WO2013054997A1 - Corrosion resistant metal and metal-surface modification method for improving corrosion resistance using oxynitriding - Google Patents

Corrosion resistant metal and metal-surface modification method for improving corrosion resistance using oxynitriding Download PDF

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WO2013054997A1
WO2013054997A1 PCT/KR2012/003438 KR2012003438W WO2013054997A1 WO 2013054997 A1 WO2013054997 A1 WO 2013054997A1 KR 2012003438 W KR2012003438 W KR 2012003438W WO 2013054997 A1 WO2013054997 A1 WO 2013054997A1
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sulfate
metal surface
acid
sulfide
nitriding
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French (fr)
Korean (ko)
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이성혁
김주헌
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중앙대학교 산학협력단
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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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/34—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in more than one step
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment

Definitions

  • the present invention relates to a corrosion-resistant metal using oxynitride and a method for modifying the metal surface for improving the corrosion resistance, and more particularly, the metal surface is sequentially exposed to sulfur (S) aqueous solution during or after nitriding step and
  • S sulfur
  • the present invention relates to a method of modifying a metal surface for improving corrosion resistance, including an oxidation step of fumigation and oxidation.
  • Oxidative nitriding treatment is a metal surface modification method that creates a nitride layer on the metal surface by nitriding process and forms an oxide layer on the nitride layer to give abrasion resistance, slidability, and corrosion resistance. A method is proposed.
  • Representative methods of oxynitride include nitrotec method based on nitrogen base method, QPQ treatment or OPO treatment after salt bath nitriding, NN method to inject oxidant during nitriding or Rogalski method. It is used.
  • the above-mentioned oxynitride method has an effect of increasing the corrosion resistance of alloy steel and high carbon steel, but has a disadvantage of not having an effect of increasing the corrosion resistance of low grade steel and low carbon steel.
  • the present inventors exposed and fumigated the metal surface to an aqueous solution vapor containing sulfur (S) during or after the nitriding step or the nitriding step in order to improve the corrosion resistance of the metal surface.
  • S aqueous solution vapor containing sulfur
  • An object of the present invention is to provide a corrosion resistant metal having the same or better corrosion resistance as alloy steel by treating oxynitride with low grade steel and low carbon steel.
  • Another object of the present invention is to provide a metal surface modification method for treating oxynitride on low grade steel and low carbon steel to give the same or better corrosion resistance as alloy steel.
  • the present invention provides a corrosion-resistant metal comprising a nitride layer and an oxide layer obtained by treating the surface of the metal with an aqueous solution containing sulfur (S) in an amount of 0.1 to 10% by weight.
  • the present invention in the metal surface modification method for improving the corrosion resistance including the surface cleaning step, preheating step and nitriding step, the aqueous solution vapor containing sulfur (S) during the nitriding step or after the nitriding step sequentially It provides a metal surface modification method for improving the corrosion resistance, characterized in that it comprises an oxidation step of the oxidation treatment by exposure and fumigation.
  • Corrosion-resistant metals and metal surface modification method is a pore layer inside the oxide layer formed on the nitride layer or the diffusion layer by adding a substance containing sulfur (S) component at the same time as the nitriding treatment or during the oxidation treatment after disease treatment Since the sulfur (S) increases the bonding strength of oxygen (O 2 ), iron (Fe) and nitrogen (N) to increase the corrosion resistance, there is an effect to increase the corrosion resistance while maintaining slidability and wear resistance.
  • S sulfur
  • O 2 oxygen
  • Fe iron
  • N nitrogen
  • Figure 2 shows a metal surface modification method according to another embodiment of the present invention.
  • the present invention provides a corrosion-resistant metal comprising a nitride layer and an oxide layer obtained by treating the metal surface with an aqueous solution containing sulfur (S) in an amount of 0.1 to 10% by weight.
  • the metal surface may be treated by surface cleaning, preheating, and nitriding, and the metal surface may be oxidized by sequentially exposing and fumigating the metal surface to an aqueous solution containing sulfur (S) during or after nitriding.
  • S sulfur
  • the aqueous solution containing sulfur (S) is sulfuric acid (H 2 SO 4 ), Sulfur dioxide (SO 2 ), Sulfur trioxide (SO 3 ), Sulfurous acid (H 2 SO 3 ), Copper sulfate anhydride (CuSO 4 ), Copper sulfate (II) pentahydrate (CuSO 4 5H 2 O), lead sulfate (PbSO 4 ), Barium sulfate (BaSO 4 ), Sodium sulfate (Na 2 SO 4 ), Sodium hydrogen sulphate (NaHSO 4 ), Zinc sulfate (ZnSO 4 ), Aluminum sulfate (Al 2 (SO 4 ) 3 ), Ammonium sulfate ((NH 4 ) 2 SO 4 )), Silver sulfate (Ag 2 SO 4 ), Calcium sulfate (CaSO 4 ), Magnesium sulfate (MgSO 4 ), Chromium Sulfate (C
  • the present invention in the metal surface modification method for improving the corrosion resistance including the surface cleaning step, preheating step and nitriding step, the aqueous solution vapor containing sulfur (S) during the nitriding step or after the nitriding step sequentially It provides a metal surface modification method for improving the corrosion resistance, characterized in that it comprises an oxidation step of the oxidation treatment by exposure and fumigation.
  • the surface washing step of removing foreign matter and oil on the metal surface A preheating step of heating and preheating the metal surface on which the surface cleaning step is performed; And an oxidation step in which at least one of a nitride layer and a diffusion layer is formed on the metal surface preheated through the preheating step, and at the same time, the metal surface is oxidized by exposing and fumigation to an aqueous vapor containing sulfur (S).
  • S aqueous vapor containing sulfur
  • the surface cleaning step of removing foreign matter and oil on the metal surface A preheating step of heating and preheating the metal surface on which the surface cleaning step is performed; A nitriding step of forming at least one of a nitride layer and a diffusion layer on the preheated metal surface through the preheating step; And an oxidation step of subjecting the metal surface treated in the nitriding step to oxidation and oxidation by exposing and fumigation to an aqueous solution vapor containing sulfur (S).
  • S aqueous solution vapor containing sulfur
  • the nitriding step includes a gas nitriding method in which only ammonia (NH 3 ) gas is added to the nitriding furnace to carry out a nitriding process;
  • nitrogen (N), carbon dioxide (CO 2 ), and ammonia (NH 3 ) may be performed using any one method selected from a gas soft nitriding method in which a nitriding process is performed.
