CN112458443B - Stainless steel and preparation method and application thereof - Google Patents

Stainless steel and preparation method and application thereof Download PDF

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Publication number
CN112458443B
CN112458443B CN201910844353.2A CN201910844353A CN112458443B CN 112458443 B CN112458443 B CN 112458443B CN 201910844353 A CN201910844353 A CN 201910844353A CN 112458443 B CN112458443 B CN 112458443B
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stainless steel
passivation layer
layer
sealing
steel substrate
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CN112458443A (en
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王�琦
杨玲
万鹏
钟春发
曹达华
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Foshan Shunde Midea Electrical Heating Appliances Manufacturing Co Ltd
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Foshan Shunde Midea Electrical Heating Appliances Manufacturing Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/34—Filling pastes
    • 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
    • C23C22/83—Chemical after-treatment

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The invention discloses stainless steel and a preparation method and application thereof, wherein the stainless steel comprises the following components: the sealing agent comprises a stainless steel substrate, a passivation layer and a sealing agent, wherein the passivation layer is arranged on at least one part of the stainless steel substrate; the sealing layer is arranged on the passivation layer and fills and/or seals the pores of the passivation layer. The stainless steel adopts the sealing layer to fill and/or plug the pores of the passivation layer, so that the density of the passivation layer can be enhanced while the exposure of the active crystal face of the stainless steel matrix is reduced, and the passivation layer forms a film protection layer which is as close to a sheet as possible on the surface of the stainless steel matrix, thereby obviously improving and strengthening the corrosion resistance of the stainless steel.

Description

Stainless steel and preparation method and application thereof
Technical Field
The invention belongs to the field of household equipment, and particularly relates to stainless steel and a preparation method and application thereof.
Background
The stainless steel pot cover and pot commonly used at present are made of ferritic stainless steel through stamping or drawing processing. Ferritic stainless steel has poor corrosion resistance due to the absence of Ni element. In order to improve the corrosion resistance of ferritic stainless steel pot covers and pots, after the processes of oil removal, polishing, wax removal and the like, chemical passivation treatment is usually carried out on ferritic stainless steel to generate a layer of protective passivation film on the surface of the ferritic stainless steel. However, in the actual processing process, the quality of the passive film is unstable due to the influence of pretreatment cleaning such as oil stain, wax, impurities and the like on the generation of the passive film, so that defects often exist on the surface of the passive film; the defects of the passive film are distributed along the radial direction to form holes and holes, which leads or is easy to lead the stainless steel active crystal to be exposed, and can not prevent the chlorine ions and the like from entering for a long time, thereby causing the phenomenon of 'pitting corrosion', and the corrosion resistance of the stainless steel is not ideal. Therefore, how to improve and strengthen the corrosion resistance of the ferritic stainless steel is under further study.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the invention is to propose stainless steel, a method for its production and its use. The stainless steel adopts the sealing layer to fill and/or plug the pores of the passivation layer, so that the density of the passivation layer can be enhanced while the exposure of the active crystal face of the stainless steel matrix is reduced, and the passivation layer forms a film protection layer which is as close to a sheet as possible on the surface of the stainless steel matrix, thereby obviously improving and strengthening the corrosion resistance of the stainless steel.
According to a first aspect of the invention, a stainless steel is proposed. According to an embodiment of the invention, the stainless steel comprises:
a stainless steel substrate;
a passivation layer disposed on at least a portion of the stainless steel substrate;
and the sealing layer is arranged on the passivation layer and fills and/or blocks the pores of the passivation layer.
According to the stainless steel provided by the embodiment of the invention, the pores of the passivation layer are filled and/or plugged by adopting the sealing layer on the basis of not damaging the original passivation layer, so that the compactness of the passivation layer is enhanced while the exposure of the active crystal face of the stainless steel substrate is reduced, and the passivation layer forms a film protection layer which is as close to a sheet as possible on the surface of the stainless steel substrate, thereby obviously improving and enhancing the corrosion resistance of the stainless steel, and effectively preventing Cl - The penetrating and penetrating action of the stainless steel greatly reduces the probability of pitting corrosion of the stainless steel, and particularly can prolong the service life of the cookware and/or the pot cover when the stainless steel is used for preparing the cookware and/or the pot cover. Specifically, the stainless steel is boiled in 40-70 KPa and 1.0wt% NaCl solution for 24h, and the rusting rate is not more than 3%, so that the stainless steel can be widely applied to products such as stainless steel pot covers, pots and the like.
In addition, the stainless steel according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the invention, the passivation layer is a chromium-containing passivation layer.
In some embodiments of the invention, the porosity of the passivation layer is 0.1 to 2%. Therefore, the bonding strength of the sealing layer and the passivation layer can be improved, and meanwhile, the flatness of the sealing layer and the sealing effect on the stainless steel substrate can be guaranteed.
In some embodiments of the present invention, the passivation layer has a thickness of 1 to 10 nm. Therefore, the corrosion resistance of the stainless steel substrate can be obviously improved, the passivation layer, the stainless steel substrate and the sealing layer can have better bonding strength, the sealing layer can be guaranteed to block or fill the passivation layer, and the anchoring effect of the sealing layer and the bonding force of the sealing layer and the stainless steel substrate are improved.
