JP2011219823A - Organic compound mg-based plated steel plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic compound Mg-based plated steel plate for solving a problem of corrosion under a coating film of a flaw part originally existing in a plated steel plate for an automobile.SOLUTION: In the organic compound Mg-based plated steel plate, on the surface of the steel plate, the Mg-based plated coating containing 30 atom% or more and 85 atom% or less of Mg, 0.03 atom% or more and 10 atom% or less of Ca, and the balance Zn and/or Al with unavoidable impurities is formed. On the surface of the Mg-based plated coating, 0.3 g/mor more and 15 g/mor less of Mg phosphate coating is formed. The content of metallic elements unavoidably mixing from a plated layer into the Mg phosphate coating is 100 mg/mor smaller in total. Organic coatings are sequentially formed on at least one surface on the top surface of the Mg phosphate coating.

Description

  The present invention relates to a coated plated steel sheet, and more particularly to an organic composite Mg-based plated steel sheet having a phosphate film.

  The performance requirements for corrosion resistance of automobile bodies are becoming stricter year by year. In automobiles, the corrosion resistance of the chipping part is regarded as important. In order to prevent rust in automobiles, the amount of Zn-based plated steel sheets is increasing. When using these Zn-based plated steel sheets or alloyed Zn-based plated steel sheets for automobile bodies, after press forming, welding, and assembling processes, they are subjected to phosphate treatment, primed by electrodeposition coating, and further A multi-layer top coat is applied.

The corrosion pattern of the plated material used in such a manner is different from the corrosion pattern of the bare plated material, and it is necessary to consider the corrosion mechanism in an alkaline environment. When scratches that reach the iron core are formed on the coated steel material by chipping or the like, this occurs under the anodic reaction where the plated metal such as Zn and Fe and the iron iron dissolve in the scratches, and under the coating near the scratches. a pair of water and oxygen combine to OH ^- cathode reaction occurs to form a. That is, under the coating film, the pH rises due to the generation of OH ⁻ , resulting in an alkaline environment, so that the plating metal and the phosphate film are dissolved, and further, the corrosion proceeds so that the coating film rises due to the corrosion products. For example, coating film peeling occurs. In particular, in the case of a plated steel sheet that is not so high in sacrificial anti-corrosion ability, such as an alloyed Zn-plated steel sheet, although the swollen width of the coating film itself is small, corrosion products accumulate due to the progress of corrosion of the buttocks, resulting in a scab shape There was also a problem in the appearance after corrosion because the ridges were prominent and the buttock was conspicuous.

  For such corrosion, means for improving corrosion resistance in an alkaline environment by adding a Mg component to the plating layer or the phosphoric acid film is known.

  For example, Patent Document 1 discloses a Zn—Al—Mg-based plated steel sheet in which Al and Mg are contained in the plating layer to improve the under-coating corrosion resistance of the plating layer. However, the main component of this plating layer is composed of Zn, and since the Mg content is low, the main component of the corrosion product is a Zn-based corrosion product, and the effect of improving corrosion resistance under coating by Mg is maintained. I can't. Therefore, a big change cannot be obtained in the form of undercoat corrosion.

  Patent Document 2 discloses an organic composite Zn-based plated steel sheet used for an automobile body, and a plated steel sheet having improved corrosion resistance and coating film adhesion by containing Mg in a phosphoric acid film is disclosed. . The present invention is a Zn phosphate treatment bath containing Mg nitrate, in which Mg is contained in the phosphate film, but this method has a limit on the concentration of Mg nitrate dissolved in the Zn phosphate treatment bath. Therefore, only a small amount of Mg can be contained in the film. For this reason, the amount of Mg contained in the Zn phosphate coating is not sufficient for the amount of zinc coating and the amount of Zn phosphate coating, so the effect of improving the corrosion resistance of Mg cannot be obtained and sufficient corrosion resistance is obtained. I can't get it. Therefore, it is not possible to improve the corrosion form in which corrosion products accumulate on the buttock and swell up and proceed in a scab shape.

  Patent Document 3 discloses a method in which Mg compound such as Mg hydroxide and Mg oxide is contained in the phosphoric acid treatment solution and Mg is contained in the phosphoric acid Zn film. In this case as well, the Mg compound is disclosed. It is difficult to control the pH change due to dissolution of metal, and, similarly to Patent Document 2, the amount of Mg contained in the Zn phosphate film is less than the amount of plating adhesion and the amount of Zn phosphate film. It cannot produce change.

