in the experimental examples 16 ⁇ 20, the ⁇ phase and the ⁇ phase are less, and the pure zinc layer has more ⁇ phases; while the comparative examples have thicker ⁇ phase and ⁇ phase, and the pure zinc layer ⁇ phase is thinner.
  • Fig. 16 shows the mean value and variance of the amount of zinc powder detached in Experimental Examples 16 to 20 and Comparative Examples 21 to 25. It can be seen that when the A1 content in the plating bath is 0.18% ⁇ A1 0.21%, the zinc powder dropping amount of the experimental examples 16 to 20 is significantly smaller than that of the comparative examples 21 to 25, and is significantly smaller than the above experimental examples 1 to 6. It shows that increasing the A1 content in the plating bath while increasing the temperature of the strip into the bath is more conducive to improving the anti-shedding performance of the coating.
  • Fig. 17 shows the results of profile measurement at the intermediate positions of the scratches of the experimental example 16 and the comparative example 21. It can be seen that the scratch depth of the plating layer of Experimental Example 16 was significantly smaller than that of Comparative Example 21 when the A1 content in the plating bath was 0.18% ⁇ A1 0.21%. (5) Coating wear resistance
  • Table 6 lists the average friction coefficients of the samples of Experimental Examples 16 to 20 and Comparative Examples 21 to 25 after 100 cycles of friction. (6) Comprehensive evaluation of coating adhesion performance
  • the thickness is 0.8 mm, the composition is C: 0.03 - 0.07%, Mn : 0.01 - 0.03%, Si: 0.19 - 0.30%,
  • the hot-dip galvanizing operation is carried out, wherein the plating bath temperature in the zinc pot is 450 ° C, the Fe content in the plating bath is ⁇ 0.03%, the A1 content is 0.16 ⁇ 0.18%, and the steel sheet temperature in the plating bath is 460 ° C, the unit speed: 110 ⁇ 120m/min. After the steel plate is discharged from the zinc pot, the steel plate is forcedly cooled by air cooling, and the cooling rate is 70 to 90%.
  • the weight of the zinc layer was controlled to about 180 g/m 2 , and the surface of the zinc layer was passivated by SiO 2 .
  • the coating orientation of the coating was evaluated by the following methods, such as the grain orientation of the plating layer and the plating adhesion resistance, scratch resistance, abrasion resistance, and the like.
  • Typical diffraction patterns for the surface of the coatings of Examples 21 and 26 and Comparative Examples 26 and 30 at a 5° glancing angle are shown in Fig. 18. It can be seen that the strongest diffraction peak of Zn in the coatings of the experimental examples 21 and 26 is much higher than that of the comparative examples 26 and 30, and the top 100 peak of Zn is transferred from Zn (101) to Zn (002). Table 8 shows the diffraction intensities of the Zn(002) peaks of each sample. It can be seen that the cooling rate of the experimental example is increased to 70 to 90%, and Zn is compared with the comparative example in which the cooling rates are 30 to 50% and 0%, respectively. The diffraction intensity of the (002) peak is enhanced, both of which are greater than 27000 cts, and the plated grains exhibit a preferred orientation in the Zn (002) direction.
  • Fig. 19 shows the mean value and variance of the amount of zinc powder shedding in the experimental examples and the comparative examples.
  • the amount of zinc powder detached in the experimental examples was significantly smaller than that in the comparative example.
  • Figure 20 shows typical profiling at intermediate positions of the coating scratches in Experimental Examples 21 and 26 and Comparative Examples 26 and 30. Quantity results. It can be seen that the scratch depth of the plating layer in the experimental example is significantly smaller than that of the comparative example.
  • Table 8 lists the average friction coefficients of the experimental and comparative samples after 100 cycles of friction.
  • the present invention increases the cooling rate of the steel sheet during the hot-dip galvanizing process to 70 to 90%, and the hot-dip galvanized steel sheet obtained under the same conditions of other processes (experimental example) is compared with the conventional steel sheet.
  • the coated grains exhibit a preferential orientation in the Zn (002) direction, and the anti-shedding performance, scratch resistance and wear resistance of the coating layer are remarkably improved, and the adhesion property between the plating layer and the substrate is remarkably improved.
  • the thickness of DX1 cold-rolled steel plate is 0.8mm, the composition is C 0.03 ⁇ 0.07%, Mn 0.01 ⁇ 0.03%, Si 0.19 ⁇ 0.30%, P0.006 ⁇ 0.019%, S 0.009-0.020%, A10.02-0.07%, the rest For Fe and inevitable miscellaneous Quality, DX1 cold-rolled steel sheet is acid-washed and annealed, and hot-dip galvanizing is carried out under the hot-dip galvanizing process conditions listed in Table 9, wherein the initial temperature of the plating bath in the zinc pot is 450 ° C, and the Fe content in the plating bath is ⁇ 0.03 %, steel plate temperature when entering the plating bath: 460 ° C, unit speed: 100 m / min, cooling section high span temperature: 240 ° C, cooling rate is 0%, the A1 content in the plating bath is adjusted to 0.21 ⁇ 0.25 % The hot-dip galvanizing operation was carried out to obtain an experimental example No.
  • the weight of the zinc layer is controlled to about 180 to 195 g/m 2 , and the surface of the zinc layer is passivated by SiO 2 .
  • Experimental Example 31 Typical plating profile electron probe (EPMA1600 type) The spectral surface scanning analysis spectrum results were the same as in Experimental Example 1 (see Fig. 1).
  • Fig. 21 shows the atomic percentage change of the A1 and Zn elements in the typical experimental sample 31 and the comparative sample 36 coated Fe-Al intermediate transition layer.
  • Fig. 22 shows the average atomic percentages of the A1 and Zn elements at the positions 2 to 4 in the intermediate layer of the Fe-Al intermediate layer of the experimental examples 31 to 35 and the comparative samples 36 to 40.
  • Table 10 shows the atomic concentration and Al/Zn ratio of A1 and Zn in the Fe-Al intermediate transition layer of each of the experimental and comparative examples.
  • the atomic percentage of A1 element in the Fe-Al intermediate transition layer is significantly larger than that in the comparative example.
  • the atomic percentage of Zn element is increased compared with the comparative example, but the experimental example Al/Zn ratio is 0.940 ⁇ Between 1.125, and the comparative example Al/Zn ratio was between 0.421 and 0.499, and the Al/Zn ratio of the experimental example was significantly larger than that of the comparative example.
  • Table 10 lists the phase structures of the respective plating layers of the experimental examples and the comparative examples. It can be seen that the ⁇ phase and the ⁇ phase are less in the coating of the experimental example, and the ⁇ phase of the pure zinc layer is more; while in the comparative example, the ⁇ phase and the ⁇ phase are thicker, and the ⁇ phase of the pure zinc layer is thinner.
  • Fig. 25 shows the mean value and variance of the amount of zinc powder detached in Experimental Examples 31 to 35 and Comparative Examples 36 to 40. It can be seen that when the A1 content in the plating bath is between 0.21 and 0.25%, the zinc powder dropping amount of the experimental examples 31 to 35 is significantly smaller than that of the comparative examples 36 to 40.
  • Fig. 26 shows the results of profile measurement at the intermediate positions of the scratches of the experimental examples 31 and 36. It can be seen that when the A1 content in the plating bath is between 0.21 and 0.25%, the scratch depth of the plating layer in the experimental example is significantly smaller than that of the comparative example.
  • Table 11 lists the average friction coefficients of the samples of the examples and the comparative examples after 100 cycles of friction.
  • the hot-dip galvanized steel sheet obtained by controlling the A1 content in the plating bath between 0.21 and 0.25% in the hot-dip galvanizing process of the present invention and the other processes are unchanged
  • the Al/Zn ratio in the Fe-Al intermediate transition layer is between 0.940 and 1.125
  • the ⁇ phase and the ⁇ phase are reduced in the coating
  • the ⁇ phase of the pure zinc layer is increased, and the orientation optimization is formed.
  • the ⁇ (002) grain, the anti-shedding property, the scratch resistance and the abrasion resistance of the plating layer are remarkably improved, and the adhesion property between the plating layer and the substrate is remarkably improved.
  • the thickness is 0.8 mm
  • the composition is C: 0.03 - 0.07 %, Mn: 0.01 - 0.03 %, Si: 0.19 - 0.30%, P: 0.006 - 0.019%, S: 0.009 - 0.020%, A1: 0.02 - 0.07 %
  • the remaining DX1 cold-rolled steel sheets with Fe and impurities are pickled and annealed, and then subjected to hot-dip galvanizing operation under the hot-dip galvanizing process conditions listed in Table 12, wherein the plating bath temperature in the zinc pot is 450 ° C, plating bath Medium Fe content ⁇ 0.03 %, A1 content: 0.16 ⁇ 0.18 %, steel plate temperature when entering the plating bath: 460 °C, unit speed: 100m/min, cooling rate is 0%, the high span temperature of the cooling section is adjusted to 210 ⁇ At 220 °C, the experimental example of 36 ⁇ 42 was obtained; the temperature of the cooling section was adjusted to 240 ⁇ 260 °C to obtain
  • Experimental Example 36 Typical plating profile electron probe (EPMA1600 type) The spectral surface scanning analysis spectrum results were the same as in Experimental Example 1 (see Fig. 1).