In some embodiments of the invention, the capping layer comprises elemental titanium and elemental silicon. Therefore, the sealing layer can be used for filling and/or plugging the pores of the passivation layer, the passivation layer and the filler can be well covered and fixed by the sealing layer, the stainless steel pitting phenomenon caused by the surface defects of the passivation layer can be obviously reduced, and the effect of further improving the corrosion resistance of the stainless steel is achieved.
In some embodiments of the invention, the sealing layer is made from silane and titanate. Therefore, the titanate hydrolysate can be used as a main substance for filling and blocking the pores on the surface of the passivation layer, the passivation layer and the filler can be covered and fixed by using the film forming property of the silane, and the bonding strength of the sealing layer, the stainless steel matrix and the passivation layer can be further improved, so that the corrosion resistance of the stainless steel is remarkably improved.
In some embodiments of the invention, the silane and the titanate are in a mass ratio of (55 to 89): (15 to 45). Therefore, the bonding strength of the sealing layer and the stainless steel matrix as well as the passivation layer is further improved, and the chemical stability and the corrosion resistance of the stainless steel are greatly improved.
In some embodiments of the invention, the silane and the titanate are present in a mass ratio of 2:1. therefore, the corrosion resistance of the stainless steel matrix can be further improved and strengthened, and the probability of pitting corrosion of the stainless steel is greatly reduced.
In some embodiments of the invention, the thickness of the sealing layer is 0.05 to 0.1 microns. Therefore, the corrosion resistance of the stainless steel can be further improved and strengthened, and the probability of pitting corrosion of the stainless steel is greatly reduced.
According to a second aspect of the present invention, there is provided a method for producing the above stainless steel. According to an embodiment of the invention, the method comprises:
(1) Pretreating a stainless steel substrate so as to remove impurities on the surface of the stainless steel substrate;
(2) Passivating the pretreated surface of the stainless steel substrate by adopting a passivating agent so as to form a passivation layer on at least one part of the surface of the stainless steel substrate; and
(3) And sealing the passivation layer by using a sealing agent so as to form a sealing layer on the passivation layer, wherein the sealing layer fills and/or seals the pores of the passivation layer.
According to the method for preparing the stainless steel, the surface of the stainless steel substrate is passivated in advance, the formed passivation layer is sealed by using the sealing agent, the pores of the passivation layer can be filled and/or plugged by using the sealing layer on the basis of not damaging the passivation layer, the exposure of the active crystal face of the stainless steel substrate is further reduced, the compactness of the passivation layer is enhanced, the passivation layer forms a film protection layer which is as close to a sheet as possible on the surface of the stainless steel substrate, the corrosion resistance of the finally prepared stainless steel is obviously improved and enhanced, and Cl is effectively prevented - The penetrating and penetrating action of the stainless steel greatly reduces the probability of pitting corrosion of the stainless steel, and particularly can prolong the service life of the cookware and/or the pot cover when the stainless steel is used for preparing the cookware and/or the pot cover. Specifically, the stainless steel prepared by the method has a rusting rate of not more than 3% after being boiled in 40-70 KPa and 1.0wt% NaCl solution for 24 hours, and can be widely applied to products such as stainless steel pot covers, pots and the like.
In some embodiments of the invention, in step (2), the passivating agent comprises anhydrous sodium dichromate, trisodium citrate dihydrate, ammonium sulfate, and water. This can facilitate formation of a passivation film on the surface of the stainless steel substrate.
In some embodiments of the invention, in step (3), the encapsulant comprises a titanate and a silane. Therefore, the passivation layer and the filler can be well covered and fixed, the stainless steel pitting phenomenon caused by the surface defects of the passivation layer can be obviously reduced, and the effect of further improving the corrosion resistance of the stainless steel is achieved.
In some embodiments of the invention, the mass ratio of the titanate to the silane is (15 to 45): (55-89). Therefore, the bonding strength of the sealing layer and the stainless steel matrix as well as the passivation layer is further improved, and the chemical stability and the corrosion resistance of the stainless steel are greatly improved.
In some embodiments of the invention, the mass ratio of the titanate and the silane is 1. Therefore, the corrosion resistance of the stainless steel matrix can be further improved and strengthened, and the probability of pitting corrosion of the stainless steel is greatly reduced.
According to a third aspect of the invention, the invention proposes a pot lid. According to an embodiment of the present invention, the pot lid is made of the above stainless steel or the stainless steel obtained by the above manufacturing method. The pot cover has remarkable corrosion resistance, can effectively prevent corrosion of chloride ions in the cooking process, reduces the probability of pitting corrosion of the pot cover, further avoids rusting of the pot cover, and improves user experience.
According to a fourth aspect of the invention, the invention provides a pot. According to the embodiment of the invention, the pot is prepared from the stainless steel or the stainless steel prepared by the preparation method. The cookware has remarkable corrosion resistance, can effectively prevent chloride ions from corroding in the cooking process, reduces the probability of pitting corrosion of the cookware, can further avoid rusting of the cookware, and improves the user experience.