  • the oxidation step is charged and heated step of charging the metal base material in the furnace, the internal temperature is 350 °C to 600 °C range;
  • a sulfur (S) aqueous solution steam input step of inputting and treating an aqueous solution steam containing sulfur (S) while maintaining the final temperature of the charging and temperature raising step.
  • the oxidation step may be charged and heated step of charging the metal base material in the furnace, the internal temperature is 350 °C to 600 °C range; And while maintaining the final temperature of the charging and the step of raising the temperature may include a sulfur (S) aqueous solution steam input step of adding 0.1 to 10% by weight of an aqueous solution steam containing sulfur (S) and processing for 1 to 60 minutes. .
  • S sulfur
  • aqueous solution steam input step of adding 0.1 to 10% by weight of an aqueous solution steam containing sulfur (S) and processing for 1 to 60 minutes.
  • Fe 2 O 3 may be generated to cause red blue crystals and to change the color of the product, and the content of the aqueous vapor containing sulfur (S) may be in the above range. If this occurs, the nitride layer and the oxide layer may not be firmly adhered to each other. If the treatment time of the aqueous solution vapor containing sulfur (S) is out of the above range, the peeling phenomenon, the sulfation phenomenon, and the vaporization of the aqueous solution may not be smooth. Unsuccessful problems may arise.
  • Sulfur (S) aqueous solution is added to the oxidation step in the present invention is sulfuric acid (H 2 SO 4 ), Sulfur dioxide (SO 2 ), Sulfur trioxide (SO 3 ), Sulfurous acid (H 2 SO 3 ), Copper sulfate anhydride (CuSO 4 ), Copper sulfate (II) pentahydrate (CuSO 4 5H 2 O), lead sulfate (PbSO 4 ), Barium sulfate (BaSO 4 ), Sodium sulfate (Na 2 SO 4 ), Sodium hydrogen sulphate (NaHSO 4 ), Zinc sulfate (ZnSO 4 ), Aluminum sulfate (Al 2 (SO 4 ) 3 ), Ammonium sulfate ((NH 4 ) 2 SO 4 )), Silver sulfate (Ag 2 SO 4 ), Calcium sulfate (CaSO 4 ), Magnesium sulfate (MgSO 4
  • the metal surface modification method according to the present invention may further include any one or more steps selected from the group consisting of rust prevention, sealing, waxing, and coating after the oxidation step.
  • the present invention can provide a corrosion-resistant metal, characterized in that the metal surface is modified through the metal surface modification method.
  • the present invention relates to a metal surface modification method for improving corrosion resistance, comprising an oxidation step of oxidizing and exposing and fusing a metal surface to an aqueous solution vapor containing sulfur (S) sequentially during or after nitriding.
  • S sulfur
  • JIS SPCC JIS SPCC
  • JIS SAPH440 JIS SAPH440
  • S45C surface-washed at about 80 to 90 degrees with T.E.C. steam for 1 hour, and then the metal surface was modified under the process conditions shown in Table 1 below.
  • JIS SPCC JIS SPCC
  • JIS SAPH440 JIS SAPH440
  • S45C S45C
  • JIS SPCC JIS SPCC
  • JIS SAPH440 JIS SAPH440
  • S45C S45C
  • the surface-treated metal as shown in Example 4 is significantly improved in the corrosion resistance compared to the surface-treated metal through the general oxynitride process as a comparative example I could confirm it.
  • Example 1 Example 2 SAPH440 120 432 160 SPCC 24 288 80 S45C 200 280 430

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Abstract

The present invention relates to a corrosion resistant metal and to a metal-surface modification method for improving corrosion resistance using oxynitriding. More specifically, the invention relates to: a metal-surface modification method for improving corrosion resistance, comprising an oxidation step in which a metal surface is sequentially exposed to the vapour of an aqueous solution comprising sulphur (S) and fumigated and an oxidation treatment carried out, either during a nitriding step or after the nitriding step; and a corrosion resistant metal. In particular, in the metal surface modification method according to the present invention, a substance comprising a sulphur (S) component is additionally introduced during the oxidation treatment that takes place either simultaneously with the nitriding treatment or after the nitriding treatment, thereby greatly increasing the number of pore layers in the oxide layer produced on the diffusion layer or nitride layer, and the sulphur (S) enhances the bonding force of oxygen (O2), iron (Fe) and nitrogen (N) such that the corrosion resistance is enhanced, and thus the present invention makes it possible to provide a metal in which sliding characteristics and abrasion resistance are maintained while even corrosion resistance is enhanced.

Description

산질화를 이용한 내식성 금속 및 내식성 향상을 위한 금속 표면 개질 방법Corrosion Resistant Metal Using Oxidation and Metal Surface Modification Method for Improving Corrosion Resistance
본 발명은 산질화를 이용한 내식성 금속 및 내식성 향상을 위한 금속 표면 개질 방법에 관한 것으로, 보다 상세하게는 질화 단계 중 또는 질화 단계 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 내식성 향상을 위한 금속 표면 개질 방법에 관한 것이다. The present invention relates to a corrosion-resistant metal using oxynitride and a method for modifying the metal surface for improving the corrosion resistance, and more particularly, the metal surface is sequentially exposed to sulfur (S) aqueous solution during or after nitriding step and The present invention relates to a method of modifying a metal surface for improving corrosion resistance, including an oxidation step of fumigation and oxidation.
일반적으로 금속 표면의 내식성 증가를 위한 처리 방법으로는 페인팅, 도금, 코팅 및 산질화 처리가 이용되고 있다. In general, painting, plating, coating and oxynitride are used as treatment methods for increasing corrosion resistance of metal surfaces.
산질화 처리는 금속 표면에 질화 공정으로 질화층을 생성하고 상기 질화층 위에 산화층을 형성시켜 내마모성, 내습동성 및 내식성을 크게 부여하는 금속 표면 개질 방법으로서, 질화처리 방법과 산화처리 방법에 따라 여러 가지 방법이 제안되어 있다. Oxidative nitriding treatment is a metal surface modification method that creates a nitride layer on the metal surface by nitriding process and forms an oxide layer on the nitride layer to give abrasion resistance, slidability, and corrosion resistance. A method is proposed.
산질화의 대표적인 공법으로는 질소베이스법을 기초한 나이트로텍(NITROTEC)법, 염욕연질화 후 처리하는 QPQ 처리법 또는 OPO 처리법, 질화처리시 산화제를 투입하는 NN법 또는 로갈스키(Rogalski)법 등이 이용되고 있다. Representative methods of oxynitride include nitrotec method based on nitrogen base method, QPQ treatment or OPO treatment after salt bath nitriding, NN method to inject oxidant during nitriding or Rogalski method. It is used.