  Therefore, although the effect of Mg content in the plating layer and phosphate film has been studied for corrosion under the coating film so far, both of them contain a small amount of Mg and can fully exhibit the effect of Mg. Since no layer or phosphate coating has been developed, there has been no means for solving the undercoat corrosion problem of the buttocks existing in the plated steel sheet for automobiles.

JP 2001-329383 A Japanese Patent Laid-Open No. 2001-131763 Japanese Patent Laid-Open No. 2001-152355

  The problem to be solved by the present invention is to develop a plated steel sheet capable of suppressing the progress of undercoat corrosion, a scab-like corrosion product, which is a problem with coated Zn-based plated steel sheets. For the purpose of solving the problem, the steel material is plated with Mg as a parent phase, and the phosphate coating contains a certain amount of Mg-based phosphate, or is composed mainly of Mg-based phosphate. An organic composite Mg-plated steel sheet with excellent corrosion resistance in an alkaline environment characterized by forming a phosphate film was investigated.

  Measures to improve corrosion resistance by the inclusion of Mg in the plating layer and phosphate coating have been studied so far, but the structure of the plated steel sheet has been shown so as to dramatically improve the corrosion resistance of undercoat corrosion. I did not come.

  Therefore, in the present invention, a plating layer structure capable of stopping the progress of undercoat corrosion is shown, and it is possible to prevent the progress of undercoat corrosion that could not be solved by an organic composite Zn-based plated steel sheet until now. The object is to provide an organic composite Mg-based plated steel sheet.

  In order to prevent the progress of corrosion under the coating film, it is effective that the corrosion product has a two-layer structure. The two-layer structure of the corrosion product optimized by the present inventors is a dense Mg-based oxide, an upper layer mainly composed of a carbonic acid compound, etc., and basic Zn chloride or Al · Mg-based hydroxide. It is the structure which consists of the lower layer which has as a main component. In other words, in the structure under the coating film, having the structure of the base iron, the plating layer, the Zn-based corrosion product, the Mg-based corrosion product and the coating film in order is the most effective in preventing the progress of corrosion under the coating film I found that there is a good means. Fig. 1 shows the structure of the corroded portion that is effective in preventing the progress of the undercoat corrosion.

  In conventional Zn plating, the corrosion products formed under the coating film are thermodynamically unstable in an alkaline environment, so they disappear immediately and can perform the anticorrosion function for the plating layer and the underlying steel plate. It cannot be done, and red rust is generated from scratches in the coating film in a short time. However, as in the present invention, the presence of an upper-layer corrosion product mainly composed of an Mg-based oxide, a carbonate compound, etc., stable in an alkaline environment, on the Zn-based corrosion product. The corrosion product is retained on the plating layer for a long time, and the corrosion protection effect of the plating by the Zn-based corrosion product is maintained. The present inventors consider that this is due to the stabilization of pH caused by Mg-based corrosion products. That is, in the aqueous solution around the Mg-based corrosion product, the pH is maintained at around 10, and an excessive increase in pH under the coating film is suppressed. At this pH, the disappearance of the Zn-based corrosion product is suppressed.

In addition, Mg-based corrosion products have the effect of inhibiting Fe corrosion in addition to stabilizing Zn-based corrosion products by stabilizing the pH, and Fe ₂ O ₃ (red rust It was found that the problem of scab-like corrosion appearance due to the accumulation of corrosion products can be solved by preventing the formation of) and the like. The present inventors consider that the formation of a passive film due to Fe (OH) ₂ is involved because the pH is fixed at around 10.

  These Mg-based corrosion products can be formed by including Mg of a certain concentration or more in the plating layer.

Further, in the undercoat corrosion, it is important to ensure the adhesion of the coating film at the same time. Ensuring coating film adhesion can be further improved by subjecting the plating containing Mg at a certain concentration or more to chemical conversion treatment. So far, in order to make Mg contained in the Zn-based phosphate film, a method of depositing phosphate by adding Mg nitrate and Mg hydroxide into the chemical conversion solution of Zn phosphate. However, in the case of such a technique, there is an upper limit to the amount of addition to maintain the stability of the bath, and there is also a limit to the amount of Mg that can be contained (actually, the Mg content Therefore, it was difficult to mix Mg phosphate with Zn phosphate on the plating layer.) However, in the present invention,
By making the underlying plating layer a plating layer containing Mg or Zn above a certain level, it is possible to apply Mg-based chemical conversion treatment, which makes it excellent in corrosion resistance in an alkaline environment mainly composed of Mg-based phosphate. An organic composite Mg-based plated steel sheet with a phosphoric acid Mg coating can be prepared.