  • Fig. 27 shows the atomic percentage change of the A1 and Zn elements in the Fe-Al intermediate transition layer of the typical experimental example 36 and the comparative example 41.
  • Fig. 28 shows the average atomic percentages of the A1 and Zn elements at the positions 2 to 4 in the Fe-Al intermediate transition layer of the experimental examples 36 to 42 and the comparative examples 41 to 47.
  • Table 13 shows the atomic concentration and Al/Zn ratio of A1 and Zn in the Fe-Al intermediate transition layer of each of the experimental and comparative examples.
  • the atomic percentage of A1 element in the Fe-Al intermediate transition layer is larger than that of the comparative example, and the atomic percentage of Zn element is smaller than that of the comparative example.
  • the Al/Zn ratio of the experimental example is between 0.757 and 0.884, and the comparative example.
  • the Al/Zn ratio was between 0.131 and 0.535, and the Al/Zn ratio of the experimental example was significantly larger than that of the comparative example.
  • Fig. 29 shows changes in the mass percentage of Fe, Zn and A1 elements in the plating layers of Experimental Example 36 and Comparative Example 41 and the metallographic structure in the plating layer.
  • Table 13 lists the phase structures of the respective plating layers of the experimental examples and the comparative examples. It can be seen that the ⁇ phase and the ⁇ phase are less in the coating of the experimental example, and the ⁇ phase of the pure zinc layer is more; while the comparative layer has a thicker ⁇ phase and a ⁇ phase, and the pure zinc layer ⁇ phase is thinner.
  • Fig. 30 shows the mean value and variance of the amount of zinc powder detached in Experimental Examples 36 to 42 and Comparative Examples 41 to 47. It can be seen that the amount of zinc powder detached in the experimental examples 36 to 42 was significantly smaller than that in the comparative examples 41 to 47.
  • FIG. 31 shows the results of profile measurement at the intermediate positions of the coating scratches of Experimental Example 36 and Comparative Example 41. It can be seen that when the temperature of the cooling section is adjusted to 210 220 ° C, the scratch depth of the coating in the experimental example is significantly smaller than that of the comparative example.
  • Table 13 lists the average friction coefficients of the experimental and comparative samples after 100 cycles of friction.

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Description

热镀锌钢板及其生产方法 技术领域
本发明属于热镀锌钢板制造领域， 具体涉及一种镀层附着性良好的热镀锌钢板及其 生产方法。
背景技术
热镀锌钢板由于其良好的耐腐蚀性能、 优良的涂镀性能和洁净的外观在家用电器、 汽车车身用板等制造业中得到了广泛的应用。对热镀锌钢板镀层的要求是镀层与基板的 附着力强， 冲压变形时不脱落， 另外要有良好的焊接性能、 耐腐蚀性能和磷化性能， 以 确保漆膜的附着力和涂漆后的耐腐蚀性。 然而， 热镀锌钢板在实际应用的冲压加工过程 中存在镀层的粉化和剥离等问题，造成了镀层的破坏,进一步影响到镀层的耐腐蚀性和涂 着性。
中国专利《公开号 CN17011130A, 公开日期： 2005年 11月 23日》及日本专利《特 开 2002— 4019号公报》、 《特开 2002— 4020号公报》中公开了控制热镀锌钢板的表面粗 糙度以抑制冲压成形时的金属模具粘附的方法， 以及改善深冲性的方法。 然而， 在对这 种热镀锌钢板进行详细研究时发现， 与金属模具的摩擦距离较短时， 能够控制与金属模 具粘附的效果， 但摩擦距离越长则此效果越小， 根据摩擦条件不同有时不能得到改善的 效果。另外， 在上述方案中， 作为提高这种粗糙度的方法， 可以列举控制光整辊的条件、 轧制条件等的方法， 但是实际上， 锌容易在辊上堆积成块， 所以难以稳定地在热镀锌钢 板表面上形成规定的粗糙度。 此外， 在日本专利《特许第 2993404号公报》 中提出母材 使用含 P: 0.010〜0.10质量％、 Si: 0.05〜0.20质量％， 且满足 Si P的 P添加钢时， 提高镀层被膜的附着性技术。然而对于其它未添加 P的钢板， 该方法则不一定能使镀层 被膜附着性增高。 日本专利 《特开 2001-335908号公报》 中公开了如下技术： 母材为使 用 C: 0.05-0.25质量％的低碳钢并适量添加 Si、 A1的高强度残余奥氏体钢时通过向钢 中适量添加 Ti、 Nb等固定晶界 C， 而提高镀覆界面强度。 然而， 这是关于残余奥氏体 钢的技术， 对于没有残余奥氏体相的高强度钢板不一定会得到足够性能的问题。
镀锌钢板镀层的附着性除了受基体钢板的成分、 工艺条件的影响外， 还主要受到镀 层的成分和组织结构的影响。 粉化和剥离与镀层的化学成分及相结构有关， 镀层粉化量 随镀层中的铁含量升高而增多。钢板与锌层之间依次为1\ δ、 ζ和 η相， Γ相是以 1¾^1 21为 基础的中间金属相， δ相是以 FeZn7为基础的中间金属相， ζ相是以？ 1 13为基础的中间金 属相， η相是由纯锌组成的含有微量铁的固溶体。镀层的粉化为 Γ相两侧的界面形成微裂 纹， 扩展后贯穿整个镀层形成。 Γ相厚度超过 Ι.Ομιη时， 粉化量随 Γ相的厚度增加而增加， 将镀层中的铁含量控制在 11%左右， 就可以阻碍厚的 Γ相形成， 因此抗粉化性能的主要 影响因素是 δ相 （细晶结构）和 ζ相 （柱状结构）。 δ相硬而脆， 对成形性不利， ζ相硬度与 基体钢板相当， 在形变时利于释放镀层中的残余应力， 但其韧性高， 易粘在模具上造成 镀层表面缺陷或者发生剥离。 因此只有当镀层中的 ζ相和 δ相具有适当比例时， 镀层才具 有好的成形性。镀层表面 ξ相消失而不均匀的致密 δ相未出现时的镀层组织是最佳镀层组 织。