하지만, 전술한 산질화법은 합금강, 고탄소강에 내식성 증가에 효과가 있으나 저급강, 저탄소강에는 내식성 증가에 효과를 볼 수 없다는 단점이 있다. However, the above-mentioned oxynitride method has an effect of increasing the corrosion resistance of alloy steel and high carbon steel, but has a disadvantage of not having an effect of increasing the corrosion resistance of low grade steel and low carbon steel.
이에, 본 발명자들은 금속 표면의 내식성 향상을 위한 산질화 처리 시 질화 단계 중 또는 질화 단계 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하고 산화 처리하여 저급강, 저탄소강에서도 개선된 내식성 특성을 확인함으로써 본 발명을 완성하였다.Accordingly, the present inventors exposed and fumigated the metal surface to an aqueous solution vapor containing sulfur (S) during or after the nitriding step or the nitriding step in order to improve the corrosion resistance of the metal surface. The present invention was completed by confirming the improved corrosion resistance properties.
본 발명의 목적은 저급강, 저탄소강에 산질화를 처리하여 합금강과 동일하거나 우수한 내식성을 갖는 내식성 금속을 제공하는 데에 있다. An object of the present invention is to provide a corrosion resistant metal having the same or better corrosion resistance as alloy steel by treating oxynitride with low grade steel and low carbon steel.
본 발명의 다른 목적은 저급강, 저탄소강에 산질화를 처리하여 합금강과 동일하거나 우수한 내식성을 부여할 수 있도록 하는 금속 표면 개질 방법을 제공하는 데에 있다. Another object of the present invention is to provide a metal surface modification method for treating oxynitride on low grade steel and low carbon steel to give the same or better corrosion resistance as alloy steel.
상기 목적을 달성하기 위하여, 본 발명은 황(S)이 포함된 수용액을 0.1 내지 10 중량%의 함량으로 금속 표면에 처리하여 얻어진 질화층 및 산화층을 포함하는 것을 특징으로 하는 내식성 금속을 제공한다. In order to achieve the above object, the present invention provides a corrosion-resistant metal comprising a nitride layer and an oxide layer obtained by treating the surface of the metal with an aqueous solution containing sulfur (S) in an amount of 0.1 to 10% by weight.
또한, 본 발명은 표면세척 단계, 예열 단계 및 질화 단계를 포함하는 내식성 향상을 위한 금속 표면 개질 방법에 있어서, 상기 질화 단계 중 또는 질화 단계 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법을 제공한다.In addition, the present invention in the metal surface modification method for improving the corrosion resistance including the surface cleaning step, preheating step and nitriding step, the aqueous solution vapor containing sulfur (S) during the nitriding step or after the nitriding step sequentially It provides a metal surface modification method for improving the corrosion resistance, characterized in that it comprises an oxidation step of the oxidation treatment by exposure and fumigation.
본 발명에 따른 내식성 금속 및 금속 표면 개질 방법은 질화 처리와 동시에 또는 질환 처리 후 산화 처리 시 황(S) 성분을 포함한 물질을 추가로 투입함으로써 질화층 또는 확산층 상에 생성되는 산화층 내부의 기공층이 매우 많아지며 황(S)이 산소(O2), 철(Fe) 및 질소(N)의 결합력을 증가시켜 내식성이 증가되므로 습동성과 내마모성을 유지하면서 내식성까지 증가되는 효과가 있다. Corrosion-resistant metals and metal surface modification method according to the present invention is a pore layer inside the oxide layer formed on the nitride layer or the diffusion layer by adding a substance containing sulfur (S) component at the same time as the nitriding treatment or during the oxidation treatment after disease treatment Since the sulfur (S) increases the bonding strength of oxygen (O 2 ), iron (Fe) and nitrogen (N) to increase the corrosion resistance, there is an effect to increase the corrosion resistance while maintaining slidability and wear resistance.
도 1은 본 발명의 일실시예에 따른 금속 표면 개질 방법을 나타낸 것이고,1 shows a metal surface modification method according to an embodiment of the present invention,
도 2는 본 발명의 다른 일실시예에 따른 금속 표면 개질 방법을 나타낸 것이다.Figure 2 shows a metal surface modification method according to another embodiment of the present invention.
본 발명은 황(S)이 포함된 수용액을 0.1 내지 10 중량%의 함량으로 금속 표면에 처리하여 얻어진 질화층 및 산화층을 포함하는 것을 특징으로 하는 내식성 금속을 제공한다. The present invention provides a corrosion-resistant metal comprising a nitride layer and an oxide layer obtained by treating the metal surface with an aqueous solution containing sulfur (S) in an amount of 0.1 to 10% by weight.
상기 금속 표면은 표면세척, 예열 및 질화를 거쳐 처리되되, 상기 질화 중 또는 질화 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리할 수 있다.The metal surface may be treated by surface cleaning, preheating, and nitriding, and the metal surface may be oxidized by sequentially exposing and fumigating the metal surface to an aqueous solution containing sulfur (S) during or after nitriding.