  Furthermore, since the generation rate of wrinkles due to chipping of automobile steel plates decreases with an increase in the hardness of the plating layer, it is important to increase the hardness of the plating layer in order to prevent wrinkles generated in the plating layer. In the case of Mg-based plating, which is a constituent requirement of the present application, it is possible to increase the plating layer hardness by including a hard amorphous phase, to reduce scratches reaching the base iron, and excellent chipping scratch resistance It is possible to provide steel sheets.

  The present invention has been made based on such findings, and the gist thereof is as follows.

(1) On at least one surface of the steel plate,
Mg is 30 atomic% or more, 85 atomic% or less,
Containing 0.03 atomic% or more and 10 atomic% or less of Ca,
Furthermore, an Mg-based plating film composed of Zn and / or Al and inevitable impurities is formed,
On the surface of the Mg-based plating film,
A phosphoric acid Mg film of 0.3 g / m ² or more and 15 g / m ² or less is formed, and the amount of inevitable impurities in the phosphoric acid Mg film is 100 mg / m ² or less,
Further, an organic composite Mg-based plated steel sheet, wherein an organic film is sequentially formed on at least one surface of the upper surface of the phosphoric acid Mg film.
(2) The organic composite Mg-based plated steel sheet according to claim 1, wherein the Mg-based plated film contains Al at 10 atomic% or less and an amorphous phase at a volume content of 5% or more.

(3) organic composite Mg plated steel sheet according to claim 1 or 2 weight per unit area of the organic coating is characterized in that it is a 0.2 to 3 g / m ^2.

  The organic composite Mg-based plated steel material of the present invention is excellent in versatility and economy because it can be manufactured by a normal hot dipping process, chemical conversion treatment process, and electrodeposition coating process. In addition, it is superior in corrosion resistance under the paint film compared to the widely used paint zinc-based plated steel material, so it is widely used even in fields where paint zinc-plated steel material could not be used due to the problem of corrosion resistance under the paint film. Is possible. In addition, it is possible to contribute to the development of the industry by extending the life of steel materials and reducing maintenance labor.

The schematic diagram of the anticorrosion structure by formation of Mg corrosion product is shown.

  Hereinafter, the organic composite Mg-based plated steel material according to the present invention will be described in detail. In order to increase the corrosion resistance of corrosion under the coating film, the present inventors examined the application of an Mg component that is stable in a high pH alkaline environment and has high corrosion resistance.

The basic undercoat corrosion of Zn-plated steel materials starts from the coating film so that it progresses under the coating film, and the corrosion mechanism is considered as follows. First, ZnCl ₂ · 4Zn (OH) ₂ which is basic Zn chloride is formed at the initial stage of corrosion, and finally changes to ZnO. Subsequent to the formation of ZnCl ₂ · 4Zn (OH) ₂ , the ground iron begins to corrode, and the corrosive organisms finally change to Fe-based porous Fe ₃ O ₄ and FeOOH. In this corrosion mechanism, the formation of ZnO is suppressed and ZnCl ₂ · 4Zn (OH) ₂ is maintained for a long period of time.

  The present invention also provides good corrosion resistance by this mechanism. That is, the improvement in corrosion resistance by Mg is due to the effect of stabilizing the formation of basic Zn chloride. Although the mechanism by which Mg stabilizes basic Zn chloride is not known in detail, the present inventors, first of all, believe that when Mg is formed as a corrosion product, the pH is around 10 This stabilizes basic Zn chloride, and secondly, Mg, C, and O bind preferentially, thereby inhibiting (inhibiting) the reaction between Zn, C, and O, and binding to Cl. As a result, we believe that the formation of basic Zn chloride may be stabilized.

