WO2023138372A1 - 一种带钢及其制造方法 - Google Patents

一种带钢及其制造方法 Download PDF

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Publication number
WO2023138372A1
WO2023138372A1 PCT/CN2023/070391 CN2023070391W WO2023138372A1 WO 2023138372 A1 WO2023138372 A1 WO 2023138372A1 CN 2023070391 W CN2023070391 W CN 2023070391W WO 2023138372 A1 WO2023138372 A1 WO 2023138372A1
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Prior art keywords
steel
phosphating
stearate
spraying
strip steel
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PCT/CN2023/070391
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English (en)
French (fr)
Chinese (zh)
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赵艳亮
魏星
戴毅刚
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Priority to US18/727,593 priority Critical patent/US20250389003A1/en
Priority to JP2024541064A priority patent/JP7838094B2/ja
Priority to EP23742688.7A priority patent/EP4446451A4/en
Priority to KR1020247024933A priority patent/KR20240128952A/ko
Publication of WO2023138372A1 publication Critical patent/WO2023138372A1/zh
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/76—Applying the liquid by spraying
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working

Definitions

  • the invention relates to the field of metal material processing, in particular to an oil-free strip steel with excellent processability and anti-corrosion performance and a manufacturing method thereof.
  • the main process types include: (1) forming a micron-scale or submicron organic coating on the surface of the steel plate by means of roller coating + baking curing in the continuous manufacturing process, such as described in Chinese patents CN104451638, CN103289569, and CN105463436; mentioned.
  • Chinese patent CN103289569 discloses "a self-lubricating passivation solution and a hot-dip galvanized self-lubricating steel plate coated with it", mainly through the addition of nano- MoS2 and modified nano-polytetrafluoroethylene particles in the treatment agent to play the role of solid lubrication of the coating.
  • a lubricating coating with an adhesion amount of 800 to 1200mg/ m2 is formed on the surface of the steel plate by rolling coating + baking curing.
  • the product of this invention is mainly suitable for the stamping needs of home appliances and micro-motor shell materials, but it cannot meet the large deformation stamping of high-precision components in the automotive and mechanical fields, and is not suitable for surface treatment of ordinary cold-rolled sheets.
  • Chinese patent CN111349867 discloses "a coating-friendly pre-phosphating electro-galvanized automobile outer panel and its preparation method".
  • a kind of Nb-containing ultra-low carbon steel plate is designed.
  • a pre-phosphating layer of 1.0 to 2.0 g/ m2 is formed by double-sided spraying at a phosphating temperature of 50 to 60 ° C.
  • a product that meets the stamping lubrication and corrosion resistance requirements of automobile body materials is formed. It can be well applied in the body production line, but it cannot meet the large deformation stamping requirements of high-precision components in the automotive and mechanical fields, and cannot realize the manufacturing requirements of double-sided differential lubrication functions.
  • Chinese patent CN105018920A discloses "a phosphorus saponification production process", which relates to a drum-type continuous phosphating/saponification process for processing small parts, mainly including: cylinder entry ⁇ degreasing ⁇ primary cleaning ⁇ phosphating ⁇ secondary cleaning ⁇ surface adjustment ⁇ saponification ⁇ cylinder discharge, 8 technological processes, wherein the phosphating temperature is 60 to 85 ° C, the immersion time is 3 to 10 minutes, the saponification temperature is 55 to 80 ° C, and the immersion time is 0.5 to 5 minutes. This process mainly realizes the surface lubrication function of finished parts through high-temperature phosphating + saponification treatment, but it is not suitable for continuous manufacturing of strip steel.
  • Chinese patent CN105296997A discloses "a phosphating-saponification treatment process for 27SiMn steel", which provides a surface lubrication treatment method suitable for high-precision cold-drawn steel pipes, including: pickling 27SiMn steel parts ⁇ high-temperature phosphating (70 ° C) ⁇ saponification treatment. Likewise, the application adopts double-sided non-differentiation treatment, and is not suitable for continuous manufacturing of strip steel.
  • the object of the present invention is to provide an oil-free steel strip with excellent processability and anti-corrosion performance and a manufacturing method thereof.