상기 황(S)이 포함된 수용액은 황산(H2SO4), 이산화황(SO2), 삼산화황(SO3), 아황산(H2SO3), 황산구리 무수물(CuSO4), 황산구리(Ⅱ) 오수화물(CuSO4·5H2O), 황산납(PbSO4), 황산바륨(BaSO4), 황산나트륨(Na2SO4), 황산소수나트륨(NaHSO4), 황산아연(ZnSO4), 황산알루미늄(Al2(SO4)3), 황산암모늄((NH4)2SO4)), 황산은(Ag2SO4), 황산칼슘(CaSO4), 황산마그네슘(MgSO4), 황산크로뮴(Cr2(SO4)3), 황산포타슘(K2SO4), 황화구리(CuS), 황화마그네슘(MgS), 황화수소(H2S), 황화수은(II)(HgS), 황화철(FeS), 황화카드늄(CdS), 메테인설폰산(CH3SO3H), 아황산수소소듐(NaHSO3), 사이클로헥세인설폰산((CH2)6SO2), 벤젠설폰산(C6H5SO3H), 이황화탄소(CS2), 황화수소나트륨(NaHS), 벤젠설폰산나트륨(C6H5SO3Na), 황화수고칼슘(Ca(SH)2), 황화알루미늄(Al2S3), 황화크로뮴(Cr2S3), 황화규소(SiS2), 싸이오페놀(thiophenol), 다이싸이올 (dithiol), 메테인싸이올(CH4S), 싸이오아세탈(thioacetal), 싸이오사이클램(thiocyclam), 싸이오아세트아마이드, 싸이오카르밤산암모늄, 설포벤조산아마이드, 알리신(allicin), 황산콘드로이친(chondroitin sulfate), 나프탈렌설폰산(naphthalenesulfonic acid), 벤젠설폰산, 나프톨설폰산(naphtholsulfonic acid), 톨루엔설폰산 및 안트라퀴논설폰산으로 이루어진 군에서 선택된 어느 하나의 수용액일 수 있지만, 이에 한정되는 것은 아니며 황을 포함하는 어떠한 물질의 수용액도 사용될 수 있다.The aqueous solution containing sulfur (S) is sulfuric acid (H2SO4), Sulfur dioxide (SO2), Sulfur trioxide (SO3), Sulfurous acid (H2SO3), Copper sulfate anhydride (CuSO4), Copper sulfate (II) pentahydrate (CuSO45H2O), lead sulfate (PbSO4), Barium sulfate (BaSO4), Sodium sulfate (Na2SO4), Sodium hydrogen sulphate (NaHSO4), Zinc sulfate (ZnSO4), Aluminum sulfate (Al2(SO4)3), Ammonium sulfate ((NH4)2SO4)), Silver sulfate (Ag2SO4), Calcium sulfate (CaSO4), Magnesium sulfate (MgSO4), Chromium Sulfate (Cr2(SO4)3), Potassium sulfate (K2SO4), Copper sulfide (CuS), magnesium sulfide (MgS), hydrogen sulfide (H2S), mercury sulfide (II) (HgS), iron sulfide (FeS), cadmium sulfide (CdS), methanesulfonic acid (CH3SO3H), sodium hydrogen sulfite (NaHSO3), Cyclohexanesulfonic acid ((CH2)6SO2), Benzenesulfonic Acid (C6H5SO3H), carbon disulfide (CS2), Sodium hydrogen sulfide (NaHS), sodium benzene sulfonate (C6H5SO3Na), hydrocalcium sulfide (Ca (SH)2), Aluminum sulfide (Al2S3), Chromium sulfide (Cr2S3), Silicon sulfide (SiS2), Thiophenol, dithiol, methanethiol (CH4S), thioacetal, thiocyclam, thioacetamide, thiocarbamate, ammonium sulfobenzoic acid, allicin, chondroitin sulfate, naphthalenesulfonic acid acid), benzenesulfonic acid, naphtholsulfonic acid, toluenesulfonic acid, and anthraquinonesulfonic acid, but may be any one aqueous solution selected from the group consisting of, but not limited to, an aqueous solution of any substance including sulfur Can be used.
또한, 본 발명은 표면세척 단계, 예열 단계 및 질화 단계를 포함하는 내식성 향상을 위한 금속 표면 개질 방법에 있어서, 상기 질화 단계 중 또는 질화 단계 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법을 제공한다.In addition, the present invention in the metal surface modification method for improving the corrosion resistance including the surface cleaning step, preheating step and nitriding step, the aqueous solution vapor containing sulfur (S) during the nitriding step or after the nitriding step sequentially It provides a metal surface modification method for improving the corrosion resistance, characterized in that it comprises an oxidation step of the oxidation treatment by exposure and fumigation.
본 발명의 일 실시예로는, 금속표면에 이물질 및 유분을 제거하는 표면세척 단계; 상기 표면세척 단계를 수행한 금속 표면을 가열하여 예열하는 예열 단계; 및 상기 예열단계를 통해 예열된 금속 표면에 질화층 및 확산층 중 적어도 어느 하나가 형성되도록 하면서 동시에 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법을 제공한다.In one embodiment of the present invention, the surface washing step of removing foreign matter and oil on the metal surface; A preheating step of heating and preheating the metal surface on which the surface cleaning step is performed; And an oxidation step in which at least one of a nitride layer and a diffusion layer is formed on the metal surface preheated through the preheating step, and at the same time, the metal surface is oxidized by exposing and fumigation to an aqueous vapor containing sulfur (S). A metal surface modification method for improving corrosion resistance is provided.
본 발명의 다른 일 실시예로는, 금속표면에 이물질 및 유분을 제거하는 표면세척 단계; 상기 표면세척 단계를 수행한 금속 표면을 가열하여 예열하는 예열 단계; 상기 예열단계를 통해 예열된 금속 표면에 질화층 및 확산층 중 적어도 어느 하나가 형성되도록 하는 질화 단계; 및 상기 질화 단계에서 처리된 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법을 제공한다.Another embodiment of the present invention, the surface cleaning step of removing foreign matter and oil on the metal surface; A preheating step of heating and preheating the metal surface on which the surface cleaning step is performed; A nitriding step of forming at least one of a nitride layer and a diffusion layer on the preheated metal surface through the preheating step; And an oxidation step of subjecting the metal surface treated in the nitriding step to oxidation and oxidation by exposing and fumigation to an aqueous solution vapor containing sulfur (S).
본 발명에서 상기 질화 단계는 암모니아(NH3) 가스만 질화로에 투입하여 질화 과정을 수행하는 가스질화법; 또는 질소(N), 이산화탄소(CO2) 및 암모니아(NH3)를 질화로에 투입하여 질화 과정을 수행하는 가스연질화법 중에서 선택된 어느 하나의 방법을 이용하여 수행할 수 있다.In the present invention, the nitriding step includes a gas nitriding method in which only ammonia (NH 3 ) gas is added to the nitriding furnace to carry out a nitriding process; Alternatively, nitrogen (N), carbon dioxide (CO 2 ), and ammonia (NH 3 ) may be performed using any one method selected from a gas soft nitriding method in which a nitriding process is performed.
본 발명에서 상기 산화단계는 로 내부에 상기 금속 모재를 장입하고, 내부 온도가 350℃ 내지 600℃의 범위가 되도록 하는 승온하는 장입 및 승온 단계; 및 상기 장입 및 승온 단계의 최종 온도를 그대로 유지하면서 황(S)이 포함된 수용액 증기를 투입하고 처리하는 황(S) 수용액 증기 투입 단계를 포함할 수 있다.In the present invention, the oxidation step is charged and heated step of charging the metal base material in the furnace, the internal temperature is 350 ℃ to 600 ℃ range; And a sulfur (S) aqueous solution steam input step of inputting and treating an aqueous solution steam containing sulfur (S) while maintaining the final temperature of the charging and temperature raising step.