在生产中常常向锌液中加铝来提高镀锌层的韧性，这时热镀锌钢板的钢基与锌层之 间的 Fe-Al 中间过渡层中的铝含量是衡量镀层粘附强度的一个重要标准。 但是， Fe-Al 中间过渡层中含有较高的铝量，仅是获得良好镀层粘附力的必要条件，而不是充分条件。 因为只有当锌在 Fe-Al中间过渡层中的不饱和溶解和形成贫锌固溶体时， 此层才能起到 粘附作用和阻止 Fe和 Zn元素扩散的作用， 并形成少量 δ和 ζ相的薄 Fe-Zn合金层， 此 时， 镀层附着性较好。 若 Zn在 Fe-Al中间过渡层中的溶解度达到过饱和并生成了富锌 固溶体时，这时中间层中的 A1绝对含量虽然没有减少，但是 A1的百分含量却显著下降， 同时因为锌的过饱和而破坏了 Fe-Al中间过渡层的均质性， 由此便使中间层丧失了粘附 作用和阻止 Fe和 Zn元素扩散作用， 并且形成含有较多 δ和 ζ相的较厚 Fe-Zn合金层， 使锌层的附着力同时变坏。
现有技术中通过改变钢板的成分或通过控制热镀锌钢板的表面粗糙度使表面形成 被膜技术来改善镀层与钢基的附着性， 但是未取得较好的效果， 目前还未出现通过控制 镀层的成分和组织结构来改善镀层与钢基的附着性的方法。
发明内容
本发明所要解决的第一个技术问题是提供一种镀层与钢基的附着性高的热镀锌钢 板。
解决该技术问题采用的技术方案是： 所述热镀锌钢板的钢板基材与锌镀层之间的 Fe-Al中间过渡层中 A1和 Zn的原子浓度 Al/Zn比值为 0.9〜1.2。
进一步的， 本发明还提供镀层与钢基的附着性高， 同时镀层的组织结构较优的热镀 锌钢板， 所述热镀锌钢板的钢板基材与锌镀层之间的 Fe-Al中间过渡层中 A1和 Zn的原 子浓度 Al/Zn比值为 0.9〜 1.2， 锌镀层晶粒取向 Zn (002) 峰强度 25000〜35000cts。 本发明所要解决的第二个技术问题是提供一种热镀锌钢板生产方法， 该方法制得的 钢板基材与锌镀层之间的 Fe-Al中间过渡层中 A1和 Zn的原子浓度 Al/Zn比值为 0.9〜 1.2。
解决上述技术问题采用的技术方案是： 钢板经酸洗、 退火后进行热镀锌操作， 热镀 锌操作过程中， 入镀浴时钢板温度为 455〜485°C， 锌锅中镀浴温度为 450〜460°C， 镀 浴中 Fe重量百分比含量<0.03%， 镀浴中 A1重量百分比含量 0.16〜0.25%， 机组速度 100〜120m/min， 冷却段的高跨温度 210〜245°C， 钢板冷却速率为 0〜90%。
优选方案之一， 热镀锌钢板生产方法， 钢板经酸洗、 退火后进行热镀锌操作， 热镀 锌操作过程中， 入镀浴时钢板温度为 455〜465°C， 锌锅中镀浴温度为 450〜460°C， 镀 浴中 Fe的重量百分比含量 <0.03%， 镀浴中 A1的重量百分比含量 0.16〜0.18%， 机组速 度 100〜110m/min， 冷却段的高跨温度 210〜220°C， 钢板冷却速率为 0%。
优选方案之二， 热镀锌钢板生产方法， 钢板经酸洗、 退火后进行热镀锌操作， 热镀 锌操作过程中， 入镀浴时钢板温度为 475〜485°C， 锌锅中镀浴温度为 450〜460°C， 镀 浴中 Fe的重量百分比含量 <0.03%， 机组速度： 100〜110m/min， 钢板冷却速率为 0%， 冷却段高跨温度： 235〜245°C， 镀浴中 A1的重量百分比含量为 0.16% A1 0.18%。
优选方案之三， 热镀锌钢板生产方法， 钢板经酸洗、 退火后进行热镀锌操作， 热镀 锌操作过程中， 入镀浴时钢板温度为 475〜485°C， 锌锅中镀浴温度为 450〜460°C， 镀 浴中 Fe的重量百分比含量 <0.03%， 镀浴中 A1的重量百分比含量为 0.18% <A1 0.21 %, 机组速度： 100〜110m/min， 钢板冷却速率为 0%， 冷却段高跨温度： 235〜245°C。
优选方案之四， 热镀锌钢板生产方法， 钢板经酸洗、 退火后进行热镀锌操作， 热镀 锌操作过程中， 入镀浴时钢板温度为 455〜465°C， 锌锅中镀浴温度为 450〜460°C， 镀 浴中 Fe的重量百分比含量 <0.03%， 镀浴中 A1的重量百分比含量 0.16〜0.18%， 机组速 度 110〜120m/min， 钢板出锌锅后用风冷进行强制冷却， 冷却速率 70〜90% (相对于冷 风喷嘴全部关闭冷却速率为 0%的自然冷却， 冷风喷嘴开启的比例为 70〜90%)。
优选方案之五， 热镀锌钢板生产方法， 钢板经酸洗、 退火后进行热镀锌操作， 热镀 锌操作过程中， 入镀浴时钢板温度为 455〜465°C， 锌锅中镀浴温度为 450〜460°C， 镀 浴中 A1的重量百分比含量： 0.21〜0.25%， 镀浴中 Fe的重量百分比含量 <0.03%， 机组 速度： 100〜110m/min， 钢板冷却速率为 0%， 冷却段高跨温度： 235〜245°C。 更进一步的， 上述待镀锌的钢板成分以重量百分比计， 含有 C: 0.03〜0.07%， Mm 0.01—0.03 % , Si: 0.19〜0.30 %， P: 0.006〜0.019%， S: 0.009〜0.020 %， A1: 0.02〜 0.07% , 其余为 Fe。
所述待镀锌的钢板厚度为 0.8mm，镀锌后锌层重量为 180〜195g/m2，锌层表面经过 Si02钝化处理。
本发明的有益效果是：
( 1 ) 本发明的热镀锌工艺条件使钢板基材与锌镀层之间的 Fe-Al 中间过渡层可以 阻止 Fe、 Zn之间的相互扩散， 减少 Fe-Zn合金层的形成， 镀层中不会形成 Γ相， δ相 较薄， ξ相很少， 镀层大部分由 η相组成， 提高了热镀锌钢板镀层的附着性， 镀层锌粉 脱落、 剥离等现象减少；
(2)本发明的热镀锌工艺条件使热镀锌钢板的镀层晶粒取向优化， 镀层的抗划性、 耐磨性及附着性能明显提高；
(3 ) 本发明的热镀锌生产工艺简单， 成本较低。
附图说明
图 1是实验例 1的镀层剖面电子探针 （EPMA1600型） 波谱面扫描分析谱图。 图 2是实验例 1和比较例 6、 11镀层扫描电镜 （SEM) 断面形貌， （a) 实验例 1 ; (b) 比较例 6; ( c) 比较例 11。
图 3是光学金相显微镜 （OLYMPUS BX51型） 倍数为 100x的金相照片， （a) 是实 验例 1， (b) 是比较例 6。
图 4是实验例 1和比较例 6、 11镀层 Fe-Al中间过渡层 A1和 Zn元素原子百分比变 化示意图。
图 5是实验例 1〜5和比较例 6〜10、11〜15镀层 Fe-Al中间过渡层中（图 1所示; )2〜 4位置处 Al、 Zn元素平均原子百分比变化示意图。
图 6是实验例 1和比较例 6、11镀层中从钢基到锌层表面各位置处 (图 1所示)的 Fe、 Zn和 A1元素的质量百分比变化及镀层中的金相组织， （a)实验例 1 ; (b)比较例 6; (c) 比较例 11。
图 7是实验例 1及比较例 6、 11典型的 XRD衍射图谱 （a) 实验例 1、 (b) 比较例 6、 （c) 比较例 11。
图 8是 U形弯曲试样形状示意图： 1 弯曲试验机夹具、 2 弯曲试样。 图 9是实验例 1〜5试样和比较例 6〜10、 11〜15试样锌粉脱落量均值及方差。 图 10是实验例 1与比较例 6和 11镀层划痕中间位置处典型的轮廓测量图： 1为实 验例 1， 2为比较例 6， 3为比较例 11。
图 11是实验例 1与比较例 6和 11镀层往复滑动磨损试验后在 SEM下观察到的磨 痕全貌。
图 12是实验例 16和比较例 21镀层中 Fe-Al中间过渡层的 Al、 Zn元素原子百分比 变化。
图 13是实验例 16〜20和比较例 21〜25镀层中 Fe-Al中间过渡层的 Al、 Zn元素平 均原子百分比。
图 14是实验例 16及比较例 21镀层中 Fe、 Zn和 A1元素的质量百分比变化及金相 组织， （a) 实验例 16， (b) 比较例 21。
图 15是实验例 16及比较例 21典型的 XRD衍射图谱 （a) 实验例 16、 (b) 比较例
21。