  • the two surfaces of the steel strip in the thickness direction have differentiated functions: the surface roughness R a of the upper surface (that is, the surface with the phosphating layer and the stearate lubricating layer) is 0.6 to 1.8 ⁇ m and the R z is 6 to 16 ⁇ m, which has good surface lubrication performance during the extension process; the surface roughness of the lower surface (that is, the surface with only the stearate lubricating layer) is R a ⁇ 0.3 ⁇ m and R z ⁇ 2 ⁇ m, which has good lubricity and high surface cleanliness.
  • the steel strip provided by the present invention can meet the requirements of the continuous and efficient stamping process in the processing of high-precision, large-deformation shell parts, eliminating the need for conventional steel plates in the stamping process of high-precision, large-deformation shell parts, coating, oiling, and cleaning after forming.
  • the invention provides a kind of strip steel, described strip steel comprises substrate and the phosphating layer and the stearate lubricating layer that are arranged on the substrate; On the thickness direction of described substrate, on the upper surface of described substrate, be provided with phosphating layer and stearate lubricating layer successively from inside to outside, the lower surface of described substrate is provided with stearate lubricating layer; a ⁇ 0.3 ⁇ m and R z ⁇ 2 ⁇ m .
  • the substrate includes, in addition to Fe and unavoidable impurities, the following chemical elements in wt %: C: 0.1-0.7%, 0.2% ⁇ Si ⁇ 2%, 0.2% ⁇ Mn ⁇ 2%, Cr: 0.2-1.4%, 0.01% ⁇ Al ⁇ 0.06%, Mo: 0.05-0.2%; among unavoidable impurities, P ⁇ 0.04%, S ⁇ 0.05%.
  • upper surface and “lower surface” are used in this application to distinguish the two surfaces (or both sides) of the substrate or steel strip in the thickness direction.
  • the surface or side with phosphating layer and stearate lubricating layer is referred to as “upper surface” or “upper side”
  • only the surface or side with stearate lubricating layer is called “lower surface” or “lower side”.
  • inside to outside refers to the direction from the side close to the substrate to the side away from the substrate.
  • inside-out refers to a direction from bottom to top.
  • the substrate contains the following chemical elements in wt %: C: 0.1-0.7%, 0.2% ⁇ Si ⁇ 2%, 0.2% ⁇ Mn ⁇ 2%, Cr: 0.2-1.4%, 0.01% ⁇ Al ⁇ 0.06%, Mo: 0.05-0.2%, the balance is Fe and inevitable impurities; among the inevitable impurities, P ⁇ 0.04%, S ⁇ 0.05%.
  • the content of element C is controlled in the range of 0.1% to 0.7%.
  • element Si can effectively improve the formability of materials under high-strength conditions. However, if the Si content is too high (>2%), it will be selectively oxidized and precipitated during the heat treatment process, and the precipitates will be enriched on the surface, affecting the subsequent phosphating and passivation film-forming reaction performance. Therefore, the content of the element Si is controlled to be in the range of 0.2% to 2%.
  • the element Mn can play a role in ensuring the strength and hardness of the material. However, if the Mn content is too high (>2%), it will also be selectively oxidized and precipitated during the heat treatment process, and the precipitates will be enriched on the surface, affecting the subsequent phosphating and passivation film-forming reaction performance. Therefore, the content of the element Mn is controlled to be in the range of 0.2% to 2%.
  • Unavoidable impurities include elements P and S. If the content of P and S is too high, it will affect the toughness of the material and cannot meet the requirements of large deformation forming performance. Therefore, the contents of impurity elements P and S are controlled to be no more than 0.04% and no more than 0.05%, respectively.
  • the substrate has a thickness of 1.0 to 6.0 mm.
  • the "thickness of the substrate” does not include the thickness of one phosphating layer and two stearate lubricating layers on the upper and lower surfaces of the substrate. If the thickness of the substrate is less than 1 mm, the shell wall of the component is likely to be too thin to meet the load-bearing performance requirements after large deformation and deep drawing. If the thickness of the substrate is greater than 6 mm, the cold-rolled product manufacturing line cannot realize effective manufacturing.
  • the steel strip of the present invention is suitable for processing high-precision, large-deformation shell parts.
  • the grain size (ie, the maximum length of the grain) in the phosphating layer is 8 to 20 ⁇ m.
  • the crystal grains are elongated, and the grain size thereof is measured according to the standard GB/T 38933-2020.
  • the phosphating layer ie, phosphating film
  • the phosphating layer has a weight of 1 to 3 g/m 2 , which is measured according to the standard GB/T 38933-2020.