보다 상세하게는, 상기 산화단계는 로 내부에 상기 금속 모재를 장입하고, 내부 온도가 350℃ 내지 600℃의 범위가 되도록 하는 승온하는 장입 및 승온 단계; 및 상기 장입 및 승온 단계의 최종 온도를 그대로 유지하면서 황(S)이 포함된 수용액 증기 0.1 내지 10 중량%를 투입하고 1 내지 60분 동안 처리하는 황(S) 수용액 증기 투입 단계를 포함할 수 있다. More specifically, the oxidation step may be charged and heated step of charging the metal base material in the furnace, the internal temperature is 350 ℃ to 600 ℃ range; And while maintaining the final temperature of the charging and the step of raising the temperature may include a sulfur (S) aqueous solution steam input step of adding 0.1 to 10% by weight of an aqueous solution steam containing sulfur (S) and processing for 1 to 60 minutes. .
상기 산화 단계에서 내부 온도가 상기 범위를 벗어나면 Fe2O3가 생성되어 적청화되고 제품의 색상이 변화되는 문제가 야기될 수 있으며, 황(S)이 포함된 수용액 증기의 함유량이 상기 범위를 벗어나면 질화층과 산화층이 견고하게 접착되지 못하는 문제가 야기될 수 있고, 황(S)이 포함된 수용액 증기의 처리 시간이 상기 범위를 벗어나면 박리현상, 황산화 현상 및 수용액의 기화가 원활하지 못한 문제가 야기될 수 있다.When the internal temperature is out of the range in the oxidation step, Fe 2 O 3 may be generated to cause red blue crystals and to change the color of the product, and the content of the aqueous vapor containing sulfur (S) may be in the above range. If this occurs, the nitride layer and the oxide layer may not be firmly adhered to each other. If the treatment time of the aqueous solution vapor containing sulfur (S) is out of the above range, the peeling phenomenon, the sulfation phenomenon, and the vaporization of the aqueous solution may not be smooth. Unsuccessful problems may arise.
본 발명에서 상기 산화 단계에 투입되는 황(S) 수용액은 황산(H2SO4), 이산화황(SO2), 삼산화황(SO3), 아황산(H2SO3), 황산구리 무수물(CuSO4), 황산구리(Ⅱ) 오수화물(CuSO4·5H2O), 황산납(PbSO4), 황산바륨(BaSO4), 황산나트륨(Na2SO4), 황산소수나트륨(NaHSO4), 황산아연(ZnSO4), 황산알루미늄(Al2(SO4)3), 황산암모늄((NH4)2SO4)), 황산은(Ag2SO4), 황산칼슘(CaSO4), 황산마그네슘(MgSO4), 황산크로뮴(Cr2(SO4)3), 황산포타슘(K2SO4), 황화구리(CuS), 황화마그네슘(MgS), 황화수소(H2S), 황화수은(II)(HgS), 황화철(FeS), 황화카드늄(CdS), 메테인설폰산(CH3SO3H), 아황산수소소듐(NaHSO3), 사이클로헥세인설폰산((CH2)6SO2), 벤젠설폰산(C6H5SO3H), 이황화탄소(CS2), 황화수소나트륨(NaHS), 벤젠설폰산나트륨(C6H5SO3Na), 황화수고칼슘(Ca(SH)2), 황화알루미늄(Al2S3), 황화크로뮴(Cr2S3), 황화규소(SiS2), 싸이오페놀(thiophenol), 다이싸이올 (dithiol), 메테인싸이올(CH4S), 싸이오아세탈(thioacetal), 싸이오사이클램(thiocyclam), 싸이오아세트아마이드, 싸이오카르밤산암모늄, 설포벤조산아마이드, 알리신(allicin), 황산콘드로이친(chondroitin sulfate), 나프탈렌설폰산(naphthalenesulfonic acid), 벤젠설폰산, 나프톨설폰산(naphtholsulfonic acid), 톨루엔설폰산 또는 안트라퀴논설폰산에서 선택된 어느 하나의 수용액일 수 있지만, 이에 한정되는 것은 아니며 황을 포함하는 어떠한 물질의 수용액도 사용될 수 있다.Sulfur (S) aqueous solution is added to the oxidation step in the present invention is sulfuric acid (H2SO4), Sulfur dioxide (SO2), Sulfur trioxide (SO3), Sulfurous acid (H2SO3), Copper sulfate anhydride (CuSO4), Copper sulfate (II) pentahydrate (CuSO45H2O), lead sulfate (PbSO4), Barium sulfate (BaSO4), Sodium sulfate (Na2SO4), Sodium hydrogen sulphate (NaHSO4), Zinc sulfate (ZnSO4), Aluminum sulfate (Al2(SO4)3), Ammonium sulfate ((NH4)2SO4)), Silver sulfate (Ag2SO4), Calcium sulfate (CaSO4), Magnesium sulfate (MgSO4), Chromium Sulfate (Cr2(SO4)3), Potassium sulfate (K2SO4), Copper sulfide (CuS), magnesium sulfide (MgS), hydrogen sulfide (H2S), mercury sulfide (II) (HgS), iron sulfide (FeS), cadmium sulfide (CdS), methanesulfonic acid (CH3SO3H), sodium hydrogen sulfite (NaHSO3), Cyclohexanesulfonic acid ((CH2)6SO2), Benzenesulfonic Acid (C6H5SO3H), carbon disulfide (CS2), Sodium hydrogen sulfide (NaHS), sodium benzene sulfonate (C6H5SO3Na), hydrocalcium sulfide (Ca (SH)2), Aluminum sulfide (Al2S3), Chromium sulfide (Cr2S3), Silicon sulfide (SiS2), Thiophenol, dithiol, methanethiol (CH4S), thioacetal, thiocyclam, thioacetamide, thiocarbamate, ammonium sulfobenzoic acid, allicin, chondroitin sulfate, naphthalenesulfonic acid acid), benzenesulfonic acid, naphtholsulfonic acid, toluenesulfonic acid or anthraquinonesulfonic acid, but may be any aqueous solution selected from, but is not limited to, an aqueous solution of any substance including sulfur may be used. .
본 발명에 따른 금속 표면 개질 방법은 상기 산화 단계 후, 방청, 실링(Sealing), 왁싱(Waxing) 및 코팅(Coating)으로 이루어진 군에서 선택된 어느 하나 이상의 단계를 더 포함할 수 있다.The metal surface modification method according to the present invention may further include any one or more steps selected from the group consisting of rust prevention, sealing, waxing, and coating after the oxidation step.