图 16是实验例 16〜20和比较例 21〜25锌粉脱落量均值及方差。
图 17是实验例 16与比较例 21镀层划痕中间位置处轮廓测量结果， 1比较例 21， 2 实验例 16。
图 18是实验例 21和 26及比较例 26和 30典型的 XRD衍射图谱 （a) 实验例 21 ; (b) 实验例 26; ( c) 比较例 26; ( d) 比较例 30， 纵坐标是衍射强度， 横坐标是 2θ/°。
图 19是实验例 21〜30、 比较例 26〜30、 比较例 31〜35锌粉脱落量均值及方差。 图 20是实验例 21和 26及比较例 26和 30镀层划痕中间位置处轮廓测量结果， 1 实 验例 21， 2 实验例 26， 3 比较例 26， 4比较例 30。
图 21是实验例 31和比较例 36镀层中 Fe-Al中间过渡层的 Al、 Zn元素原子百分比 变化。
图 22是实验例 31〜35和比较例 36〜40镀层中 Fe-Al中间过渡层的 Al、 Zn元素平 均原子百分比。
图 23是实验例 31和比较例 36镀层中 Fe、 Zn和 A1元素的质量百分比变化及金相 组织， （a) 实验例 31， (b) 比较例 36。
图 24是实验例 31及比较例 36典型的 XRD衍射图谱 （a) 实验例 31、 (b) 比较例 图 25是实验例 31〜35和比较例 36〜40锌粉脱落量均值及方差。
图 26是实验例 31与比较例 36镀层划痕中间位置处轮廓测量结果， 1比较例 36、 2 实验例 31。
图 27是实验例 36和比较例 41镀层中 Fe-Al中间过渡层的 Al、 Zn元素原子百分比 变化。
图 28是实验例 36〜42和比较例 41〜47镀层中 Fe-Al中间过渡层的 Al、 Zn元素平 均原子百分比。
图 29是实验例 36和比较例 41镀层中 Fe、 Zn和 A1元素的质量百分比变化及金相 组织， （a) 实验例 36质量百分比变化， （b) 实验例 36金相组织， （c) 比较例 41质量 百分比变化， （d) 比较例 41金相组织。
图 30是实验例 36〜42和比较例 41〜47锌粉脱落量均值及方差。
图 31是实验例 36与比较例 41镀层划痕中间位置处轮廓测量结果， 1 : 实验例 36; 2： 比较例 41。
具体实施方式
以下通过具体实施方式结合实施例对本发明作进一步的阐述。实施例仅用于说明本 发明， 而不是以任何方式来限制本发明。
本发明热镀锌钢板的钢板基材与锌镀层之间的 Fe-Al中间过渡层中 A1和 Zn的原子 浓度 Al/Zn比值为 0.9〜 1.2。进一步地，锌镀层晶粒取向 Zn( 002 )峰强度 25000〜35000cts。
热镀锌钢板具体生产方法如下：
钢板经酸洗、 退火后进行热镀锌操作， 热镀锌操作过程中， 入镀浴时钢板温度为
455〜485 °C， 锌锅中镀浴温度为 450〜460°C， 镀浴中 Fe重量百分比含量<0.03 %， 镀浴 中 A1重量百分比含量 0.16〜0.25 %，机组速度 100〜120m/min，冷却段的高跨温度 210〜 245 °C ,钢板冷却速率为 0〜90 %。镀后钢板从锌锅拉出垂直向上到冷却塔第一转向辊称 为预冷段（一般 15〜30米）， 为使镀锌层在第一转向辊前就凝固， 在仅靠气刀上方装设 有一排冷风喷嘴， 采用喷吹冷风进行强制冷却； 带钢经第一转向辊进入冷却塔的水平冷 却段称为高跨段， 高跨段设有 4组风箱调节温度。 高跨温度为传送的钢板进入高跨段时 的温度。
优选方案之一， 热镀锌钢板生产方法， 钢板经酸洗、 退火后进行热镀锌操作， 热镀 锌操作过程中， 入镀浴时钢板温度为 455〜465 °C， 锌锅中镀浴温度为 450〜460°C， 镀 浴中 Fe的重量百分比含量 <0.03 %， 镀浴中 A1的重量百分比含量 0.16〜0.18 %， 机组速 度 100〜110m/min， 冷却段的高跨温度 210〜220°C， 钢板冷却速率为 0%。 该热镀锌钢 板的生产方法通过热镀锌工艺中的冷却段的高跨温度控制 Fe-Al中间过渡层中的 Al/Zn 比例， 减少 Fe-Zn合金层的形成， 提高镀层的附着性。 其中， 所述钢板冷却速率为 0% 是指预冷段全部关闭冷风喷嘴， 仅靠热辐射和对流进行自然冷却。 该方法制得的钢板基 材与锌镀层之间的 Fe-Al中间过渡层中 A1和 Zn的原子浓度 Al/Zn比值为 0.9〜1.2。
优选方案之二， 热镀锌钢板生产方法， 钢板经酸洗、 退火后进行热镀锌操作， 热镀 锌操作过程中， 入镀浴时钢板温度为 475〜485°C， 锌锅中镀浴温度为 450〜460°C， 镀 浴中 Fe的重量百分比含量 <0.03 %， 机组速度： 100〜110m/min， 钢板冷却速率为 0%， 冷却段高跨温度： 235〜245°C， 镀浴中 A1的重量百分比含量为 0.16% A1 0.18 %。 该方法制得的钢板基材与锌镀层之间的 Fe-Al中间过渡层中 A1和 Zn的原子浓度 Al/Zn 比值为 0.9〜1.2， 且锌镀层晶粒取向 Zn (002) 峰强度 25000〜35000cts。
优选方案之三， 热镀锌钢板生产方法， 钢板经酸洗、 退火后进行热镀锌操作， 热镀 锌操作过程中， 入镀浴时钢板温度为 475〜485°C， 锌锅中镀浴温度为 450〜460°C， 镀 浴中 Fe的重量百分比含量 <0.03 %， 镀浴中 A1的重量百分比含量为 0.18 % <A1 0.21 % , 机组速度： 100〜110m/min， 钢板冷却速率为 0%， 冷却段高跨温度： 235〜245°C。 该方法制得的钢板基材与锌镀层之间的 Fe-Al中间过渡层中 A1和 Zn的原子浓度 Al/Zn 比值为 0.9〜1.2， 且锌镀层晶粒取向 Zn (002) 峰强度 25000〜35000cts。
前述两种热镀锌钢板的生产方法， 通过热镀锌工艺中的钢板入镀浴温度控制 Fe-Al 中间过渡层中的 Al/Zn比例， 减少 Fe-Zn合金层的形成， 调整镀层的最优晶粒取向， 提 高镀层的附着性。
优选方案之四， 热镀锌钢板生产方法， 钢板经酸洗、 退火后进行热镀锌操作， 热镀 锌操作过程中， 入镀浴时钢板温度为 455〜465°C， 锌锅中镀浴温度为 450〜460°C， 镀 浴中 Fe的重量百分比含量 <0.03 %， 镀浴中 A1的重量百分比含量 0.16〜0.18 %， 机组速 度 110〜120m/min， 钢板出锌锅后用风冷进行强制冷却， 冷却速率 70〜90% (相对于冷 风喷嘴全部关闭冷却速率为 0%的自然冷却， 冷风喷嘴开启的比例为 70〜90% )。 该方 法制得的钢板基材与锌镀层之间的 Fe-Al中间过渡层中 A1和 Zn的原子浓度 Al/Zn比值 为 0.9〜1.2， 且锌镀层晶粒取向 Zn (002) 峰强度 25000〜35000cts。 该热镀锌钢板的生 产方法通过热镀锌工艺中的钢板出锌锅后冷却速率控制 Fe-Al中间过渡层中的 Al/Zn比 例， 减少 Fe-Zn合金层的形成， 调整镀层的最优晶粒取向， 提高镀层的附着性。
优选方案之五， 热镀锌钢板生产方法， 钢板经酸洗、 退火后进行热镀锌操作， 热镀 锌操作过程中， 入镀浴时钢板温度为 455〜465°C， 锌锅中镀浴温度为 450〜460°C， 镀 浴中 A1的重量百分比含量： 0.21〜0.25 %， 镀浴中 Fe的重量百分比含量 <0.03 %， 机组 速度： 100〜110m/min， 钢板冷却速率为 0%， 冷却段高跨温度： 235〜245°C。 该方法 制得的钢板基材与锌镀层之间的 Fe-Al中间过渡层中 A1和 Zn的原子浓度 Al/Zn比值为 0.9〜1.2， 且锌镀层晶粒取向 Zn (002) 峰强度 25000〜35000cts。 该热镀锌钢板的生产 方法， 通过热镀锌工艺中的镀浴中铝含量控制 Fe-Al中间过渡层中的 Al/Zn比例， 减少 Fe-Zn合金层的形成， 调整镀层的最优晶粒取向， 提高镀层的附着性。
上述待镀锌的钢板成分以重量百分比计， 含有 C: 0.03-0.07% , Mn: 0.01-0.03
% , Si: 0.19—0.30% , P: 0.006〜0.019%， S: 0.009〜0.020%， Ah 0.02〜0.07%， 其 余为 Fe。
所述待镀锌的钢板厚度为 0.8mm，镀锌后锌层重量为 180〜195g/m2，锌层表面经过 Si02钝化处理。
实施例 1 热镀锌钢板实验例 1〜5和比较例 6〜15的制备及性能测定