  • the phosphating layer of the present invention is a non-dense phosphating film with coarse crystals, which can effectively reduce the amount of wear debris in the stamping process, thereby improving the life of the mold.
  • the upper surface of the steel strip in the present invention includes a phosphating layer and a stearate lubricating layer sequentially from inside to outside, that is, the upper surface adopts a structural design of a phosphating layer+stearate coating.
  • Both the phosphating film and the stearate saponification film have a lubricating function, and the combination of the two can effectively improve the lubrication stability during the tensile deformation process.
  • the surface roughness Ra is 0.6 to 1.8 ⁇ m and R z is 6 to 16 ⁇ m, which can ensure that the surface of the strip has good surface lubrication performance during the elongation process.
  • the lower surface of the steel strip in the present invention is a stearate lubricating layer.
  • Stearate is a material processing lubricant with both internal and external lubrication functions. It has good thermal stability and excellent mold release performance during continuous rapid stamping (avoids adhesion and accumulation on the surface of the mold), avoids the influence of abnormal grinding particles on the inner surface of the formed part, and achieves lubricity and high surface cleanliness on the surface.
  • the upper and lower surfaces of the steel strip in the present invention have a structural design with differentiated functions, which can provide personalized functional requirements in the high-efficiency and high-precision forming and stamping process.
  • the strip steel surface of the present invention that contacts the die during the forming process is a phosphating layer and a stearate lubricating layer.
  • the surface has good surface lubrication performance during the extension process, and the surface roughness Ra : 0.6 to 1.8 ⁇ m, R z : 6 to 16 ⁇ m.
  • the surface of the steel strip in contact with the punch during the strip forming process of the present invention is a stearate lubricating layer, which has good lubricity and high surface cleanliness.
  • the surface roughness is R a ⁇ 0.3 ⁇ m and R z ⁇ 2 ⁇ m.
  • the surface of the strip steel in contact with the punch is the inner surface of the forming part.
  • the smoother surface design can meet the high dimensional accuracy requirements of the forming part. When the surface roughness in contact with the punch is too high, that is, Ra > 0.3 or R z > 2, the risk of poor dimensional accuracy and smoothness of the inner surface of the molded part increases.
  • the upper and lower surfaces of the steel strip described in the present invention are designed with differentiated functions, wherein the surface of the steel strip in contact with the punch has good lubricity and high surface cleanliness, and the surface of the steel strip in contact with the die has good surface lubrication performance during the stretching process, which meets the requirements of continuous and efficient stamping process during the processing of high-precision, large-deformation shell parts, and eliminates the need for coating and oiling operations of conventional steel plates during the stamping process of high-precision, large-deformation shell parts.
  • both the upper and lower surfaces of the strip have stearate. After the stearate is formed into a film, it has an excellent corrosion medium barrier function at room temperature, which can effectively improve the anti-rust and anti-corrosion performance of the strip surface. The parts produced with this strip do not need to be coated with anti-rust oil.
  • the present invention provides a method of manufacturing steel strip, such as the steel strip described above, comprising the steps of:
  • the steel material enters the degreasing tank equipped with alkaline degreasing agent through the tension roller, and the steel material is degreased at a degreasing temperature of 30 to 60°C; the oil stain on the surface of the steel material can be cleaned by using the alkaline degreasing agent;
  • the rinsing water is industrial pure water with a conductivity of ⁇ 10us/cm, or the rinsing water is tap water+0.2 to 1.1wt% corrosion inhibitor;
  • Spraying a surface conditioner on the upper surface of the rinsed steel to activate the upper surface of the steel wherein the spray pressure is 0.4 to 1.2 bar, and the spray direction is at an angle of 90 to 135° to the running direction of the steel; the lower surface of the steel is coated with a passivation treatment agent with a phosphating barrier function to passivate the lower surface of the steel;
  • Phosphating treatment is carried out on the upper surface of the activated steel through high-pressure spraying phosphating agent, wherein, the phosphating treatment time is 6 to 12s, and the spraying pressure is 5 to 8bar; the spraying direction and the running direction of the steel form an angle of 90 to 135°;
  • step 2) the steel surface is rinsed by spraying, and the spraying pressure is 2 to 4 bar.
  • the corrosion inhibitor is selected from one or more of sodium phosphate, sodium nitrite, sodium benzoate and sodium silicate.
  • the surface regulator is selected from colloidal titanium salt system surface regulators, such as commercially available Pacase PL-Z or similar products.