  Referring to FIG. 1, Mg corrosion products are formed in the outer layer of Zn-based corrosion products. The main corrosion products of Mg are carbonate compounds and oxides. That is, the collar portion 7 has the structure of the coating film 6, the Mg-based corrosion product 5, the Zn-based corrosion product 3, and the ground iron 1 from the outside. This two-layer structure is formed by corrosion of the plating layer 2 containing Mg and Zn at the same time (particularly when Mg is in the range of 30 atomic% to 85 atomic%). The mechanism of formation of Mg-based corrosion products in the outer layer and Zn-based corrosion products in the inner layer has not been elucidated in detail, but it is related to the ease of binding of Mg ions, Zn ions to O, C, Cl. It is estimated that.

  The Mg-based corrosion product 5 formed in the outer layer has a denser structure than the Zn-based corrosion product 3, and the Mg-based corrosion product 5 having this dense structure covers the flange 7, so that ions from the outside world are present. It becomes a barrier that blocks the diffusion of, and has the effect of greatly suppressing the progress of corrosion.

  Therefore, by taking this two-layer corrosion product structure, since basic Zn chloride is protected for a long period of time, corrosion of the base iron is suppressed, and therefore volume expansion due to the formation of Fe-based oxides can also be suppressed. Corrosion resistance under coating film is greatly improved, such as suppression of scab-like wrinkles.

As will be described later, there are cases where Al is contained in the plating layer for the purpose of improving the corrosion resistance, but in this case as well, the lower layer is formed of corrosion such as Mg ₂ Al (OH) ₇ and Mg ₄ Al ₂ (OH) _14. The anticorrosion mechanism is the same except that it is composed of objects. However, the stability of corrosion products in an alkaline environment is higher for Zn-based corrosion products than for Al-based corrosion products, so the constituents of the underlying corrosion products are Zn-based corrosion products. Is preferred. For this reason, the plating layer has a tendency to prevent corrosion of the base iron for a long time when the Zn concentration is higher than the Al concentration.

  Mg-based corrosion products are rapidly formed at the same time as the soot formation and close the soot. For this reason, in the very initial stage of corrosion, the swelling around the buttock may be larger than the existing organic composite Zn-plated steel sheet, but in the long term, the organic composite Mg-based steel sheet Is also excellent in appearance.

  In order to rapidly form Mg-based corrosion products in the buttock, the Mg concentration in the plating layer needs to be a certain concentration or higher. By setting Mg in the plating layer to 30 atomic% or more (hereinafter, “%” unless otherwise specified means atomic%), Mg-based corrosion products are rapidly formed in the heel. It was found that a two-layered corrosion product formed. The upper limit concentration of Mg in the plating layer is 85%. This is because Mg has poor reactivity with Fe, and when the Mg concentration exceeds 85%, it is difficult to adhere to the steel sheet as a plating layer.

  Ca is an indispensable element for industrially performing Mg-based plating. Although Mg in a molten state may be rapidly oxidized and ignited, Mg can be prevented from being ignited by adding Ca that is more easily oxidized than Mg. If plating is performed in an inert atmosphere, addition of Ca is not necessary, but in the case of atmospheric operation, addition of Ca is essential. Addition of 0.03% or more of Ca has the effect of preventing the ignition of Mg, so this is the lower limit concentration. If Ca is added up to 10%, it can be added while lowering the melting point of the plating bath. However, Ca is a metal that is easier to oxidize than Mg, so if it exceeds 10%, the oxidation of Ca becomes too intense, Ca sudden oxidation and ignition occur, and the plating bath viscosity becomes high, Since the plating operation itself becomes difficult, the upper limit of Ca addition is 10%.

  The plating remainder other than Mg and Ca is preferably Zn. A preferable Zn concentration range from the viewpoint of corrosion resistance of the plating layer, plating bath temperature, dross generation, and the like is 20% or more and 40% or less. The plating remainder may be Al other than Zn. The preferable concentration range of Al is the same as that of Zn, and is 20% or more and 40% or less. Both Zn and Al are suitable for plating production because the melting point of the plating bath can be kept low in this concentration range. Further, from the viewpoint of improving corrosion resistance, it is preferable that both Zn and Al are contained. However, if the Al concentration is high, the corrosion resistance of the plating layer itself is improved, but a lot of Al-based corrosion products are contained in the corrosion products. Corrosion product stability is higher for Zn-based corrosion products than for Al-based corrosion products, so when considering the anticorrosion period of the base iron, the remainder of the plating other than Mg and Ca is mainly Zn. Preferably there is.