또한, 본 발명은 상기 금속 표면 개질 방법을 통해 금속 표면이 개질된 것을 특징으로 하는 내식성 금속을 제공할 수 있다.In addition, the present invention can provide a corrosion-resistant metal, characterized in that the metal surface is modified through the metal surface modification method.
본 발명은 질화 단계 중 또는 질화 단계 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 내식성 향상을 위한 금속 표면 개질 방법에 관한 것으로, 하기 실시예를 통해 본 발명을 보다 상세하게 설명한다. 다만, 이러한 실시예에 의해 본 발명이 한정되는 것은 아니다.The present invention relates to a metal surface modification method for improving corrosion resistance, comprising an oxidation step of oxidizing and exposing and fusing a metal surface to an aqueous solution vapor containing sulfur (S) sequentially during or after nitriding. The present invention will be described in more detail with reference to Examples. However, the present invention is not limited by these examples.
<실시예 1> 본 발명에 따른 산질화를 이용한 금속 표면 처리Example 1 Metal Surface Treatment Using Oxidation according to the Present Invention
JIS SPCC, JIS SAPH440, S45C 재질의 시편을 JIG에 배열하여 T.E.C.증기로 약 80~90도에서 1시간 먼저 표면 세척한 후, 하기 표 1과 같은 공정 조건 하에서 금속 표면을 개질하였다.The specimens made of JIS SPCC, JIS SAPH440, and S45C were arranged in JIG, and then surface-washed at about 80 to 90 degrees with T.E.C. steam for 1 hour, and then the metal surface was modified under the process conditions shown in Table 1 below.
표 1
단계 온도(℃) 반응가스 처리시간(분)
예열단계 575 N2: 50부피%, NH3: 50부피% 90
질화단계 585 NH3: 70부피%, N2: 20부피%, CO2 :10부피% 110
산화단계 585 황산수용액 3중량% 증기 30
Table 1
step Temperature (℃) Reaction gas Processing time (minutes)
Preheating stage 575 N 2 : 50% by volume, NH 3 : 50% by volume 90
Nitriding Step 585 NH 3 : 70% by volume, N 2 : 20% by volume, CO 2 : 10% by volume 110
Oxidation stage 585 Sulfuric acid aqueous solution 3% by weight steam 30
<실시예 2> 본 발명에 따른 산질화를 이용한 금속 표면 처리Example 2 Metal Surface Treatment Using Oxidation according to the Present Invention
JIS SPCC, JIS SAPH440, S45C 재질의 시편을 JIG에 배열하여 T.E.C.증기로 약 80~90도에서 1시간 먼저 표면 세척한 후, 하기 표 2와 같은 공정 조건 하에서 금속 표면을 개질하였다.The specimens made of JIS SPCC, JIS SAPH440, and S45C were arranged in JIG to be first surface-washed at about 80 to 90 degrees with T.E.C. steam for 1 hour, and then the metal surface was modified under the process conditions shown in Table 2 below.
표 2
단계 온도(℃) 반응가스 처리시간(분)
예열단계 575 N2: 50부피%, NH3: 50부피% 90
질화단계 585 NH3: 70부피%, N2: 20부피%, CO2 :10부피% 110
산화단계 575 황산수용액 1중량% 증기 120
TABLE 2
step Temperature (℃) Reaction gas Processing time (minutes)
Preheating stage 575 N 2 : 50% by volume, NH 3 : 50% by volume 90
Nitriding Step 585 NH 3 : 70% by volume, N 2 : 20% by volume, CO 2 : 10% by volume 110
Oxidation stage 575 Sulfuric acid aqueous solution 1% by weight steam 120
<비교예 1> 일반 산질화를 이용한 금속 표면 처리Comparative Example 1 Metal Surface Treatment Using General Oxidation
JIS SPCC, JIS SAPH440, S45C 재질의 시편을 JIG에 배열하여 T.E.C.증기로 약 80~90도에서 1시간 먼저 표면 세척한 후, 하기 표 3과 같은 공정 조건 하에서 금속 표면을 개질하였다.The specimens made of JIS SPCC, JIS SAPH440, and S45C were arranged in JIG to be first surface-washed at about 80 to 90 degrees with T.E.C. steam for 1 hour, and then the metal surface was modified under the process conditions shown in Table 3 below.
표 3
단계 온도(℃) 반응가스 처리시간(분)
예열단계 575 N2: 50부피%, NH3: 50부피% 40~90
질화단계 585 NH3: 70부피%, N2: 20부피%, CO2 :10부피% 60~150
산화단계 575 일반 수증기 10
TABLE 3
step Temperature (℃) Reaction gas Processing time (minutes)
Preheating stage 575 N 2 : 50% by volume, NH 3 : 50% by volume 40-90
Nitriding Step 585 NH 3 : 70% by volume, N 2 : 20% by volume, CO 2 : 10% by volume 60-150
Oxidation stage 575 General water vapor 10
<실험예 1> 내식성 평가Experimental Example 1 Evaluation of Corrosion Resistance
염수분무시험(KSM2109)을 이용하여 내식성 시험을 수행한 결과, 하기 표 4와 같이 실시예와 같이 표면 처리된 금속이 비교예인 일반 산질화 공정을 통해 표면 처리된 금속에 비해 내식성이 크게 향상되는 것을 확인할 수 있었다. As a result of performing a corrosion resistance test using the salt spray test (KSM2109), as shown in Table 4, the surface-treated metal as shown in Example 4 is significantly improved in the corrosion resistance compared to the surface-treated metal through the general oxynitride process as a comparative example I could confirm it.
표 4
강종(JIS) 방청 시간
비교예 1 실시예 1 실시예 2
SAPH440 120 432 160
SPCC 24 288 80
S45C 200 280 430
Table 4
Steel grade (JIS) Antirust time
Comparative Example 1 Example 1 Example 2
SAPH440 120 432 160
SPCC 24 288 80
S45C 200 280 430
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다. Having described the specific parts of the present invention in detail, it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, thereby not limiting the scope of the present invention. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (11)

  1. 황(S)이 포함된 수용액을 0.1 내지 10 중량%의 함량으로 금속 표면에 처리하여 얻어진 질화층 및 산화층을 포함하는 것을 특징으로 하는 내식성 금속.Corrosion-resistant metal, characterized in that it comprises a nitride layer and an oxide layer obtained by treating the metal surface with an aqueous solution containing sulfur (S) in an amount of 0.1 to 10% by weight.
  2. 청구항 1에 있어서, The method according to claim 1,
    상기 금속 표면은 표면세척, 예열 및 질화를 거쳐 처리되되, 상기 질화 중 또는 질화 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 것을 특징으로 하는 내식성 금속.The metal surface is treated through surface cleaning, preheating and nitriding, and the metal surface is sequentially oxidized by exposing and fumigation with an aqueous solution vapor containing sulfur (S) during or after nitriding.