  • the passivation treatment agent with phosphating barrier function is a Zrate-based passivation treatment agent or a Crate-based passivation treatment agent.
  • the phosphating agent is selected from the phosphating solution of the zinc-manganese-nickel ternary system, such as commercially available Pacaseline PB-181 or similar products.
  • the spraying direction and the running direction of the steel form an included angle of 100 to 120°.
  • step 5 the steel surface is rinsed by spraying, the spraying pressure is 1 to 4 bar, and the spraying direction and the running direction of the steel form an included angle of 90 to 120°.
  • the stearate treatment agent is applied by spraying.
  • the stearate in the stearate treating agent is C18 or C16 stearate.
  • the stearate treatment agent comprises one or more of sodium stearate, magnesium stearate and zinc stearate.
  • movable baffles are respectively provided at 2 to 6 cm, preferably 3 to 5 cm, from both sides of the steel in the width direction of the steel.
  • the movable baffle is roughly on the same plane as the steel, and perpendicular to the length direction of the steel (ie running direction), and the gap between the movable baffle and the edge of the steel is 2 to 6 cm, preferably 3 to 5 cm.
  • the running speed of the steel is 40 to 80 m/min.
  • the main purpose of degreasing is to effectively clean the dirt on the steel surface.
  • the temperature of the degreasing agent is controlled at 30 to 60°C. If the temperature is too low ( ⁇ 30°C), the cleaning ability will be significantly reduced, and the surface cleaning effect will be difficult to guarantee, or a large amount of cleaning aids will be added, which is not environmentally friendly; if the temperature is too high (>60°C), the energy consumption will be too large to meet the requirements of low-carbon production.
  • the first rinse removes the residual degreasing agent on the steel surface, and the cleaning effect of the surface oil is confirmed through the continuous state of the surface water film.
  • Corrosion problems are prone to occur during the first rinsing process, which can be effectively avoided mainly through rinsing water quality and corrosion inhibition technology.
  • the corrosion process of metal materials in water is mainly electrochemical reaction, and the conductivity of water directly affects the difficulty of corrosion reaction.
  • the conductivity of water is affected by the number of anions and cations of impurities in it, and it is mainly characterized by conductivity.
  • the surface of fresh metal materials after degreasing is prone to rust.
  • the rinsing process uses industrial pure water with a conductivity of ⁇ 10us/cm, which can effectively control the occurrence of corrosion problems.
  • the rinsing water uses tap water + 0.2 to 1.1wt% corrosion inhibitor, which can effectively reduce the risk of surface corrosion during the washing process while the surface is fully cleaned.
  • the added corrosion inhibitor is selected from one or more of sodium phosphate, sodium nitrite, sodium benzoate and sodium silicate.
  • the surface conditioner is sprayed on the upper surface of the steel to form a surface adjustment activation layer that promotes the uniform nucleation of phosphating; on the other hand, a passivation treatment agent with a phosphating barrier function is coated on the lower surface of the steel to form a rust-proof passivation layer with a phosphating barrier function.
  • the spray pressure is controlled at 0.4 to 1.2 bar. When the pressure is too low, less than 0.4bar, the spraying amount of the surface conditioner is insufficient and the activation is insufficient.
  • the spraying direction and the running direction of the steel form an included angle of 90 to 135°, preferably 100 to 120°, which can better avoid the influence of the surface conditioner on the lower surface.
  • the passivation treatment agent with phosphating barrier function on the steel surface can be applied by spraying, roller coating, brushing, etc.
  • spraying it is necessary to control the angle range between the spraying direction and the running direction of the steel, which can reduce the interaction between the upper and lower surface treatment agents caused by spray splashing.
  • movable baffles In order to avoid the interference between the two surfaces during the spraying process, it is preferable to set movable baffles at a distance of 2 to 6 cm from the edges on both sides of the steel.
  • the main purpose is to avoid the mutual contamination of the two surface treatment agents during the spraying process.
  • the gap between the steel and the movable baffle is too large (>6cm), different treatment agents on the upper and lower surfaces will significantly affect each other during the spraying process; when the gap between the steel and the movable baffle is too small ( ⁇ 2cm), there is a greater risk of steel edge collision during normal production.
  • the gap between the steel material and the movable baffle is preferably 3 to 5 cm.