  The Mg-based plating of the present invention contains elements such as Ni, Cu, Ag, Si, Co, Mn, Nb, Mo, Ti, Cr, etc., in an amount of about 0.1 to 5% for the purpose of imparting corrosion resistance. It is possible. For example, by adding these metals, the electrochemical properties change, the metal dissolution reaction (anode reaction) is suppressed, the corrosion current density is reduced, and the corrosion resistance is improved. The present inventors presume that these effects of improving corrosion resistance are caused by the dispersion of electrochemically noble elements in the plating layer.

  In the corrosion under the coating film, it is important for the organic composite plated steel material to improve the coating film adhesion. Ensuring film adhesion can be improved by including Mg in the chemical conversion coating. When Mg is contained in the chemical conversion film, the structure of the phosphate crystal changes. Phosphate crystals that do not contain Mg are candy-shaped, and crystals with a size of 5 to 10 μm are formed, whereas phosphate crystals that contain Mg are columnar and fine crystals of 2 to 3 μm. Form.

The chemical conversion treatment used for the paint base is generally a phosphorylation chemical treatment. For example, Zn phosphate, Fe (II) phosphate, Mn phosphate, Zn-Ca phosphate, and Ca phosphate treatment are known. These can also be applied to Mg-based plating. Among these, the application of Zn phosphate treatment is common for plated steel sheets for automobiles. The treatment bath used to form this Zn phosphate film contains phosphate ions, Mn ions, Zn ions, Fe ions, etc., and further contains reaction accelerators (F ions, SiF ₆ ions, Ni ions), etc. May be contained.

  In the present invention, the underlying plating layer is a plating layer containing a certain amount of Mg and Zn, and the Mg in the plating layer is a certain concentration or more, for example, 30 atomic% or more, thereby performing a chemical conversion treatment applied to the Mg alloy. By applying, it is possible to form a chemical conversion film on the plating layer. If it is less than 30 atomic%, the Mg concentration in the plating layer is low, and even if the chemical conversion treatment used for the Mg-based alloy is applied, a stable chemical conversion treatment film cannot be formed.

The chemical conversion treatment applied to Mg alloys is the formation of Mg ₃ (PO ₃ ) ₄ , Mg ₂ PO ₄ (OH), etc. on the Mg alloy surface by the potassium permanganate solution, which has recently attracted attention as an alternative treatment technology for chromate film. This is a phosphoric acid film treatment.
For example, potassium permanganate, phosphoric acid, ammonium dihydrogen phosphate dissolved in the solution, permanganate ion, phosphate ion, hydrogen ion, ammonium ion (in some cases, vanadium ion, chromium ion, etc. are also included) ) And the like in a solution containing Mg alloy for several minutes.
Normally, the chemical conversion treatment of Mg alloy with potassium permanganate solution involves immersing the Mg alloy in an acidic potassium permanganate solution containing phosphoric acid, and simultaneously dissolving the surface of the Mg alloy and depositing phosphoric acid. Then, Mg phosphate is deposited on the alloy surface. The immersion time of the solution is reasonable for several minutes, but the Mg alloy has a thickness reduction of several tens of g / m ² (10 to 20 μm) due to the pickling treatment before chemical conversion and the continuous dissolution reaction during solution immersion. The reaction between Mg ions and phosphate ions generated during dipping causes precipitation of Mg phosphates of 20 g / m ² or less.

  Based on this, when this chemical conversion treatment is applied to Mg-based plating, the thickness of the plating layer is significantly reduced, so it seems that Mg conversion treatment is difficult to apply. Although the thickness of the plating layer is reduced by the pickling treatment, the dissolution reaction at the time of immersion in the solution is not as violent as that of the Mg alloy, occurs for a certain time, and the dissolution reaction stops halfway. The present inventors presume that this involves the Zn, Al, and Ca concentrations contained in the plating layer. Therefore, this Mg alloy treatment can be applied even to a plating layer of 20 μm or less. Further, whether or not this reaction can proceed is a reaction that depends on the concentration of a metal element other than Mg. Therefore, the processing does not become impossible by including an amorphous phase or a non-equilibrium phase in the plating layer. The Zn and Al concentrations necessary to stop this Mg dissolution reaction are estimated to be 15 atomic% or more. At concentrations below that, Mg concentration is severely dissolved, and potassium permanganate solution is used for Mg-based plating. This phosphoric acid film treatment is not applicable. Further, the Ca concentration is a concentration defined by the production conditions for Mg-based plating.