将厚度为 0.8mm， 成分为 C: 0.03—0.07% , Mn: 0.01—0.03 % , Si: 0.19〜0.30%， P: 0.006〜0.019%， S: 0.009—0.020 % , A1: 0.02〜0.07%， 其余为 Fe及不可避免杂质 的 DX51D冷轧钢板经酸洗、退火后， 在表 1所列出的各个热镀锌工艺条件下进行热镀锌 操作， 锌锅中镀浴初始温度为 450°C， 镀浴 Fe含量 <0.03 %， A1含量为 0.160〜0.180%， 机组速度 100m/min， 冷却段高跨温度 240°C， 冷却速率 0%， 将入镀浴时钢板温度调整 为 475〜485°C进行热镀锌操作得到 1〜5号实施例试样； 入镀浴时钢板温度分别调整为 455〜465°C和 440〜450°C进行热镀锌操作得到 6〜10号和 11〜15号比较例试样。 锌层 重量控制到 180〜195g/m2， 锌层表面经过 Si02钝化处理。
表 1热镀锌工艺条件
Figure imgf000010_0001
实验例 4 DX51D 0.80 191 100 479 0.170 240 实验例 5 DX51D 0.80 191 100 485 0.168 240 比较例 6 DX51D 0.80 181 100 456 0.170 240 比较例 7 DX51D 0.80 181 100 460 0.172 240 比较例 8 DX51D 0.80 181 100 462 0.170 240 比较例 9 DX51D 0.80 181 100 458 0.171 240 比较例 10 DX51D 0.80 181 100 461 0.174 240 比较例 11 DX51D 0.80 183 100 440 0.170 240 比较例 12 DX51D 0.80 183 100 442 0.171 240 比较例 13 DX51D 0.80 183 100 444 0.170 240 比较例 14 DX51D 0.80 183 100 448 0.175 240 比较例 15 DX51D 0.80 183 100 445 0.172 240 热镀锌钢板实验例 1〜5和比较例 6〜15的性能测定：
( 1 ) 镀层 Fe-Al中间过渡层、 断面形貌及组织结构
由于 Fe-Al中间过渡层厚度在几十至几百纳米之间， 常规的金相制样手段很难将这 一中间层显示出来。 本发明金相制样采用斜镶样， 镶样材料为电木粉。 将 3块热镀锌钢 板试样用 502强力胶粘在一起， 并排放置在与水平面的倾斜角度呈 30°的斜垫块上， 然 后在热镶样机上进行镶样， 磨制和抛光后钢板整个断面的可视范围大约增大了 1倍， 各 镀层和钢基界面之间的 Fe-Al中间层过渡层均明显显示出来。
镀层 Fe-Al中间过渡层中各主要元素原子及质量百分比通过电子探针 （EPMA1600 型）波谱面扫描和点成分分析进行测定。 EPMA所用试样全部采用斜镶样的未浸蚀的金 相试样。 从 EPMA面扫描结果看， 所有实验例和比较例均具有如图 1所示的暗色黑带 —Fe-Al 中间过渡层， 两边分别为钢基和锌层。 对实验例和比较例各镀层剖面从钢基开 始到锌层表面按等距离进行波谱点成分分析，具体位置如图 1所示，其中 0为钢基位置， 1〜5为 Fe-Al中间层位置， 6〜12为锌层位置。
镀层典型的金相试样用 EPMA测量所得的 EPMA线扫描分析谱图显示： A1元素在 中间层中含量最高， Zn元素从钢基开始到镀层表面逐渐增加， Fe元素从钢基开始到镀 层表面逐渐减少。
图 2是实验例 1、 比较例 6和比较例 11的金相试样用扫描电镜（SEM)测量的断面 形貌。 由于采用斜镶样， 各锌层和钢基界面之间厚度几十至几百纳米的 Fe-Al中间过渡 层均明显显示出来， 呈细密晶粒形貌。 由于斜镶样， Fe-Al 中间层的宽度以及整个镀层 的宽度不做比较。 图中实验例 1具有细小均匀的纯锌枝晶断面形状； 比较例 6镀层中有 较多的裂纹， 说明它们之间形成了硬脆的组织， 在加工中锌层极易脱落； 比较例 11 中 间层和镀层之间已经形成裂纹， 镀层已经失去了黏附性。
金相试样经磨制和抛光， 用 2%硝酸酒精浸蚀液进行浸蚀后， 在高性能光学金相显 微镜 （OLYMPUS BX51型） 下进行金相摄影， 物镜放大倍数为 100x。 图 3为实验例和 比较例的金相照片。 图 3 (a)可看到镀层中有 Fe-Al中间过渡层， 较薄的 δ相， 少量分 散的 ξ相， 镀层大部分由纯锌层 η相组成。 经镀层的附着性能检测， 此实验例 （1 ) 镀 层具有良好的附着性。 若 Zn在 Fe-Al中间过渡层中的溶解度达到过饱和并生成了富锌 固溶体时，这时中间层中的 A1绝对含量虽然没有减少，但是 A1的百分含量却显著下降， 同时因为锌的过饱和而破坏了 Fe-Al中间过渡层的均质性， 由此便使中间层丧失了粘附 作用和阻止扩散作用， 并且形成较厚的 Fe-Zn合金层， δ相和 ξ相增多， 使锌层的附着 力同时变坏。 如图 3 (b) 示出的比较例 （6) 的金相照片， 虽然也形成了 Fe-Al中间过 渡层， 但 A1的百分含量却下降， 使 Fe-Zn合金层增多， 形成了较厚的 δ相和 ξ相， 纯 锌层 η相较薄， 镀层的附着性相对于实验例 1明显变坏。
图 4为实验例 1和比较例 6、 11镀层 Fe-Al中间过渡层 A1和 Zn元素原子百分比变 化示意图。 图 5为实验例 1和比较例 6和 11镀层 Fe-Al中间过渡层中 2〜4位置处 Al、 Zn元素平均原子百分比。 表 2列出了实施例和比较例各镀层 Fe-Al中间过渡层中 A1和 Zn的原子浓度及 Al/Zn比值。 从以上结果可见， 实验例 Fe-Al中间过渡层中 A1元素原 子百分含量均大于比较例， Zn元素原子百分含量与比较例相差不大， 但实验例 Al/Zn 比值均大于 0.9， 而比较例 Al/Zn比值在 0.358〜0.553之间。
镀层组织中各相元素质量百分比通过 EPMA波谱点成分分析进行测定。根据镀层各 相 Fe、 Zn元素的质量百分比， 以及对照镀层组织的金相照片， 可以判断镀层中存在的 δ、 ζ禾 Ρ η相。 图 6示出了实验例 1 (图 6a)、 和比较例 6 (图 6b) 和比较例 11 (图 6c) 镀层中钢基开始到锌层表面各位置处的 Fe、 Zn和 A1元素的质量百分比变化及镀层中的 金相组织。表 2根据锌层 7〜12六个位置处测量的相组织类别列出了实验例和比较例各 镀层的相组织。 可见， 实验例镀层中 δ相和 ξ相均较少， 纯锌层 η相较多； 而比较例镀 层中均具有较厚的 δ相和 ξ相， 纯锌层 η相较薄。
对于附着性良好的热镀锌钢板， 钢基与镀层之间要形成含有较高 A1含量的 Fe-Al 中间过渡层， 而且， 只有锌在 Fe-Al中间过渡层中不饱和溶解和形成贫锌固溶体时， 此 层才能起到粘附作用和阻止 Fe-Zn扩散的作用， 并形成薄的 Fe-Zn合金层， δ相和 ξ相 减少， 此时， 镀层附着性较好。
表 2 热镀锌钢板性能
Figure imgf000013_0001
(2) 镀层晶粒取向
镀层表面未作任何处理， 在 X射线衍射仪（XRD)上分别进行镀层小角衍射 （掠射 角 5°) ， 测定镀层的衍射峰强度。 实验例 1及比较例 6和 1 1镀层表面在 5°掠射角时的 典型衍射图谱见图 7。表 2列出了各试样 Zn(002)峰的衍射强度。可见， 钢板入镀浴温度 提高到 475〜485 °C后，实验例试样 1〜5镀层晶粒呈现出 Zn(002)方向的择优取向， Zn(002) 峰的衍射强度显著增强， 均大于 34000cts。 而钢板入镀浴温度 465 °C的比较例 6〜15 中， Zn(002)峰的衍射强度在 14000〜17000cts之间。
( 3 ) 镀层抗脱落性能
通过" U"形弯曲试验来检验镀层的抗脱落性能。 弯曲试验按照国标 GB/T 232- 1999 (金属材料 弯曲试验方法）进行， 试样制备参考 GB/T 2975— 1998 (钢及钢产品力学性 能试验取样位置及试样制备）。 图 8示出了弯曲试样的最终形状。 试样用线切割机加工， 试验前用乙醇擦拭试样表面，然后在所有试样弯曲部位内外表面粘贴相同大小的透明胶 带， 试样连同胶带在弯曲试验机上进行弯曲加工， 通过胶带收集弯曲部位剥落的锌粉， 对各镀层的锌粉脱落量用 ICP法进行测量。图 9示出了实验例和比较例试样锌粉脱落量 的均值及方差， 实验例的锌粉脱落量均明显小于比较例。 表 3根据下述标准对实施例和 比较例各试样的镀层抗脱落性能进行评价： ©特别良好 （锌粉脱落量： ≤0.0100mg); o 良好（锌粉脱落量： 在 0.0100〜0.0300mg之间）； 八稍微不良（锌粉脱落量： 在 0.0300〜 0.0360mg之间）； X不良 （锌粉脱落量： ≥0.0440mg)。
(4) 镀层抗划性能