According to a fifth aspect of the present invention, a cooking appliance is provided. According to the embodiment of the invention, the cooking appliance is provided with the pot cover and/or the pot. This cooking utensil has apparent corrosion resisting property's pot cover and/or pan through adopting the aforesaid, can further avoid cooking utensil to rust, prolongs cooking utensil's life, promotes user experience.
In some embodiments of the invention, the cooking appliance is an electric rice cooker, an electric pressure cooker, a soup cooker or an electric saucepan.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic structural view of a stainless steel according to one embodiment of the present invention.
Fig. 2 is a schematic diagram of sealing a passivation layer with a capping layer according to an embodiment of the present invention.
Fig. 3 is a schematic structural view of stainless steel according to yet another embodiment of the present invention.
Fig. 4 is a schematic view showing a microscopic state of film formation of silane on the surface of a stainless steel substrate according to an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to a first aspect of the invention, a stainless steel is proposed. According to an embodiment of the present invention, as shown in fig. 1, the stainless steel includes: a stainless steel substrate 10, a passivation layer 20 and a sealing layer 30, wherein the passivation layer 20 is disposed on at least a portion of the stainless steel substrate 10; the capping layer 30 is disposed on the passivation layer 20 and fills and/or blocks pores of the passivation layer 20.
The inventor finds that the surface of the stainless steel substrate needs to be cleaned before the chemical passivation treatment is carried out on the stainless steel substrate so as to remove oil stain, polishing wax, free impurities and the like on the surface, and the quality of the cleaning degree directly influences the quality of the passivation film, so that defects are formed on the surface of the passivation filmOn the basis of recognizing the technical problems, a great deal of research shows that the pores of the passivation layer 20 are filled and/or blocked by the sealing layer 30 on the basis of not damaging the original passivation layer, so that the density of the passivation layer 20 can be enhanced while the exposure of the active crystal face of the stainless steel matrix 10 is reduced, the passivation layer 20 forms a film layer protection layer which is as close to a sheet as possible on the surface of the stainless steel matrix 10, the corrosion resistance of the stainless steel is remarkably improved and enhanced, the permeation and penetration of Cl < - > are effectively prevented, and the pitting corrosion probability of the stainless steel is greatly reduced. Specifically, referring to fig. 2, when a passivation agent is used to passivate a stainless steel substrate, the surface of the passivation layer formed tends to have holes or pores distributed therein, which cannot prevent chloride ions (Cl) for a long time - ) And the like, thereby causing a 'pitting' phenomenon, and after a sealing treatment is further performed to form a sealing layer, the size or diameter of the mesh holes can be obviously reduced, as shown in sealing effects 1 and 2 in fig. 2, because of the filling and sealing effects of the sealing layer, and the original passivation layer morphology is also subjected to microscopic change. Wherein, the sealing effect 1 is an ideal hole sealing effect, at the moment, the grid holes of the passivation layer are almost completely sealed, the capability of preventing external ions from penetrating is obviously enhanced, and the corrosion resistance of the stainless steel reaches the best; the sealing effect 2 is a better hole sealing effect, although the grid holes of the passivation layer are not completely sealed, the size is obviously reduced, and the corrosion resistance of the stainless steel is also improved to a certain extent. Wherein, the stainless steel of the above embodiment of the invention has a rusting ratio of not more than 3% after being boiled in 40-70 KPa and 1.0wt% NaCl solution for 24h, and when the stainless steel is used for preparing a pot and/or a pot cover, the service life of the pot and/or the pot cover can be further prolonged.
The stainless steel according to the above embodiment of the present invention will be described in detail with reference to fig. 1 to 4.
According to one embodiment of the present invention, the passivation layer 20 may be a chromium-containing passivation layer. The inventors found that defects are more likely to form on the surface of a passivation layer when a stainless steel substrate is passivated with a chromium-containing passivator, and thus, with respect to a stainless steel substrate having a chromium-containing passivation layer, the corrosion resistance of the stainless steel may be significantly improved by further providing a seal layer on the chromium-containing passivation layer and allowing the seal layer to fill and/or block the pores of the passivation layer, and the rust rate of the stainless steel after being boiled in a 1.0wt% NaCl solution at 40 to 70KPa after the seal layer is provided is also not more than 3%.
According to yet another embodiment of the present invention, the porosity of the passivation layer 20 may be 0.1 to 2%, for example, may be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%. Therefore, the bonding strength of the sealing layer and the passivation layer can be further improved, and meanwhile, the flatness of the sealing layer and the sealing effect on the stainless steel substrate can be guaranteed.
According to yet another embodiment of the present invention, as shown in FIG. 3, the thickness H of the passivation layer 20 1 The thickness of the passivation layer 20 is too small, the passivation effect on the stainless steel substrate 10 is difficult to ensure, and the corrosion resistance of the stainless steel substrate 10 cannot be guaranteed; when the thickness of the passivation layer 20 is too large, the corrosion resistance of the stainless steel substrate 10 is further improved without significant effect, the bonding strength between the passivation layer 20 and the stainless steel substrate 10 is affected, the passivation treatment efficiency on the stainless steel substrate 10 is also affected, the plugging or filling effect of the sealing layer on the passivation layer is weakened, the anchoring effect of the sealing layer is significantly reduced, and the bonding force between the sealing layer and the stainless steel substrate is reduced. According to the invention, by controlling the thickness of the passivation layer 20 to be 1-10 nm, the corrosion resistance of the stainless steel substrate can be obviously improved, the passivation layer, the stainless steel substrate and the sealing layer can have better bonding strength, the sealing layer can be guaranteed to block or fill the passivation layer, and the anchoring effect of the sealing layer and the bonding force with the stainless steel substrate are improved.