  • the main purpose of phosphating is to quickly form evenly distributed phosphating crystal particles on one side of the steel to form a film quickly, uniformly, and non-densely (see Figure 1).
  • a phosphating film is formed within 6 to 12 seconds. It is a non-dense phosphating film composed of elongated plate-like phosphating crystal particles. The size and length of the crystal particles are 8 to 20 ⁇ m.
  • the phosphating film layer can better provide a three-dimensional space for the subsequent stearate film formation, effectively increasing the storage capacity of the stearate lubricant on the product surface; on the other hand, it can better ensure the uniform distribution of the lubricant during the deformation process, and use its own good friction and lubrication characteristics to provide further lubrication functions.
  • the design of non-dense phosphating film with coarse crystals can effectively reduce the amount of wear debris in the stamping process, thereby improving the life of the die.
  • Conventional continuous steel phosphating treatment generally takes more than 15s.
  • the present invention can control the effective surface phosphating treatment in 6 to 12s by controlling the spraying pressure at 4 to 10bar through high-pressure spraying, which greatly improves the phosphating efficiency.
  • the spray pressure is low ( ⁇ 4bar)
  • the phosphating efficiency in the continuous manufacturing process does not meet the requirements of fast (6 to 12s) phosphating treatment, and the phosphating crystal size produced is too small (particle size length ⁇ 8 ⁇ m), which cannot meet the surface requirements of continuous steel production products.
  • the spray pressure is too high (>10bar)
  • excessive splashing will occur, which will easily affect the lower surface, and adversely affect the stability of the phosphating effect and the uniform distribution of phosphating crystals.
  • the spraying direction and the running direction of the steel form an included angle of 90 to 135°, preferably 100 to 120°.
  • the second rinse the main function is to effectively clean the phosphating treatment agent remaining on the surface. Due to the effect of the phosphating film and the surface passivation film on the steel surface, the risk of corrosion in this process is significantly reduced, and no special anti-rust control is required.
  • the surface of the steel is rinsed with industrial pure water with a conductivity of ⁇ 10us/cm.
  • the temperature of the rinsing water is room temperature
  • the spray pressure is 1 to 4bar
  • the spray direction and the running direction of the steel are at an angle of 90 to 120°.
  • Stearate treatment (saponification treatment): Apply stearate liquid at 70 to 90°C to the surface of the steel by spraying, and use a wiping roller to treat the surface film evenly.
  • the stearate is C18 or C16 stearate.
  • the stearate treating agent is formulated from one or more of sodium stearate, magnesium stearate and zinc stearate. After the liquid stearate is sprayed onto the surface of the steel, it is blown by compressed air, and the surface film is evenly treated by the wiping roller.
  • the steel coil manufactured by the above method has excellent anti-rust and anti-corrosion properties, and does not need to be coated with anti-rust oil during storage and transportation.
  • the present invention obtains a steel strip with differentiated functions on both sides, wherein only the surface with the stearate lubricating layer has good lubricity and high surface cleanliness, and the surface with the phosphating layer and the stearate lubricating layer has good surface lubricity during the extension process, which meets the requirements of continuous and efficient stamping process during the processing of high-precision, large-deformation shell parts; while traditional steel plates need to be coated and oiled during the stamping process of high-precision, large-deformation shell parts, and the parts need to be cleaned after being processed into parts.
  • the steel strip described in the present invention can be used for direct punching and processing of high-precision and large-deformation housing parts.
  • the two surfaces of the substrate are activated and passivated respectively, and the parameters in the process are controlled to prevent interference in the two surface treatment processes, and then the single-side phosphating spray process + double-side saponification process is adopted to realize the continuous production of strip steel with differentiated functions on the two surfaces.
  • the present invention adopts the phosphating process of high-pressure spraying, which greatly reduces the effective processing time under the condition of appropriate equipment length, and the overall running speed of the strip can be controlled at 40 to 80 m/min, which meets the requirements of high-efficiency manufacturing of conventional strip steel, so that the method can be directly connected to the existing continuous annealing and smoothing process of cold-rolled strip steel, and can also be used as a separate strip surface treatment method to realize continuous production of strip steel with two different surface functions.
  • Fig. 1 is a structural schematic diagram of strip steel in the present invention.
  • Fig. 1 it shows the structure of steel strip of the embodiment of the present invention, and described oil-free steel strip comprises substrate, and the A face of described substrate comprises phosphating layer 1 and stearate lubricating layer 2 successively from inside to outside, and the B face of substrate is stearate lubricating layer 2.