镀层抗划性能试验在美国 CETR UMT-2型多功能摩擦磨损试验机上完成，抗划性能 试验应用划痕试验装置部分， 划痕试验的压头为铲形金刚石， 头部曲率半径为 800μιη。 划痕试验采用线性增加的加载方式， 选用加载载荷从 0.5Ν 增加至 2Ν。 试验后应用 Ambios XP2型轮廓仪测量各镀层试验后的划痕轮廓形貌。 图 10示出了实验例 1与比较 例 6和 11中镀层划痕中间位置处典型的轮廓测量结果。 可见， 实验例 1中的镀层划痕 深度均明显小于比较例 6和 11。表 3根据下述标准对实验例和比较例各试样的镀层抗划 性能进行评价： o良好 （划痕深度 7.00μιη); 稍微不良 （划痕深度在 7.00〜8.00μιη 之间）； X不良 （划痕深度 8.00μιη)。
(4) 镀层耐磨性能
镀层耐磨性能试验在美国 CETR UMT-2 型多功能摩擦磨损试验机往复滑动摩擦试 验平台上完成。 上试样（对磨试样）为直径 10mm的不锈钢圆球， 下试样为热镀锌钢板。 往复滑动摩擦磨损试验参数为： 法向载荷 =2 ^^， 往复位移幅值 D=2 mm， 相对运动速 度 =2 mm/s， 运行时间 t=1000 s， 循环次数 N=500。 试验后应用 Ambios XP2型轮廓仪测 量各镀层试验后的磨痕轮廓形貌。 图 11示出了实验例 1 (图 l la)、 比较例 6 (图 l ib) 和比较例 11 (图 l ie) 往复滑动磨损试验后在 SEM下观察到的磨痕全貌。 可见实验例 1 (图 11a) 的磨损程度最轻； 比较例 6 (图 l ib ) 的磨痕宽度增大； 比较例 11 (图 11c) 的磨痕宽度最大， 损伤最严重。 表 3列出了实施例和比较例各试样 100次摩擦循环后的 平均摩擦系数， 并根据下述标准对磨痕轮廓进行评价： o良好（磨痕深度 8.00μιη); Δ 稍微不良 （磨痕深度在 8.00〜10.00μιη之间）； x不良 （磨痕深度 10.00μιη)。
( 5 ) 镀层附着性能综合评价
表 3 根据下述标准对实施例和比较例各试样的镀层附着性能进行综合评价： ο良好 (良好 ο计数在 2个以上， 稍微不良 Δ最多只有 1个）； Δ稍微不良（良好 ο计数有 1个， 稍微不良 Δ计数有 2个）； X不良 （不良 X计数在 2个以上或稍微不良 Δ计数有 2个， 不 良 X计数有 1个）。 表 3 热镀锌钢板性能评价
Figure imgf000015_0001
由表 3 的评价结果可知， 本发明将热镀锌工艺过程中钢板的入锌锅温度提高到 475〜485 °C， 其他工艺不变的条件下得到的热镀锌钢板（实验例 1〜5 )与以往钢板（比 较例 6〜15 ) 相比， 镀层 Fe-Al中间过渡层中的 Al/Zn比值均大于 0.9， 镀层中 δ相和 ξ 相均减少， 纯锌层 η相增多； 而且实验例 （试样 1〜5 ) 镀层晶粒呈现出 Ζη(002)方向的 择优取向， Ζη(002)峰的衍射强度显著增强， 均大于 34000cts。 镀层的抗脱落性能、 抗划 性能和耐磨性能显著提高， 镀层与基材的附着性能明显改善。
上述实验例和比较例中， 通过测量 Fe-Al中间过渡层中 A1和 Zn的原子浓度比值， 以及镀层中存在的各个相组织，镀层的晶粒择优取向，并且对照各镀层的附着性能评价， 可以判断： 当 Al/Zn比值大于 0.9， 并且镀层中主要为 η相， 镀层的 Ζη(002)峰的衍射强 度大于 34000cts时， 镀层的附着性较好。
实施例 2热镀锌钢板实验例 16〜20和比较例 21〜25的制备和性能测定
DX1冷轧钢板厚度为 0.8mm， 成分为 C 0.03〜0.07 %， Mn 0.01〜0.03 %， Si 0.19〜 0.30 % , P 0.006〜0.019%， S 0.009—0.020 % , A1 0.02—0.07 % , 其余为 Fe及不可避免杂 质， DX1冷轧钢板经酸洗、 退火后， 在表 4列出的热镀锌工艺条件下进行热镀锌操作， 其中锌锅中镀浴初始温度为 450°C， 镀浴中 Fe含量 <0.03 %， 机组速度： 100m/min， 冷却 段高跨温度： 240°C， 冷却速率为 0 %。 将入镀浴时钢板温度调整为 475 °C， 镀浴中的 A1 含量调整为 0.18 % <A1 0.21 %进行热镀锌操作得到 16〜20号实验例，将入镀浴时钢板 温度调整为 460°C，镀浴中的 A1含量调整为 0.16〜0.17%进行热镀锌操作得到 21〜25比 较例。 对锌层重量控制到 180〜195g/m2左右， 锌层表面经过 Si02钝化处理。
表 4热镀锌工艺条件
Figure imgf000016_0001
热镀锌钢板实验例 16〜20和比较例 21〜25的性能测定
以下测定方法与评价标准均与实施例 1相同。
( 1 ) 镀层 Fe-Al中间过渡层及组织结构
实验例 16〜20的镀层剖面电子探针 （EPMA1600型） 波谱面扫描分析谱图结果与 实验例 1相同（参见图 1 )。图 12示出了典型的实验例 16〜20和比较例 21〜25镀层 Fe-Al 中间过渡层中 A1和 Zn元素原子百分比变化。图 13示出了实验例 16〜20和比较例 21〜 25镀层 Fe-Al中间过渡层中 2〜4位置处 A1和 Zn元素平均原子百分比。 表 5列出了实 验例 16〜20和比较例 21〜25各镀层 Fe-Al中间过渡层中 A1和 Zn的原子浓度及 Al/Zn 比值。 从以上结果可见， 实验例 16〜20镀层 Fe-Al中间过渡层中 A1元素原子百分含量 显著大于比较例 21〜25， Zn元素原子百分含量与比较例各试样相比有所增加， 但实验 例 16〜20 Fe-Al中间过渡层 Al/Zn比值在 0.963〜1.134之间，而比较例 21〜25 Al/Zn比 值在 0.421〜0.499之间， 实验例 16〜20 Al/Zn比值显著大于比较例 21〜25， 而且大于 上述实验例 1〜5 Fe-Al中间过渡层 Al/Zn比值。
图 14示出了实验例 16〜20和比较例 21镀层中 Fe、 Zn和 A1元素的质量百分比变 化及镀层中的金相组织。 表 5列出了实验例 16〜20和比较例 21〜25各镀层的相组织。 可见， 实验例 16〜20镀层中 δ相和 ξ相均较少， 纯锌层 η相较多； 而比较例镀层中均 具有较厚的 δ相和 ξ相， 纯锌层 η相较薄。
表 5热镀锌钢板性能
Figure imgf000017_0001
(2) 镀层晶粒取向
实验例 16及比较例 21镀层表面在 5°掠射角时的典型衍射图谱见图 15。 表 5列出 了各试样 Zn(002)峰的衍射强度。可见， 热镀锌工艺镀浴中的 A1含量控制在 0.18%<A1 0.21%后， 实验例 16〜20镀层晶粒同样呈现出 Zn(002)方向的择优取向， Zn(002)峰的 衍射强度显著增强， 均大于 24000cts。 而镀浴中的 A1含量控制在 0.16〜0.17%的比较例 21〜25中， Zn(002)峰的衍射强度在 15000cts以下。
(3) 镀层抗脱落性能
图 16示出了实验例 16〜20和比较例 21〜25锌粉脱落量的均值及方差。 可见， 镀 浴中的 A1含量在 0.18%<A1 0.21%时， 实验例 16〜20的锌粉脱落量均明显小于比较 例 21〜25， 而且明显小于上述实验例 1〜6。 说明在提高带钢入镀浴温度的同时增加镀 浴中 A1含量更有利于提高镀层的抗脱落性能。
(4) 镀层抗划性能
图 17示出了实验例 16与比较例 21镀层划痕中间位置处轮廓测量结果。可见，镀浴 中的 A1含量为 0.18%<A1 0.21%时， 实验例 16的镀层划痕深度明显小于比较例 21。 (5) 镀层耐磨性能
表 6列出了实验例 16〜20和比较例 21〜25 各试样 100次摩擦循环后的平均摩擦系 数。 (6) 镀层附着性能综合评价
表 6 热镀锌钢板性能评价
Figure imgf000018_0001
由表 6的评价结果可知， 本发明热镀锌工艺过程中带钢入镀浴温度提高到 475°C， 并且镀浴中的 A1含量控制为 0.18%<A1 0.21%，其他工艺不变的条件下得到的热镀锌 钢板 （实验例 16〜20) 与以往钢板 （比较例 21〜25) 相比， 镀层 Fe-Al中间过渡层中 的 Al/Zn比值在 0.963〜1.134之间， 并且高于实验例 1〜6。镀层中 δ相和 ξ相均明显减 少， 纯锌层 η相增多， 并形成取向优化的 Ζη(002)晶粒， 镀层的抗脱落性能、 抗划性能 和耐磨性能显著提高， 镀层与基材的附着性能明显改善。
实施例 3热镀锌钢板实验例 21〜30和比较例 26〜35的制备