According to yet another embodiment of the present invention, the capping layer 30 may contain elemental titanium and elemental silicon. The inventor finds that if the sealant 30 contains titanium and silicon, when the passivation layer 20 is sealed, the titanium component can play a good role in filling and blocking the pores of the passivation layer, and the silicon component is mainly distributed at the interface of the passivation layer and the sealing layer and can play a good role in anchoring and fixing the passivation layer, so that the sealant is beneficial to filling and/or blocking the pores of the passivation layer, the sealing layer can also well cover and fix the passivation layer and the filler, the stainless steel pitting phenomenon caused by the surface defects of the passivation layer can be obviously reduced, and the effect of further improving the corrosion resistance of the stainless steel can be achieved.
According to yet another embodiment of the present invention, the sealing layer 30 may be made of silane and titanate. The inventor finds that when the passivating layer is sealed by using a sealing agent containing silane and titanate to form the sealing layer, the titanate hydrolysate can be used as a main substance for plugging pores on the surface of the passivating layer, the passivating layer and a filler can be covered and fixed by using the film forming property of the silane, and the bonding strength of the sealing layer and a stainless steel matrix and the passivating layer can be further improved, so that the corrosion resistance of the stainless steel is remarkably improved. When the passivation layer and the filler are covered and fixed by using the film-forming property of silane, si-OH groups in a silane solution and Me-OH groups (Me is a metal substrate) on the surface of a stainless steel substrate are condensed to form Si-O-Me covalent bonds with strong binding force on an interface, and the bonds and the Si-O-Si bonds form a new structure in an interface region, so that the stainless steel substrate is well protected, the corrosion resistance of the stainless steel is greatly improved, and as shown in figure 4, a formed metal silanization film layer mainly comprises two parts: firstly, the silane treating agent forms a metal silane composite film on the surface of the stainless steel matrix through film forming reaction, and secondly, a large amount of oligosiloxane is formed through condensation reaction, so that not only is a complete silane film formed, but also the chemical stability of the stainless steel matrix is greatly improved. In conclusion, when the sealing agent containing silane and titanate is used for sealing the stainless steel substrate with the passivation layer, the filling and/or the plugging of the pores of the passivation layer can be realized, the exposure of the active crystal face of the stainless steel substrate is reduced, the compactness of the passivation layer is enhanced, the bonding strength of the sealing layer and the stainless steel substrate as well as the passivation layer can be obviously improved, and the chemical stability and the corrosion resistance of the stainless steel are greatly improved.
According to another embodiment of the present invention, the sealing layer 30 may be formed by using silane and titanate in a mass ratio of (55-89): (15 to 45), for example, 55, 89. The inventor finds that when the passivation layer is subjected to sealing treatment, if the mass ratio of silane to titanate in the sealing agent is too large, the content of titanate in the sealing agent is too small, which is unfavorable for titanate hydrolysis, and sufficient titanate hydrolysate is difficult to form to fill the pores of the passivation layer, and if the mass ratio of silane to titanate in the sealing agent is too small, which is equivalent to relatively low content of silane, which is unfavorable for forming a stable metal silanized film layer, and the interfacial bonding force between the sealing layer and the stainless steel substrate is unstable. When the sealing layer is prepared, the mass ratio of silane to titanate is controlled to be (55-89): (15-45), not only can make the sealant form enough titanate hydrolyzate to fully fill the gap on the surface of the passivation layer, further obviously reduce the exposure of the active crystal face of the stainless steel matrix, but also can form a complete and stable silane film layer when the passivation layer and the filler are covered and fixed by utilizing the film forming property of silane, so that the finally formed sealing layer is bonded with the stainless steel matrix through a Si-O-Me covalent bond, thereby further improving the bonding strength of the sealing layer with the stainless steel matrix and the passivation layer, and greatly improving the chemical stability and the corrosion resistance of the stainless steel. Preferably, the mass ratio of silane to titanate used to make the sealing layer 30 may be 2:1, therefore, the compactness of the passivation layer can be further improved, the exposure of the active crystal face of the stainless steel substrate is reduced, and the sealing layer and the stainless steel substrate and the passivation layer have higher bonding strength, so that the corrosion resistance of the stainless steel substrate can be further improved and strengthened, and the probability of pitting corrosion of the stainless steel is greatly reduced.