As the chemical conversion treatment, the present inventors used a chemical conversion treatment bath adjusted to pH = 4 with potassium permanganate (20 g / l), ammonium dihydrogen phosphate (100 g / l), and phosphoric acid. As pretreatment, the Mg-based plating was immersed in a 3 vol% phosphoric acid aqueous solution for 1 second, and then immersed in a chemical conversion bath.
In this case, a phosphate film is rapidly deposited on the surface by immersion for 5 seconds or less. At this time, since the surface of the plating layer becomes light brown, this treatment is also effective as an anti-fading treatment for Mg. Up to about 15 seconds, the basis weight of the chemical conversion film deposited increases (the plating surface turns brown). The reaction of Mg phosphate precipitated on the surface in about 1 minute is considered to stop. By this treatment, the basis weight of the obtained Mg phosphate film amount is about 15 g / m ^{2 at} maximum when the plating layer is 20 μm.

The basis weight of the phosphoric acid Mg film is preferably 0.3 g / m ² or more. If the phosphoric acid Mg film is less than 0.3 g / m ² , the adhesion of the coating film is deteriorated and the swollen width of the coating film tends to be large.
When the phosphate film obtained under the above-mentioned conditions was analyzed by XRD, Mg ₃ (PO ₄ ) ₂ was detected as a diffraction peak. Is done. The formed Mg phosphate was dissolved in 5vol% chromic acid (VI) and analyzed for components. The main component of the film was Mg phosphate, but other metal ions were used in the plating layer. A small amount of Mn contained in Zn, Al, Ca, and potassium permanganate solution contained in. Depending on the composition of the plating layer, the amount of Zn, Al, Ca and Mn inevitably mixed in the phosphoric acid Mg film varies, but the total content does not exceed 100 mg / m ² .
In XRD, since compounds containing these elements are not detected in XRD, it is considered that Mg and substituted compounds are formed and contained in the phosphate film as oxides or phosphate compounds. These elements are inevitable impurities.
The corrosion resistance of this chemical conversion treatment is not significantly different from that of a Zn-based phosphoric acid film containing Mg phosphate, but since the treatment can be completed in a few seconds, it has a feature that the coating ground treatment can be simplified.

The present application exhibits excellent corrosion resistance by further coating an organic film on the phosphoric acid Mg film upper layer on at least one side. The coating conditions are as described above.
That is, the organic film to be coated may be a single organic resin, but considering the corrosion resistance, the organic resin and SiO ₂ , Al ₂ O ₃ , MgO, Fe ₂ O ₃ , Fe ₃ O ₄ , ZrO ₂ , It is desirable to be a powder selected from TiO ₂ and SnO ₂ or a composite film combined with one or more colloids. In addition, in this organic film, a wax component, a color pigment, a rust preventive agent, etc. can be contained, and when a wax component is added, it can be processed without oil depending on molding processing conditions. Become. There are no particular restrictions on the type of organic resin, but when considering automotive steel sheet applications, epoxy resin (such as bisphenol A type epoxy resin) is used as the current electrodeposition coating. From the viewpoint of ensuring compatibility and adhesion, an epoxy resin is preferred.

The formation of Mg-based phosphate film has almost no effect on coating film formation, and the same coating treatment as that of Zn-based phosphate film is possible, and a thin organic composite film can also be formed.
In the case of a thin film organic composite Mg-plated steel sheet premised on welding after painting, the amount of organic coating attached is preferably 0.2 to 3 g / m ² . If it is less than 0.2 g / m ^2, it is difficult to produce a uniform organic thin film with a roll coater, and if it exceeds 3 g / m ² , the weldability tends to deteriorate.

  Moreover, undercoat corrosion is corrosion that occurs when plating or scratches that reach the ground iron are formed. Therefore, if it is possible to prevent scratches reaching the ground iron, it is not necessary to sacrificial corrosion protection of Fe, so that the progress of corrosion can be suppressed. In order to prevent scratches that reach the iron core, it is only necessary to improve the hardness of the plating layer. In the Mg-based plating adopted in this application, the hardness of the plating layer can be increased by including an amorphous phase in the plating layer. Is possible. Specifically, corrosion under the coating film can be suppressed by setting the Al concentration in the plating layer to 10 atomic% or less and further containing amorphous in a volume content of 5% or more. The volume fraction of the amorphous phase necessary to make the average hardness of the plating layer composition described in the present application about 100 Hv or more is 5%.