  3. 청구항 1 또는 청구항 2에 있어서, The method according to claim 1 or 2,
    상기 황(S)이 포함된 수용액은 황산(H2SO4), 이산화황(SO2), 삼산화황(SO3), 아황산(H2SO3), 황산구리 무수물(CuSO4), 황산구리(Ⅱ) 오수화물(CuSO4·5H2O), 황산납(PbSO4), 황산바륨(BaSO4), 황산나트륨(Na2SO4), 황산소수나트륨(NaHSO4), 황산아연(ZnSO4), 황산알루미늄(Al2(SO4)3), 황산암모늄((NH4)2SO4)), 황산은(Ag2SO4), 황산칼슘(CaSO4), 황산마그네슘(MgSO4), 황산크로뮴(Cr2(SO4)3), 황산포타슘(K2SO4), 황화구리(CuS), 황화마그네슘(MgS), 황화수소(H2S), 황화수은(II)(HgS), 황화철(FeS), 황화카드늄(CdS), 메테인설폰산(CH3SO3H), 아황산수소소듐(NaHSO3), 사이클로헥세인설폰산((CH2)6SO2), 벤젠설폰산(C6H5SO3H), 이황화탄소(CS2), 황화수소나트륨(NaHS), 벤젠설폰산나트륨(C6H5SO3Na), 황화수고칼슘(Ca(SH)2), 황화알루미늄(Al2S3), 황화크로뮴(Cr2S3), 황화규소(SiS2), 싸이오페놀(thiophenol), 다이싸이올 (dithiol), 메테인싸이올(CH4S), 싸이오아세탈(thioacetal), 싸이오사이클램(thiocyclam), 싸이오아세트아마이드, 싸이오카르밤산암모늄, 설포벤조산아마이드, 알리신(allicin), 황산콘드로이친(chondroitin sulfate), 나프탈렌설폰산(naphthalenesulfonic acid), 벤젠설폰산, 나프톨설폰산(naphtholsulfonic acid), 톨루엔설폰산 및 안트라퀴논설폰산으로 이루어진 군에서 선택된 어느 하나의 수용액인 것을 특징으로 하는 내식성 금속.The aqueous solution containing sulfur (S) is sulfuric acid (H2SO4), Sulfur dioxide (SO2), Sulfur trioxide (SO3), Sulfurous acid (H2SO3), Copper sulfate anhydride (CuSO4), Copper sulfate (II) pentahydrate (CuSO45H2O), lead sulfate (PbSO4), Barium sulfate (BaSO4), Sodium sulfate (Na2SO4), Sodium hydrogen sulphate (NaHSO4), Zinc sulfate (ZnSO4), Aluminum sulfate (Al2(SO4)3), Ammonium sulfate ((NH4)2SO4)), Silver sulfate (Ag2SO4), Calcium sulfate (CaSO4), Magnesium sulfate (MgSO4), Chromium Sulfate (Cr2(SO4)3), Potassium sulfate (K2SO4), Copper sulfide (CuS), magnesium sulfide (MgS), hydrogen sulfide (H2S), mercury sulfide (II) (HgS), iron sulfide (FeS), cadmium sulfide (CdS), methanesulfonic acid (CH3SO3H), sodium hydrogen sulfite (NaHSO3), Cyclohexanesulfonic acid ((CH2)6SO2), Benzenesulfonic Acid (C6H5SO3H), carbon disulfide (CS2), Sodium hydrogen sulfide (NaHS), sodium benzene sulfonate (C6H5SO3Na), hydrocalcium sulfide (Ca (SH)2), Aluminum sulfide (Al2S3), Chromium sulfide (Cr2S3), Silicon sulfide (SiS2), Thiophenol, dithiol, methanethiol (CH4S), thioacetal, thiocyclam, thioacetamide, thiocarbamate, ammonium sulfobenzoic acid, allicin, chondroitin sulfate, naphthalenesulfonic acid acid), benzenesulfonic acid, naphtholsulfonic acid (naphtholsulfonic acid), toluenesulfonic acid and anthraquinonesulfonic acid.
  4. 표면세척 단계, 예열 단계 및 질화 단계를 포함하는 내식성 향상을 위한 금속 표면 개질 방법에 있어서, 상기 질화 단계 중 또는 질화 단계 후 순차적으로 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.In the metal surface modification method for improving the corrosion resistance including a surface cleaning step, a preheating step and a nitriding step, during and after the nitriding step, the metal surface is sequentially exposed and fumed by an aqueous vapor containing sulfur (S) A metal surface modification method for improving corrosion resistance, comprising an oxidation step of oxidizing.
  5. 청구항 4에 있어서, The method according to claim 4,
    금속표면에 이물질 및 유분을 제거하는 표면세척 단계; A surface washing step of removing foreign substances and oil from the metal surface;
    상기 표면세척 단계를 수행한 금속 표면을 가열하여 예열하는 예열 단계; 및A preheating step of heating and preheating the metal surface on which the surface cleaning step is performed; And
    상기 예열단계를 통해 예열된 금속 표면에 질화층 및 확산층 중 적어도 어느 하나가 형성되도록 하면서 동시에 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계At least one of a nitride layer and a diffusion layer is formed on the preheated metal surface through the preheating step, and an oxidation step of subjecting the metal surface to an aqueous solution vapor containing sulfur (S) and fumigation to oxidize it.
    를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.Metal surface modification method for improving the corrosion resistance comprising a.
  6. 청구항 4에 있어서, The method according to claim 4,
    금속표면에 이물질 및 유분을 제거하는 표면세척 단계; A surface washing step of removing foreign substances and oil from the metal surface;
    상기 표면세척 단계를 수행한 금속 표면을 가열하여 예열하는 예열 단계; A preheating step of heating and preheating the metal surface on which the surface cleaning step is performed;
    상기 예열단계를 통해 예열된 금속 표면에 질화층 및 확산층 중 적어도 어느 하나가 형성되도록 하는 질화 단계; 및 A nitriding step of forming at least one of a nitride layer and a diffusion layer on the preheated metal surface through the preheating step; And
    상기 질화 단계에서 처리된 금속 표면을 황(S)이 포함된 수용액 증기에 노출 및 훈증하여 산화 처리하는 산화 단계An oxidation step of subjecting the metal surface treated in the nitriding step to an oxidation process by exposing and fumigation to an aqueous solution vapor containing sulfur (S).