According to yet another embodiment of the present invention, as shown in FIG. 3, the thickness H of the sealing layer 30 2 Which may be 0.05 to 0.1 μm, the inventors have found that, if the thickness of the capping layer 30 is too thin, the covering and fixing effects on the passivation layer and the passivation layer pore fillers are not good, the interfacial bonding force between the capping layer and the stainless steel substrate is not stable, and the thickness of the capping layer 30 is too thickThe thickness of the sealing layer also has a negative influence on the bonding force of the sealing layer with the stainless steel substrate and the passivation layer, and the raw material is wasted. According to the invention, by controlling the thickness of the sealing layer 30 to be 0.05-0.1 micron, the utilization rate of raw materials can be improved, the covering and fixing effects on the passivation layer and the filler can be obviously improved, and the bonding strength of the sealing layer, the stainless steel substrate and the passivation layer is further improved, so that the corrosion resistance of the stainless steel can be further improved and strengthened, and the probability of pitting corrosion of the stainless steel is greatly reduced.
According to a second aspect of the present invention, there is provided a method for producing the above stainless steel. According to an embodiment of the invention, the method comprises: (1) Pretreating the stainless steel substrate so as to remove impurities on the surface of the stainless steel substrate; (2) Passivating the surface of the pretreated stainless steel substrate by adopting a passivating agent so as to form a passivation layer on at least one part of the surface of the stainless steel substrate; and (3) carrying out sealing treatment on the passivation layer by using a sealing agent so as to form a sealing layer on the passivation layer, wherein the sealing layer fills and/or seals the pores of the passivation layer. The method is characterized in that the surface of the stainless steel substrate is passivated in advance, and then the formed passivation layer is sealed by using a sealing agent, so that the pores of the passivation layer can be filled and/or plugged by using a sealing layer on the basis of not damaging the passivation layer, the exposure of the active crystal face of the stainless steel substrate is further reduced, the compactness of the passivation layer is enhanced, the passivation layer forms a film protection layer which is as close to a sheet as possible on the surface of the stainless steel substrate, the corrosion resistance of the finally prepared stainless steel is obviously improved and enhanced, and Cl is effectively prevented - The penetrating and penetrating action of the stainless steel greatly reduces the probability of pitting corrosion of the stainless steel, and particularly can prolong the service life of the cookware and/or the pot cover when the stainless steel is used for preparing the cookware and/or the pot cover. Specifically, the stainless steel prepared by the method has a rusting rate of not more than 3% after being boiled in 40-70 KPa and 1.0wt% NaCl solution for 24 hours, and can be widely applied to products such as stainless steel pot covers, pots and the like.
According to a specific embodiment of the present invention, the step of pretreating the stainless steel substrate may include the steps of degreasing the stainless steel substrate, washing with water, drying and polishing, dewaxing, spraying and washing with water, and the like, and the step of passivating the pretreated stainless steel substrate may be the step of immersing the pretreated stainless steel substrate in a passivating agent to form a passivation layer on the surface of the stainless steel substrate. Further, the soaking temperature may be 50-60 ℃ and the soaking time may be not less than 30 minutes, so that a uniform and stable passivation film may be formed on the surface of the stainless steel substrate.
According to still another embodiment of the present invention, in the step (2), the passivating agent may include a film forming agent, a complexing agent, a film forming promoter, and a diluent, and may include, for example, anhydrous sodium dichromate as the film forming agent, trisodium citrate dihydrate as the complexing agent, ammonium sulfate as the film forming promoter, and water as the diluent. This can facilitate the formation of a passive film on the surface of stainless steel.
According to still another embodiment of the present invention, in the step (3), the sealing agent may include titanate and silane. The inventor finds that when the passivation layer is sealed by using a sealing agent containing silane and titanate to form the sealing layer, not only can the titanate hydrolysate be used as a main substance for filling and/or sealing the pores on the surface of the passivation layer, so that the pores of the passivation layer can be filled and/or sealed, the exposure of the active crystal face of the stainless steel matrix can be reduced, and the compactness of the passivation layer can be enhanced, but also the bonding strength between the sealing layer and the stainless steel matrix and between the sealing layer and the passivation layer can be further improved by covering and fixing the passivation layer and the filler by using the film forming property of the silane, so that the corrosion resistance of the stainless steel can be remarkably improved.
According to another embodiment of the present invention, the mass ratio of silane to titanate in the sealant can be (55-89): (15 to 45), for example, 55, 89. The inventor finds that when the passivation layer is subjected to sealing treatment, if the mass ratio of silane to titanate in the sealing agent is too large, the content of titanate in the sealing agent is too small, which is unfavorable for titanate hydrolysis, and sufficient titanate hydrolysate is difficult to form to fill the pores of the passivation layer, and if the mass ratio of silane to titanate in the sealing agent is too small, which is equivalent to relatively low content of silane, which is unfavorable for forming a stable metal silanized film layer, and the interfacial bonding force between the sealing layer and the stainless steel substrate is unstable. When the sealing layer is prepared, the mass ratio of silane to titanate is controlled to be (55-89): (15-45), not only can make the sealant form enough titanate hydrolyzate to fully fill the gap on the surface of the passivation layer, further obviously reduce the exposure of the active crystal face of the stainless steel matrix, but also can form a complete and stable silane film layer when the passivation layer and the filler are covered and fixed by utilizing the film forming property of silane, so that the finally formed sealing layer is bonded with the stainless steel matrix through a Si-O-Me covalent bond, thereby further improving the bonding strength of the sealing layer with the stainless steel matrix and the passivation layer, and greatly improving the chemical stability and the corrosion resistance of the stainless steel. Preferably, the mass ratio of silane to titanate in the sealant may be 2:1, therefore, the compactness of the passivation layer can be further improved, the exposure of the active crystal face of the stainless steel substrate is reduced, and the sealing layer and the stainless steel substrate and the passivation layer have higher bonding strength, so that the corrosion resistance of the stainless steel substrate can be further improved and strengthened, and the probability of pitting corrosion of the stainless steel is greatly reduced.