  The amorphous phase is a hard phase obtained when the molten metal is rapidly cooled, and the cooling conditions necessary for the formation of the amorphous phase vary depending on the alloy composition, but in the composition range disclosed as the Mg-based plating of the present invention. If Al is 10% or less, it can be obtained by rapidly cooling the plated layer in a molten state after plating at a cooling rate of about 1000 ° C./sec or more. The upper limit of the Al concentration is because Al is an element that reduces the amorphous forming ability.

  Confirmation of the formation of the amorphous phase can be confirmed by obtaining a halo pattern in the X-ray diffraction image of the plating layer. If it is a single amorphous phase, it can be confirmed only by a halo pattern (in some cases, an Fe diffraction peak of a steel material may be detected).

  When the amorphous phase and the crystalline phase are mixed and the amorphous volume fraction is low, the plating layer is detected by detecting the exothermic peak when the amorphous phase crystallizes during the temperature rising process using a differential thermal analyzer. The presence of the amorphous phase can be confirmed.

  In order to obtain the amorphous volume fraction, the plated steel material is cut, its cross section, polished and etched, and the cross section of the plated layer on the steel material surface is observed with an optical microscope (hereinafter, light microscope). No structure is observed in the amorphous part even by etching, but in the part where the crystal phase remains, the structure due to the crystal grain boundaries, sub-grain boundaries, precipitates, and the like is observed. Thereby, since the area | region of an amorphous part and a crystal | crystallization part is distinguished clearly, it can convert into a volume ratio by the line segment method or image analysis.

  When the structure is too fine and measurement with a light microscope is difficult, a thin piece is produced from the cross section of the plating layer and observed with a transmission electron microscope, so that the measurement can be performed in the same manner. In the case of a transmission electron microscope, it is also possible to confirm an amorphous structure by a halo pattern of an electron beam diffraction image in a region where no tissue is observed. Therefore, in the light microscope observation, if the structure is not observed on the entire surface, or if there is a part where the structure is not observed even if it is suspected to be a coarse and undistorted crystal grain, a thin slice for an electron microscope is further collected. Thus, it is desirable to confirm that the phase is an amorphous phase by observing a halo pattern without a diffraction spot in the electron diffraction pattern.

  In both the light microscope and the electron microscope, it is desirable to obtain the area ratio by image processing using a computer for 10 or more different fields of view and average them to obtain the volume ratio.

  A plating bath having the components shown in Table 1 was prepared, and a surface-treated steel material was prepared using a cold-rolled steel plate having a thickness of 0.8 mm as a base material. Cold-rolled steel sheets (thickness 0.8 mm) were cut into 200 mm × 100 mm, and then plated with a batch-type hot dipping test apparatus manufactured in-house. The bath temperature of the plating bath was maintained at 480 to 670 ° C. and 50 ° C. higher than the melting point of the plating bath. The basis weight was adjusted by air wiping. The plated layer containing the amorphous phase is subjected to Cu plate pressing immediately after air wiping. All of the produced plating thicknesses were set to about 12 μm. Before being subjected to each test, the plated steel sheet was cut into 50 × 100 mm.

  As a pretreatment for the phosphorylation treatment, each plated steel plate was immersed in 3 vol% phosphoric acid for 1 second. As the phosphorylation treatment bath, a chemical treatment bath adjusted to pH = 4 with potassium permanganate (20 g / l), ammonium dihydrogen phosphate (100 g / l) and phosphoric acid was used. The temperature of the chemical conversion bath was 40 ° C., and the amount of adhesion was controlled by changing the immersion time from 0.5 seconds to 300 seconds.

The phosphate coating of the sample after the phosphate treatment was dissolved in chromic acid (chromium oxide (VI) (5% solution, immersed at 20 ° C. for 3 minutes). The amount of phosphate adhered was measured.
When electrodeposition coating was used as the organic coating, Powernicks 110 gray paint made by Nihon Paint Kogyo Co., Ltd. was applied as a coating treatment with a film thickness of 20 μm. The baking heat treatment conditions were 150 ° C. and 20 minutes.