将厚度为 0.8mm， 成分为 C: 0.03—0.07%, Mn: 0.01—0.03%, Si: 0.19〜0.30%，
P: 0.006〜0.019%， S: 0.009—0.020%, A1: 0.02—0.07%, 其余为 Fe及杂质的 DX51D 冷轧钢板经酸洗、 退火后， 在表 7所列出的热镀锌工艺条件下进行热镀锌操作， 其中锌 锅中镀浴温度为 450°C， 镀浴中 Fe含量 <0.03%， A1含量： 0.16〜0.18%， 入镀浴时钢板 温度： 460 °C,机组速度： 110〜120m/min。钢板出锌锅后采用风冷对钢板进行强制冷却， 冷却速率为 70〜90%，得到 21〜30号实验例，冷却速率调整为 30〜50%时得到 26〜30 号比较例， 冷却速率调整为 0% (空气自然冷却）时得到 31〜35号比较例。对锌层重量 控制到 180g/m2左右， 锌层表面经过 Si02钝化处理。 通过以下方法对镀层的晶粒取向以 及镀层抗脱落性能、 抗划性、 耐磨性等镀层附着性能进行评价。
表 7热镀锌工艺条件
试验 厚度 热镀锌工艺条件
锌层重量 g
样品 mm 机组速度 入镀浴钢板 镀浴铝 快速冷却速率 m/min 温度 V 3里 /o
实验例 21 0.80 186 110 460 0.170 90% 实验例 22 0.80 186 110 460 0.171 90% 实验例 23 0.80 186 110 460 0.170 90% 实验例 24 0.80 186 120 460 0.172 80% 实验例 25 0.80 186 120 460 0.171 90% 实验例 26 0.80 184 110 460 0.170 70% 实验例 27 0.80 184 110 460 0.171 70% 实验例 28 0.80 184 110 460 0.170 80% 实验例 29 0.80 184 120 460 0.172 70% 实验例 30 0.80 184 120 460 0.170 70% 比较例 26 0.80 183 110 460 0.170 40% 比较例 27 0.80 183 110 460 0.171 40% 比较例 28 0.80 183 110 460 0.170 30% 比较例 29 0.80 184 120 460 0.170 40% 比较例 30 0.80 184 120 460 0.171 30% 比较例 31 0.80 183 110 460 0.170 0% 比较例 32 0.80 183 110 460 0.171 0% 比较例 33 0.80 183 110 460 0.170 0% 比较例 34 0.80 183 120 460 0.171 0% 比较例 35 0.80 183 120 460 0.170 0% 热镀锌钢板实验例 21〜30和比较例 26〜35的性能测定
以下测定方法与评价标准均与实施例 1相同。
( 1 ) 镀层晶粒取向
实验例 21和 26及比较例 26和 30镀层表面在 5°掠射角时的典型衍射图谱见图 18。 可见实验例 21和 26镀层中 Zn的最强衍射峰 Zn(002)强度远高出比较例 26和 30， Zn 的百强峰由 Zn ( 101 ) 转移至 Zn ( 002)。 表 8列出了各试样 Zn(002)峰的衍射强度， 可 见， 与冷却速率分别为 30〜50 %和 0 %的比较例相比， 实验例冷却速率提高到 70〜90 %以后， Zn(002)峰的衍射强度增强， 均大于 27000cts， 镀层晶粒呈现出 Zn(002)方向的 择优取向。
( 3 ) 镀层抗脱落性能
图 19 示出了实验例和比较例试样锌粉脱落量的均值及方差。 实验例的锌粉脱落量 均明显小于比较例。
( 3 ) 镀层抗划性能
图 20示出了实验例 21和 26及比较例 26和 30中镀层划痕中间位置处典型的轮廓测 量结果。 可见， 实验例中的镀层划痕深度均明显小于比较例。
(4) 镀层耐磨性能
表 8列出了实验例和比较例各试样 100次摩擦循环后的平均摩擦系数。
(5) 镀层附着性能综合评价
表 8 热镀锌钢板性能
Figure imgf000020_0001
由表 8的评价结果可知，本发明将热镀锌工艺过程中钢板的冷却速率提高到 70〜90 %, 其他工艺不变的条件下得到的热镀锌钢板 （实验例） 与以往钢板 （比较例） 相比， 镀层晶粒呈现出 Zn(002)方向的择优取向， 镀层的抗脱落性能、 抗划性能和耐磨性能显 著提高， 镀层与基材的附着性能明显改善。
实施例 4热镀锌钢板实验例 31〜35和比较例 36〜40的制备
DX1冷轧钢板厚度为 0.8mm， 成分为 C 0.03〜0.07%， Mn 0.01〜0.03 %， Si 0.19〜 0.30%, P0.006〜0.019%， S 0.009—0.020%, A10.02—0.07% , 其余为 Fe及不可避免杂 质， DX1冷轧钢板经酸洗、 退火后， 在表 9列出的热镀锌工艺条件下进行热镀锌操作， 其中锌锅中镀浴初始温度为 450°C， 镀浴中 Fe含量 <0.03 %， 入镀浴时钢板温度： 460°C， 机组速度： 100m/min， 冷却段高跨温度： 240°C， 冷却速率为 0%， 将镀浴中的 A1含量 调整为 0.21〜0.25 %进行热镀锌操作得到 31〜35 号实验例， 将镀浴中的 A1含量调整为 0.16〜0.18 %进行热镀锌操作得到 36〜40比较例。对锌层重量控制到 180〜195g/m2左右， 锌层表面经过 Si02钝化处理。
表 9热镀锌工艺条件
Figure imgf000021_0001
热镀锌钢板实验例 31〜35和比较例 36〜40的性能测定
以下测定方法与评价标准均与实施例 1相同。
( 1 ) 镀层 Fe-Al中间过渡层及组织结构
实验例 31 典型的镀层剖面电子探针 （EPMA1600型） 波谱面扫描分析谱图结果与 实验例 1相同（参见图 1 )。图 21示出了典型的实验例试样 31和比较例试样 36镀层 Fe-Al 中间过渡层中 A1和 Zn元素原子百分比变化。图 22示出了实验例试样 31〜35和比较例 试样 36〜40镀层 Fe-Al中间过渡层中 2〜4位置处 A1和 Zn元素平均原子百分比。表 10 列出了实验例和比较例各镀层 Fe-Al中间过渡层中 A1和 Zn的原子浓度及 Al/Zn比值。 从以上结果可见， 实验例 Fe-Al中间过渡层中 A1元素原子百分含量显著大于比较例， Zn元素原子百分含量与比较例相比有所增加，但实验例 Al/Zn比值在 0.940〜1.125之间， 而比较例 Al/Zn比值在 0.421〜0.499之间， 实验例 Al/Zn比值显著大于比较例。
图 23示出了实验例 31和比较例 36镀层中 Fe、 Zn和 A1元素的质量百分比变化及 镀层中的金相组织。 表 10列出了实验例和比较例各镀层的相组织。 可见， 实验例镀层 中 δ相和 ξ相均较少， 纯锌层 η相较多； 而比较例镀层中均具有较厚的 δ相和 ξ相， 纯 锌层 η相较薄。
表 10热镀锌钢板性能
Figure imgf000022_0001
(2) 镀层晶粒取向
实验例 31及比较例 36镀层表面在 5°掠射角时的典型衍射图谱见图 24。 表 10列出 了各试样 Zn(002)峰的衍射强度。可见，热镀锌工艺镀浴中的 A1含量控制在 0.21〜0.25% 后， 实验例试样 31〜35镀层晶粒呈现出 Zn(002)方向的择优取向， Zn(002)峰的衍射强 度显著增强，均大于 24000cts。而镀浴中的 A1含量控制在 0.16〜0.18%的比较例 36〜40 中， Zn(002;>峰的衍射强度在 15000cts以下。
( 3 ) 镀层抗脱落性能
图 25示出了实验例 31〜35和比较例 36〜40锌粉脱落量的均值及方差。 可见， 镀 浴中的 A1含量在 0.21〜0.25%之间时， 实验例 31〜35的锌粉脱落量均明显小于比较例 36〜40。
(4) 镀层抗划性能
图 26示出了实验例 31与比较例 36镀层划痕中间位置处轮廓测量结果。可见，镀浴 中的 A1含量在 0.21〜0.25%之间时， 实验例中的镀层划痕深度明显小于比较例。
( 5 ) 镀层耐磨性能
表 11列出了实施例和比较例各试样 100次摩擦循环后的平均摩擦系数。
( 6) 镀层附着性能综合评价 表 11 热镀锌钢板性能评价
Figure imgf000023_0001