According to another embodiment of the present invention, the sealing treatment of the passivation layer using the sealing agent may be performed at a temperature of 50 to 60 ℃ for a time of more than 30 seconds.
It should be noted that the features and advantages described above for stainless steel apply equally to the method of making stainless steel and are not described in detail here.
According to a third aspect of the invention, the invention proposes a pot lid. According to an embodiment of the present invention, the pot lid is made of the above stainless steel or the stainless steel obtained by the above manufacturing method. The pot cover has remarkable corrosion resistance, can effectively prevent chloride ions from being corroded in the cooking process, reduces the probability of pitting corrosion of the pot cover, further avoids the pot cover from rusting, and improves user experience. It should be noted that the features and advantages described above for stainless steel and the method of making stainless steel apply equally to the lid and are not described in detail here.
According to a fourth aspect of the invention, the invention provides a pot. According to the embodiment of the invention, the pot is prepared from the stainless steel or the stainless steel prepared by the preparation method. The cookware has remarkable corrosion resistance, can effectively prevent chloride ions from corroding in the cooking process, reduces the probability of pitting corrosion of the cookware, can further avoid rusting of the cookware, and improves the user experience. It should be noted that the features and advantages described above for stainless steel and the method of making stainless steel are equally applicable to the cookware, and are not described herein again. In addition, the pot in the invention can be a pot without a pot cover.
According to a fifth aspect of the present invention, a cooking appliance is provided. According to the embodiment of the invention, the cooking appliance is provided with the pot cover and/or the pot. This cooking utensil is through adopting above-mentioned pot cover and/or pan that has apparent corrosion resisting property, can further avoid cooking utensil to rust, prolongs cooking utensil's life, promotes user experience. It should be noted that the features and advantages described above for the lid and/or the pot also apply to the cooking appliance, and are not described in detail here.
According to an embodiment of the present invention, the type of the cooking utensil in the present invention is not particularly limited, and those skilled in the art can select the cooking utensil according to actual needs. For example, the cooking appliance may be an electric rice cooker, an electric pressure cooker, a soup cooker or an electric saucepan.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The stainless steel comprises a stainless steel substrate, a passivation layer and a sealing layer, wherein the passivation layer is arranged on at least one part of the stainless steel substrate, and the sealing layer is arranged on the passivation layer and fills and/or seals pores of the passivation layer. Wherein, the thickness of the passivation layer is 3nm, the porosity is 1.5%, and the thickness of the sealing layer is 0.08 microns.
The preparation method of the stainless steel comprises the following steps:
(1) Pretreating a stainless steel substrate to remove impurities on the surface of the stainless steel substrate;
(2) Passivating the surface of the pretreated stainless steel substrate by adopting a passivating agent to form a passivating layer on at least one part of the surface of the stainless steel substrate, wherein the passivating agent comprises anhydrous sodium dichromate, trisodium citrate dihydrate, ammonium sulfate and water, and the passivating treatment is to place the pretreated stainless steel substrate in the passivating agent at the temperature of 55 ℃ for soaking for 30 minutes;
(3) Sealing the passivation layer by using a sealing agent to form a sealing layer on the passivation layer, so that the sealing layer fills and/or seals the pores of the passivation layer, wherein the sealing agent comprises titanate and silane, and the mass ratio of the titanate to the silane is 15: the blocking treatment was carried out by immersing the substrate in a blocking solution at a temperature of 50 ℃ for 45 seconds.
Example 2
The stainless steel comprises a stainless steel substrate, a passivation layer and a sealing layer, wherein the passivation layer is arranged on at least one part of the stainless steel substrate, and the sealing layer is arranged on the passivation layer and fills and/or seals pores of the passivation layer. Wherein, the thickness of the passivation layer is 10nm, the porosity is 0.1%, and the thickness of the sealing layer is 0.1 micron.
Wherein, the preparation method of the stainless steel comprises the following steps:
(1) Pretreating a stainless steel substrate to remove impurities on the surface of the stainless steel substrate;
(2) Passivating the surface of the pretreated stainless steel substrate by adopting a passivating agent to form a passivating layer on at least one part of the surface of the stainless steel substrate, wherein the passivating agent comprises: anhydrous sodium dichromate, trisodium citrate dihydrate, ammonium sulfate and water, wherein the passivation treatment is to place a pretreated stainless steel substrate in a passivator at 55 ℃ and soak the pretreated stainless steel substrate for 30 minutes;
(3) And (2) sealing the passivation layer by adopting a sealing agent to form a sealing layer on the passivation layer, so that the sealing layer fills and/or seals the pores of the passivation layer, wherein the sealing agent comprises titanate and silane, and the mass ratio of the titanate to the silane is 45: the blocking treatment was carried out by immersing the substrate in a blocking solution at 55 ℃ for 45 seconds.