  As a comparative material, an organic composite Mg-based plating treated with chromate was prepared. For the chromate treatment, No. 20 Modified Chrome Pickle (Dow Chemical Co., Midland, Mich 'Operation in Magnesium finishing' 1986 p. 36) was used. Those subjected to the chromate treatment are indicated by “Re” in Table 1.

  In the center of the sample, from the surface, make a cross-cut scissors with a diagonal length of 70 mm that reaches the base iron with a cutter knife, then CCT test (salt spray (0.5% NaCl, 35 ° C) 6 hours → dry (50 ° C, 45 ° C) % RH) 3 hours → wet (50 ° C., 95% RH) 14 hours → drying (50 ° C., 45% RH) 1 hour). The wound appearance was examined after 140 cycles, and the film swelling width was measured. In Table 1, “X” indicates that a scab-like corrosion product was detected on the buttock, and “◯” indicates that no scab corrosion product was detected. By visual inspection, the swollen width of the coating film (average of 4 points around the cut ridge) was 2 mm or less as “◎”, 2 to 3 mm as “◯”, 3 to 3.5 mm as “△”, and 3.5 mm or more as “x”. . What was not evaluated was set to "-".

  The amorphous volume fraction of the plating layer was determined by taking two pieces of transmission electron microscope slices each at a position where the thickness of the plating layer of the test piece was equally divided into five pieces, and analyzing the image by using a computer. The area ratio of the amorphous region was measured, and the average value of the area ratio of the amorphous region in the entire visual field was defined as the amorphous volume fraction. In Table 1, when the plating layer contained an amorphous phase of 5% or more in volume fraction, “◯” and less than 5% were designated as “x”.

For other thin film organic coatings, vinyl-modified epoxy ester resin is used and blended with blocked isocyanate curing agent, modified polyethylene wax, and condensed azo red pigment (each solid content ratio is 100: 10: 5: 3) Based on water-based resin, using a coating material with colloidal silica added to a solid content mass ratio of 16%, the basis weight of the dry film is 1 g / m ² per side while controlling the number of revolutions with a roll coater. It was applied to both sides and then baked to reach 150 ° C. at the ultimate plate temperature and cooled with water. The ones that have been painted are
For the evaluation of weldability, a Cu-Cr CF-type electrode tip (5 mmφ) was used, and an appropriate current range was measured with a pressure of 1961 N (200 kgf) and an energization time of 13 cycles. In Table 1, “1.5” for over 1.5 kA, “O” for 1.0-1.5 kA, “△” for 0.3-1.0 kA, “×” for less than 0.3 kA, and “−” "

  The organic composite Mg-based plated steel material of the present invention is excellent in versatility and economy because it can be manufactured by a normal hot dipping process, chemical conversion treatment process, and electrodeposition coating process. In addition, it is superior in corrosion resistance under the paint film compared to the widely used paint zinc-based plated steel material, so it is widely used even in fields where paint zinc-plated steel material could not be used due to the problem of corrosion resistance under the paint film. Is possible. In addition, it is possible to contribute to the development of the industry by extending the life of steel materials and reducing maintenance labor.

1 Fe
2 Plating layer 3 Zn-based corrosion product 4 Phosphoric acid film 5 Mg-based corrosion product 6 Coating film 7 Cut collar

Claims (3)

On at least one side of the surface of the steel plate,
Mg is 30 atomic% or more, 85 atomic% or less,
Containing 0.03 atomic% or more and 10 atomic% or less of Ca,
Furthermore, an Mg-based plating film composed of Zn and / or Al and inevitable impurities is formed,
On the surface of the Mg-based plating film,
A phosphoric acid Mg film of 0.3 g / m ² or more and 15 g / m ² or less is formed, and the amount of inevitable impurities in the phosphoric acid Mg film is 100 mg / m ² or less in total.
Further, an organic composite Mg-based plated steel sheet, wherein an organic film is sequentially formed on at least one surface of the upper surface of the phosphoric acid Mg film.   2. The organic composite Mg-based plated steel sheet according to claim 1, wherein the Mg-based plating film contains Al at 10 atomic% or less and an amorphous phase at a volume content of 5% or more. Organic composite Mg plated steel sheet according to claim 1 or 2 weight per unit area of the organic coating is characterized in that it is a 0.2 to 3 g / m ^2.

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