由表 11 的评价结果可知， 本发明热镀锌工艺过程中使镀浴中的 A1 含量控制在 0.21〜0.25%之间， 其他工艺不变的条件下得到的热镀锌钢板（实验例）与以往钢板（比 较例） 相比， 镀层 Fe-Al中间过渡层中的 Al/Zn比值在 0.940〜1.125之间， 镀层中 δ相 和 ξ相均减少， 纯锌层 η相增多， 并形成取向优化的 Ζη(002)晶粒， 镀层的抗脱落性能、 抗划性能和耐磨性能显著提高， 镀层与基材的附着性能明显改善。
实施例 5热镀锌钢板实验例 36〜42和比较例 41〜47的制备
将厚度为 0.8mm， 成分为 C: 0.03—0.07 % , Mn: 0.01—0.03 % , Si: 0.19〜0.30 %， P: 0.006〜0.019%， S: 0.009—0.020 % , A1: 0.02—0.07 % , 其余为 Fe及杂质的 DX1冷 轧钢板经酸洗、 退火后， 在表 12所列出的热镀锌工艺条件下进行热镀锌操作， 其中锌 锅中镀浴温度为 450°C， 镀浴中 Fe含量 <0.03 %， A1含量： 0.16〜0.18 %， 入镀浴时钢板 温度： 460 °C ,机组速度： 100m/min，冷却速率为 0 %，将冷却段的高跨温度调整为 210〜 220 °C , 得到 36〜42号实验例； 冷却段高跨温度调整为 240〜260°C得到 41〜47号比较 例。 锌层重量控制到 180〜195g/m2， 锌层表面经过 Si02钝化处理。
表 12 热镀锌工艺条件
Figure imgf000023_0002
实验例 38 0.80 182 100 460 0.170 210 实验例 39 0.80 182 100 460 0.171 220 实验例 40 0.80 182 100 460 0.170 220 实验例 41 0.80 182 100 460 0.171 210 实验例 42 0.80 182 100 460 0.170 210 比较例 41 0.80 182 100 460 0.170 260 比较例 42 0.80 182 100 460 0.171 250 比较例 43 0.80 182 100 460 0.170 250 比较例 44 0.80 182 100 460 0.171 260 比较例 45 0.80 182 100 460 0.172 260 比较例 46 0.80 182 100 460 0.170 250 比较例 47 0.80 182 100 460 0.171 260 热镀锌钢板实验例 36〜42和比较例 41〜47的性能测定
( 1 ) 镀层 Fe-Al中间过渡层及组织结构
实验例 36典型的镀层剖面电子探针 （EPMA1600型） 波谱面扫描分析谱图结果与 实验例 1相同 （参见图 1 )。 图 27显示典型的实验例 36和比较例 41镀层 Fe-Al中间过 渡层中 A1和 Zn元素原子百分比变化。 图 28显示实验例 36〜42和比较例 41〜47镀层 Fe-Al中间过渡层中 2〜4位置处 A1和 Zn元素平均原子百分比。 表 13列出了实验例和 比较例各镀层 Fe-Al中间过渡层中 A1和 Zn的原子浓度及 Al/Zn比值。从以上结果可见， 实验例 Fe-Al中间过渡层中 A1元素原子百分含量大于比较例， Zn元素原子百分含量小 于比较例，实验例 Al/Zn比值在 0.757〜0.884之间，而比较例 Al/Zn比值在 0.131〜0.535 之间， 实验例 Al/Zn比值显著大于比较例。
图 29显示实验例 36和比较例 41镀层中 Fe、 Zn和 A1元素的质量百分比变化及镀 层中的金相组织。表 13列出了实验例和比较例各镀层的相组织。可见， 实验例镀层中 δ 相和 ξ相均较少， 纯锌层 η相较多； 而比较例镀层中均具有较厚的 δ相和 ξ相， 纯锌层 η相较薄。
(2) 镀层抗脱落性能
图 30显示实验例 36〜42和比较例 41〜47锌粉脱落量的均值及方差。 可见， 实验 例 36〜42的锌粉脱落量均明显小于比较例 41〜47。
( 3 ) 镀层抗划性能 图 31显示实验例 36与比较例 41镀层划痕中间位置处轮廓测量结果。可见，冷却 段高跨温度调整为 210 220°C时， 实验例中的镀层划痕深度明显小于比较例。
(4) 镀层耐磨性能
表 13列出了实验例和比较例各试样 100次摩擦循环后的平均摩擦系数。
( 5 ) 镀层附着性能综合评价
表 13热镀锌钢板性能
Figure imgf000025_0001
由表 13 的评价结果可知， 本发明在热镀锌工艺过程中将冷却段高跨温度调整为 210 220°C， 其他工艺不变的条件下得到的热镀锌钢板（实验例）与以往钢板（比较例） 相比， 镀层 Fe-Al中间过渡层中的 Al/Zn比值在 0.757 0.884之间， 镀层中 δ相和 ξ相 均减少， 纯锌层 η相增多， 镀层的抗脱落性能、 抗划性能和耐磨性能显著提高， 镀层与 基材的附着性能明显改善。

Claims

权利要求书
1、 热镀锌钢板， 钢板基材与锌镀层之间为 Fe-Al 中间过渡层， 其特征在于： 所述 Fe-Al中间过渡层中 A1和 Zn的原子浓度 Al/Zn比值为 0.9〜1.2。
2、 根据权利要求 1所述的热镀锌钢板， 其特征在于： 锌镀层晶粒取向 Zn (002) 峰强度 25000〜35000cts。
3、 热镀锌钢板的生产方法， 钢板经酸洗、 退火后进行热镀锌操作， 其特征在于： 热镀锌操作过程中， 入镀浴时钢板温度为 455〜485°C， 锌锅中镀浴温度为 450〜460°C， 镀浴中 Fe重量百分比含量<0.03 %， 镀浴中 A1重量百分比含量 0.16〜0.25 %， 冷却段的 高跨温度 210〜245°C， 钢板冷却速率为 0〜90 %。
4、 根据权利要求 3所述的热镀锌钢板的生产方法， 其特征在于： 热镀锌操作过程 中， 入镀浴时钢板温度为 455〜465°C， 锌锅中镀浴温度为 450〜460°C， 镀浴中 Fe的重 量百分比含量 <0.03 %， 镀浴中 A1 的重量百分比含量 0.16〜0.18 %， 机组速度 100〜 llOm/min, 冷却段的高跨温度 210〜220°C， 钢板冷却速率为 0%。
5、 根据权利要求 3所述的热镀锌钢板的生产方法， 其特征在于： 热镀锌操作过程 中， 入镀浴时钢板温度为 475〜485°C， 锌锅中镀浴温度为 450〜460°C， 镀浴中 Fe的重 量百分比含量 <0.03 %， 机组速度： 100〜110m/min， 钢板冷却速率为 0%， 冷却段高跨 温度： 235〜245°C， 镀浴中 A1的重量百分比含量为 0.16% A1 0.18 %。
6、 根据权利要求 3所述的热镀锌钢板的生产方法， 其特征在于： 热镀锌操作过程 中， 入镀浴时钢板温度为 475〜485°C， 锌锅中镀浴温度为 450〜460°C， 镀浴中 Fe的重 量百分比含量 <0.03 %， 镀浴中 A1的重量百分比含量为 0.18 % <A1 0.21 %， 机组速度： 100〜110m/min， 钢板冷却速率为 0%， 冷却段高跨温度： 235〜245°C。
7、 根据权利要求 3所述的热镀锌钢板的生产方法， 其特征在于： 热镀锌操作过程 中， 入镀浴时钢板温度为 455〜465°C， 锌锅中镀浴温度为 450〜460°C， 镀浴中 Fe的重 量百分比含量 <0.03 %， 镀浴中 A1 的重量百分比含量 0.16〜0.18 %， 机组速度 110〜 120m/min, 钢板出锌锅后用风冷进行强制冷却， 冷却速率 70〜90%。
8、 根据权利要求 3所述的热镀锌钢板的生产方法， 其特征在于： 热镀锌操作过程 中， 入镀浴时钢板温度为 455〜465°C， 锌锅中镀浴温度为 450〜460°C， 镀浴中 A1的重 量百分比含量： 0.21〜0.25 %， 镀浴中 Fe的重量百分比含量 <0.03 %， 机组速度： 100〜 llOm/min, 钢板冷却速率为 0%， 冷却段高跨温度： 235〜245°C。
9、 根据权利要求 3〜8任一项所述的热镀锌钢板的生产方法， 其特征在于： 所述待 镀锌的钢板成分以重量百分比计， 含有 C: 0.03〜0.07%， Mn: 0.01—0.03%, Si: 0.19— 0.30%, P: 0.006〜0.019%， S: 0.009—0.020%, Ah 0.02—0.07%, 其余为 Fe。
10、 根据权利要求 3〜8任一项所述的热镀锌钢板的生产方法， 其特征在于： 所述 待镀锌的钢板的厚度为 0.8mm。
11、 根据权利要求 3〜8任一项所述的热镀锌钢板的生产方法， 其特征在于： 待镀 锌的钢板镀锌后锌层重量为 180〜195g/m2， 锌层表面经过 Si02钝化处理。
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