Example 3
The stainless steel comprises a stainless steel substrate, a passivation layer and a sealing layer, wherein the passivation layer is arranged on at least one part of the stainless steel substrate, and the sealing layer is arranged on the passivation layer and fills and/or seals pores of the passivation layer. Wherein, the thickness of the passivation layer is 1nm, the porosity is 2%, and the thickness of the sealing layer is 0.08 microns.
The preparation method of the stainless steel comprises the following steps:
(1) Pretreating a stainless steel substrate to remove impurities on the surface of the stainless steel substrate;
(2) Passivating the surface of the pretreated stainless steel substrate by adopting a passivating agent to form a passivating layer on at least one part of the surface of the stainless steel substrate, wherein the passivating agent comprises: the method comprises the following steps of (1) anhydrous sodium dichromate, trisodium citrate dihydrate, ammonium sulfate and water, wherein the passivation treatment is to place a pretreated stainless steel substrate in a passivator at 50 ℃ and soak the stainless steel substrate for 30 minutes;
(3) And (2) sealing the passivation layer by adopting a sealing agent to form a sealing layer on the passivation layer, so that the sealing layer fills and/or seals the pores of the passivation layer, wherein the sealing agent comprises titanate and silane, and the mass ratio of the titanate to the silane is 1: the blocking treatment was carried out by immersing the substrate in a blocking solution at a temperature of 50 ℃ for 45 seconds.
Example 4
The stainless steel comprises a stainless steel substrate, a passivation layer and a sealing layer, wherein the passivation layer is arranged on at least one part of the stainless steel substrate, and the sealing layer is arranged on the passivation layer and fills and/or seals pores of the passivation layer. Wherein, the thickness of the passivation layer is 6nm, the porosity is 1.0%, and the thickness of the sealing layer is 0.05 microns.
The preparation method of the stainless steel comprises the following steps:
(1) Pretreating a stainless steel substrate to remove impurities on the surface of the stainless steel substrate;
(2) Passivating the surface of the pretreated stainless steel substrate by adopting a passivating agent to form a passivating layer on at least one part of the surface of the stainless steel substrate, wherein the passivating agent comprises: the method comprises the following steps of (1) anhydrous sodium dichromate, trisodium citrate dihydrate, ammonium sulfate and water, wherein the passivation treatment is to place a pretreated stainless steel matrix in a passivator at 55 ℃ and soak the pretreated stainless steel matrix for 30 minutes;
(3) And (2) sealing the passivation layer by adopting a sealing agent to form a sealing layer on the passivation layer, so that the sealing layer fills and/or seals the pores of the passivation layer, wherein the sealing agent comprises titanate and silane, and the mass ratio of the titanate to the silane is 1: the blocking treatment was carried out by immersing the substrate in a blocking solution at a temperature of 50 ℃ for 45 seconds.
Example 5
The stainless steel comprises a stainless steel substrate, a passivation layer and a sealing layer, wherein the passivation layer is arranged on at least one part of the stainless steel substrate, and the sealing layer is arranged on the passivation layer and fills and/or seals pores of the passivation layer. Wherein, the thickness of the passivation layer is 8nm, the porosity is 0.5%, and the thickness of the sealing layer is 0.09 micron.
The preparation method of the stainless steel comprises the following steps:
(1) Pretreating a stainless steel substrate to remove impurities on the surface of the stainless steel substrate;
(2) Passivating the surface of the pretreated stainless steel substrate by adopting a passivator, and forming a passivating layer on at least one part of the surface of the stainless steel substrate, wherein the passivator comprises: the method comprises the following steps of (1) anhydrous sodium dichromate, trisodium citrate dihydrate, ammonium sulfate and water, wherein the passivation treatment is to place a pretreated stainless steel substrate in a passivator at 55 ℃ and soak the stainless steel substrate for 35 minutes;
(3) And (2) sealing the passivation layer by adopting a sealing agent to form a sealing layer on the passivation layer, so that the sealing layer fills and/or seals the pores of the passivation layer, wherein the sealing agent comprises titanate and silane, and the mass ratio of the titanate to the silane is 35: the blocking treatment was carried out by immersing the substrate in a blocking solution at a temperature of 50 ℃ for 60 seconds.
Example 6
The stainless steel comprises a stainless steel substrate, a passivation layer and a sealing layer, wherein the passivation layer is arranged on at least one part of the stainless steel substrate, and the sealing layer is arranged on the passivation layer and fills and/or seals pores of the passivation layer. Wherein, the thickness of the passivation layer is 5nm, the porosity is 1.3%, and the thickness of the sealing layer is 0.05 microns.