  • Table 1 for the substrate composition of the examples and comparative examples of the present invention, and the balance is Fe and unavoidable impurities except P and S.
  • Table 2 is the manufacturing process parameter of embodiment and comparative example. The evaluation results of the process implementation effect of the embodiment of the present invention and the comparative example are shown in Table 3. Two kinds of surface roughness R a ("contour arithmetic mean deviation") and R z ("micro-roughness ten-point height") of the strip steel were measured by using the Mahr MARSURF PS 10 mobile roughness measuring instrument in Germany (measuring reference standard GB/T 1031).
  • the degreasing and cleaning effect on the strip surface was evaluated by the continuous state of the water film on the surface during the water washing process after degreasing. Visually observe the state of the water film on the washed surface after degreasing:
  • the surface water film is uniform and continuous, with a coverage rate of 100%;
  • ⁇ The water film on the surface is obviously discontinuous, and the coverage is less than 100%.
  • ⁇ There are rust spots on the surface, and the rust area is more than 0%.
  • the phosphating crystal size on the upper surface is 8 to 20 ⁇ m, and the crystals are evenly distributed, 1g/m 2 ⁇ phosphating film weight ⁇ 3g/m 2 ;
  • the phosphating crystal size on the upper surface is 8 to 20 ⁇ m, but the local distribution of crystals is uneven, 1g/m 2 ⁇ phosphating film weight ⁇ 3g/m 2 ;
  • the phosphating crystal size on the upper surface is ⁇ 8 ⁇ m or >20 ⁇ m, and the weight of the phosphating film is ⁇ 1 g/m 2 or the weight of the phosphating film is >3 g/m 2 ;
  • embodiment 1-6 is processed according to the procedure described in the present invention, and the strip steel technological effect that obtains all shows excellent, and the lower surface of strip steel is a stearate lubricating layer, and its surface roughness R a ⁇ 0.3 ⁇ m and R z ⁇ 2 ⁇ m, has good lubricity and high surface cleanliness; m, the surface has good surface lubricity during the extension process, realizes the differential functional design of the two surfaces of the strip steel, and meets the continuous and efficient stamping process requirements in the processing of high-precision, large-deformation shell parts.
  • Comparative Example 1 the phosphating barrier treatment process was not adopted in the phosphating process, resulting in the formation of obvious phosphating crystals on the lower surface partially affected by phosphating.
  • Comparative Example 2 the degreasing temperature was close to room temperature, which could not satisfy the effective cleaning of the surface. At the same time, due to the short phosphating time and too low spray pressure, no significant phosphating crystals were formed on the upper surface.
  • Comparative Example 3 since the tap water with relatively high conductivity was used as the rinse water 1, the washing process after degreasing was obviously rusted, which had a negative impact on the subsequent phosphating.
  • the strip steel that the embodiment of the present invention obtains carries out neutral salt spray test on the strip steel surface with reference to ASTM B117 standard, and strip steel surface 24h does not have corrosion to produce, and its corrosion resistance is obviously better than conventional oiled steel plate (neutral salt spray test surface appears corrosion time is about 12h), illustrates that the strip steel obtained by the present invention has good antirust and anticorrosion performance, can satisfy the corrosion resistance requirement of 4 months storage and transportation strip steel surface without corrosion.
  • Example 1 0.1 0.2 1.22 1.02 0.04 0.05 0.02 0.015
  • Example 2 0.5 1.2 0.8 0.23 0.06 0.11 0.04 0.04
  • Example 3 0.2 0.8 1.7 0.61 0.01 0.15 0.02 0.01
  • Example 4 0.7 1.8 0.2 1.4 0.05 0.20 0.03 0.05
  • Example 5 0.3 2.0 0.3 0.82 0.03 0.08 0.015 0.03
  • Example 6 0.4 1.0 2.0 0.74 0.02 0.06 0.02 0.022 Comparative example 1 0.4 1.1 0.9 1.3 0.03 0.06 0.03 0.02 Comparative example 2 0.1 0.2 1.22 1.02 0.04 0.05 0.02 0.015 Comparative example 3 0.3 2.0 0.3 0.82 0.03 0.08 0.015 0.03

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EP23742688.7A EP4446451A4 (en) 2022-01-19 2023-01-04 STRIP STEEL AND MANUFACTURING METHODS THEREFOR
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