    를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.Metal surface modification method for improving the corrosion resistance comprising a.
  7. 청구항 4에 있어서, The method according to claim 4,
    상기 질화 단계는 암모니아(NH3) 가스만 질화로에 투입하여 질화 과정을 수행하는 가스질화법; 또는 질소(N), 이산화탄소(CO2) 및 암모니아(NH3)를 질화로에 투입하여 질화 과정을 수행하는 가스연질화법 중에서 선택된 어느 하나의 방법을 이용하여 수행할 수 있는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.The nitriding step includes a gas nitriding method in which only ammonia (NH 3 ) gas is added to the nitriding furnace to carry out a nitriding process; Alternatively, nitrogen (N), carbon dioxide (CO 2 ), and ammonia (NH 3 ) may be performed by using any one method selected from a gas soft nitriding method in which a nitriding process is carried out. Metal surface modification method.
  8. 청구항 4에 있어서, The method according to claim 4,
    상기 산화단계는 로 내부에 상기 금속 모재를 장입하고, 내부 온도가 350℃ 내지 600℃의 범위가 되도록 하는 승온하는 장입 및 승온 단계; 및 상기 장입 및 승온 단계의 최종 온도를 그대로 유지하면서 황(S)이 포함된 수용액 증기를 투입하고 처리하는 황(S) 수용액 증기 투입 단계를 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.The oxidation step is charged and heated step of charging the metal base material in the furnace, the temperature rising so that the internal temperature is in the range of 350 ℃ to 600 ℃; And a sulfur (S) aqueous solution steam input step of injecting and treating an aqueous solution vapor containing sulfur (S) while maintaining the final temperature of the charging and temperature raising step as it is. .
  9. 청구항 4에 있어서, The method according to claim 4,
    상기 산화 단계에 투입되는 황(S) 수용액은 황산(H2SO4), 이산화황(SO2), 삼산화황(SO3), 아황산(H2SO3), 황산구리 무수물(CuSO4), 황산구리(Ⅱ) 오수화물(CuSO4·5H2O), 황산납(PbSO4), 황산바륨(BaSO4), 황산나트륨(Na2SO4), 황산소수나트륨(NaHSO4), 황산아연(ZnSO4), 황산알루미늄(Al2(SO4)3), 황산암모늄((NH4)2SO4)), 황산은(Ag2SO4), 황산칼슘(CaSO4), 황산마그네슘(MgSO4), 황산크로뮴(Cr2(SO4)3), 황산포타슘(K2SO4), 황화구리(CuS), 황화마그네슘(MgS), 황화수소(H2S), 황화수은(II)(HgS), 황화철(FeS), 황화카드늄(CdS), 메테인설폰산(CH3SO3H), 아황산수소소듐(NaHSO3), 사이클로헥세인설폰산((CH2)6SO2), 벤젠설폰산(C6H5SO3H), 이황화탄소(CS2), 황화수소나트륨(NaHS), 벤젠설폰산나트륨(C6H5SO3Na), 황화수고칼슘(Ca(SH)2), 황화알루미늄(Al2S3), 황화크로뮴(Cr2S3), 황화규소(SiS2), 싸이오페놀(thiophenol), 다이싸이올 (dithiol), 메테인싸이올(CH4S), 싸이오아세탈(thioacetal), 싸이오사이클램(thiocyclam), 싸이오아세트아마이드, 싸이오카르밤산암모늄, 설포벤조산아마이드, 알리신(allicin), 황산콘드로이친(chondroitin sulfate), 나프탈렌설폰산(naphthalenesulfonic acid), 벤젠설폰산, 나프톨설폰산(naphtholsulfonic acid), 톨루엔설폰산 및 안트라퀴논설폰산으로 이루어진 군에서 선택된 어느 하나의 수용액인 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.Sulfur (S) aqueous solution added to the oxidation step is sulfuric acid (H2SO4), Sulfur dioxide (SO2), Sulfur trioxide (SO3), Sulfurous acid (H2SO3), Copper sulfate anhydride (CuSO4), Copper sulfate (II) pentahydrate (CuSO45H2O), lead sulfate (PbSO4), Barium sulfate (BaSO4), Sodium sulfate (Na2SO4), Sodium hydrogen sulphate (NaHSO4), Zinc sulfate (ZnSO4), Aluminum sulfate (Al2(SO4)3), Ammonium sulfate ((NH4)2SO4)), Silver sulfate (Ag2SO4), Calcium sulfate (CaSO4), Magnesium sulfate (MgSO4), Chromium Sulfate (Cr2(SO4)3), Potassium sulfate (K2SO4), Copper sulfide (CuS), magnesium sulfide (MgS), hydrogen sulfide (H2S), mercury sulfide (II) (HgS), iron sulfide (FeS), cadmium sulfide (CdS), methanesulfonic acid (CH3SO3H), sodium hydrogen sulfite (NaHSO3), Cyclohexanesulfonic acid ((CH2)6SO2), Benzenesulfonic Acid (C6H5SO3H), carbon disulfide (CS2), Sodium hydrogen sulfide (NaHS), sodium benzene sulfonate (C6H5SO3Na), hydrocalcium sulfide (Ca (SH)2), Aluminum sulfide (Al2S3), Chromium sulfide (Cr2S3), Silicon sulfide (SiS2), Thiophenol, dithiol, methanethiol (CH4S), thioacetal, thiocyclam, thioacetamide, thiocarbamate, ammonium sulfobenzoic acid, allicin, chondroitin sulfate, naphthalenesulfonic acid acid), benzenesulfonic acid, naphtholsulfonic acid (naphtholsulfonic acid), toluenesulfonic acid and anthraquinonesulfonic acid, any one aqueous solution selected from the group consisting of metal surface modification method for improving corrosion resistance.
  10. 청구항 4에 있어서, The method according to claim 4,
    상기 금속 표면 개질 방법은 산화 단계 후, 방청, 실링(Sealing), 왁싱(Waxing) 및 코팅(Coating)으로 이루어진 군에서 선택된 어느 하나 이상의 단계를 더 포함하는 것을 특징으로 하는 내식성 향상을 위한 금속 표면 개질 방법.The metal surface modification method further includes any one or more steps selected from the group consisting of rust prevention, sealing, waxing, and coating after an oxidation step. Way.
  11. 청구항 4 내지 청구항 10 중 어느 한 항에　따른 금속 표면 개질 방법을 통해 금속 표면이 개질된 것을 특징으로 하는 내식성 금속.The metal surface is modified by the metal surface modification method according to any one of claims 4 to 10.
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