The preparation method of the stainless steel comprises the following steps:
(1) Pretreating a stainless steel substrate to remove impurities on the surface of the stainless steel substrate;
(2) Passivating the surface of the pretreated stainless steel substrate by adopting a passivating agent to form a passivating layer on at least one part of the surface of the stainless steel substrate, wherein the passivating agent comprises: the method comprises the following steps of (1) anhydrous sodium dichromate, trisodium citrate dihydrate, ammonium sulfate and water, wherein the passivation treatment is to place a pretreated stainless steel substrate in a passivator at 50 ℃ and soak the stainless steel substrate for 30 minutes;
(3) And sealing the passivation layer by adopting a sealing agent to form a sealing layer on the passivation layer, so that the sealing layer fills and/or seals the pores of the passivation layer, wherein the sealing agent comprises titanate and silane, and the mass ratio of the titanate to the silane is 28: the blocking treatment was carried out by immersing the substrate in a blocking solution at a temperature of 55 ℃ for 40 seconds.
Comparative example 1
The difference from example 3 is that the stainless steel does not include a sealing layer, and the method for manufacturing the stainless steel does not include step (3).
Comparative example 2
The difference from example 3 is that step (3) is: and sealing the passivation layer by adopting the dehydrated antirust oil to form a sealing layer on the passivation layer. The dehydrating antirust oil consists of a dehydrating agent and an antirust agent, wherein the dehydrating agent is an inorganic acid, and the antirust agent comprises mineral oil, an organic acid and salts thereof.
Evaluation of Corrosion resistance of stainless steels in examples 1 to 6 and comparative examples 1 to 2
The evaluation method comprises the following steps: the appearance of the stainless steel was observed after boiling in NaCl solution and the rust rate was calculated, and the evaluation results are shown in table 1.
Note: the test number of each example was not less than 100 pieces, the standard of rust generation was macroscopic rust generation on the surface of the substrate, and the test condition was boiling in a 1.0wt% NaCl solution at 40 to 70kPa for 24 hours.
TABLE 1 Corrosion resistance test results of stainless steels in examples 1-6 and comparative examples 1-2
Examples of the experiments Degree of visible rust on stainless steel surface Percentage of rusting (%)
Example 1 Light and slight 1.8
Example 2 Light and slight 0.5
Example 3 In general 2.0
Example 4 In general 2.4
Example 5 Light and slight 1.0
Example 6 In general terms 2.8
Comparative example 1 Severe severity of disease 13.5
Comparative example 2 Severe severity of disease 10.8
The above examples 1 to 6 are preferred examples of the present invention, and it can be seen from the results of the examples and comparative examples that the rust rate of the stainless steel after the sealing process is increased is significantly reduced compared with the stainless steel after only the passivation treatment, and the effect of the solution using other sealing treatment is not ideal.
In summary, the preferred embodiments of the present invention belong to the protection scope of the present invention when the functional function of the change made according to the technical scheme of the present invention is not beyond the scope of the technical scheme of the present invention.
In the description of the specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (13)

1. A stainless steel, comprising:
a stainless steel substrate;
a passivation layer disposed on at least a portion of the stainless steel substrate;
the sealing layer is arranged on the passivation layer and fills and/or plugs the pores of the passivation layer; the sealing layer contains titanium and silicon, the sealing layer is made of silane and titanate, and the thickness of the passivation layer is 1-10 nanometers; the thickness of the sealing layer is 0.05 to 0.1 micrometer; the mass ratio of the silane to the titanate is (55 to 89): (15 to 45).
2. The stainless steel of claim 1, wherein the passivation layer is a chromium-containing passivation layer.
3. Stainless steel according to claim 1 or 2, characterized in that the porosity of the passivation layer is 0.1 to 2%.
4. The stainless steel of claim 1, wherein the silane and the titanate are present in a mass ratio of 2:1.
5. a method of making the stainless steel of any of claims 1-4, comprising:
(1) Pretreating a stainless steel substrate so as to remove impurities on the surface of the stainless steel substrate;
(2) Passivating the pretreated surface of the stainless steel substrate by adopting a passivating agent so as to form a passivation layer on at least one part of the surface of the stainless steel substrate; and
(3) And sealing the passivation layer by using a sealing agent so as to form a sealing layer on the passivation layer, wherein the sealing layer fills and/or seals the pores of the passivation layer.
6. The method of claim 5, wherein in step (2), the passivating agent comprises anhydrous sodium dichromate, trisodium citrate dihydrate, ammonium sulfate, and water.
7. The method of claim 5, wherein in step (3), the encapsulant comprises a titanate and a silane.
8. The method according to claim 7, wherein the mass ratio of the titanate to the silane is (15 to 45): (55 to 89).
9. The method according to claim 7 or 8, wherein the mass ratio of the titanate and the silane is 1.
10. A lid for a pot, characterized in that it is made of stainless steel according to any one of claims 1 to 4 or obtained by the method according to any one of claims 5 to 9.
11. A cookware, characterized in that it is made of stainless steel according to any of claims 1-4 or obtained by a method according to any of claims 5-9.
12. A cooking appliance, characterized in that it has a lid as claimed in claim 10 and/or a pot as claimed in claim 11.
13. The cooking appliance of claim 12, wherein the cooking appliance is an electric rice cooker, an electric pressure cooker, a soup cooker, or an electric saucepan.
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