KR900005843B1 - Method to make a phosphate film with a copper coating on steel substrates - Google Patents

Method to make a phosphate film with a copper coating on steel substrates Download PDF

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KR900005843B1
KR900005843B1 KR1019880001696A KR880001696A KR900005843B1 KR 900005843 B1 KR900005843 B1 KR 900005843B1 KR 1019880001696 A KR1019880001696 A KR 1019880001696A KR 880001696 A KR880001696 A KR 880001696A KR 900005843 B1 KR900005843 B1 KR 900005843B1
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steel substrates
phosphate
copper
plating
phosphate coating
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KR890013221A (en
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김동욱
이영화
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김동욱
이영화
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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
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates

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  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Copper plating layer and phosphate film are simultaneously formed on steel substrates by dipping the steel substrates in acid treating solution consisting of a copper ion compound for example Cu(NO3)2, Cu(H2PO4)2, CuSO4, an agent for phosphate film for example NaH2PO4, NaPO3, Zn(H2PO4)2, Mn(H2PO4)2, a redcting agent for example formalin, and an oxidizing agent for example NaNO3, NaNO2.

Description

철소지면에 구리도금과 동시에 인산염피막을 형성하는 방법How to Form Phosphate Film on Copper Plated at the Same Time

본 발명은 철강소지면에 구리화학도금과 동시에 인산염피막의 화성(化成)을 처리용액에 디핑함으로서 한 공정으로 얻는 방법에 관한 것이다.The present invention relates to a method of obtaining by one step by dipping the chemical solution of the steel sheet at the same time as the chemical solution of the phosphate coating in the treatment solution.

더 자세히는 구리원으로서 Cu염, 예로서 Cu(NO3)2, Cu(H2PO4), CuSO4과 인산피막제로서 제1인산염, 예로서, NaH2P04, NaF03, Zn(H2PO4)2, Mn(H2PO4)2, 및 환원제로서 통상의 호루마린과 산화제로서 질산염, 예로서 NaN03, NaN02등으로 된 안정된 상성용액에 피도금 철 재를 침지하였다. 인상함으로서 철소지면에 밀착성이 좋고 균일 두께의 구리도금과 동시에 구리도금 면상에 내식성 내산화성의 견고한 불용성인 제2 및 제3인산염성피막을 형성시키는 방법에 관한 것이다.More specifically, Cu salts as copper sources, eg Cu (NO 3 ) 2 , Cu (H 2 PO 4 ), CuSO 4 and monophosphates as phosphate coatings, eg NaH 2 P0 4 , NaF0 3 , Zn (H The iron material to be plated was immersed in a stable aqueous solution of 2 PO 4 ) 2 , Mn (H 2 PO 4 ) 2 , and a common horumarin as a reducing agent and a nitrate as an oxidant, such as NaN0 3 , NaN0 2 , and the like. The present invention relates to a method of forming second and third phosphate coatings having good adhesion to iron surface and having a uniform thickness of copper plating and at the same time corrosion resistant oxidation resistant solid insoluble coating on copper plating surfaces.

종래에도 호르마린이나 차아인산염(次亞燐酸鹽) 등의 강력한 환원제를 첨가한 산성구리용액을 사용하여 Cu를 화학 도금하는 방법이 알려져 있고 주로 Ni,Cr등의 하지 도금으로서 시행되어 왔다.Background Art Conventionally, a method of chemically plating Cu using an acidic copper solution to which a strong reducing agent such as hormones or hypophosphite is added has been known, and has been mainly performed as a base plating such as Ni and Cr.

그 이유는 Cu는 Fe보다 전기화학적 순위가 낮아 Cu 도금용액 중에 철소지를 침지하면 Cu 이온이 철소지를 침식 Fe와 치환석출되어 철소지면에 Cu 도금이나 일단 철소지면이 Cu로 덮이면 Cu 이온의 Fe와의 치환이 방해되어 그 석출이 느리게 되어 두꺼운 Cu 도금층을 형성하기 어렵게 되고 뿐만 아니라 도금액중의 Cu 이온 농도가 희박하게 되어 액의 교환 등 여러 가지 여건이 나빠져 결국은 화학도금의 이점이 감소되므로 구리의 화학도금은 Ni, Cr 도금 중의 하지도금으로서 많이 이용되고 있는 것이다.The reason is that Cu has lower electrochemical ranking than Fe, so that when copper material is immersed in Cu plating solution, Cu ions are substituted and precipitated by eroding Fe, and Cu plating on the iron surface or once the iron surface is covered with Cu, Substitution with Fe is hindered, and the precipitation is slowed, making it difficult to form a thick Cu plating layer. Moreover, the concentration of Cu ions in the plating solution is diminished, which leads to various conditions such as exchange of liquids. Chemical plating of is widely used as base plating during Ni and Cr plating.

또 한편 산성 인산염욕 중에 철강재를 침지하여 철강재표면에 불용성 인산염피막을 형성하여 방청성 내마모성, 소성가공성 및 도장성 등을 향상시키는 인산염화성피막을 형성시키는 것도 일반적으로 시행되고 있는 잘 알려진 방법이다.On the other hand, it is a well-known method that is generally practiced to form a phosphate coating which is immersed in the acidic phosphate bath to form an insoluble phosphate coating on the surface of the steel to improve the corrosion resistance wear resistance, plastic workability and paintability.

그러나 이와 같은 철강재에 구리화학 도금이나 인산염화성피막의 형성처리를 이제까지는 각기 독립적으로 별개로 개발시행되고 있는 것이다.However, the copper chemical plating and the formation of phosphate coating on such steel materials have been independently developed until now.

본 발명인들은 다년간 연구끝에 본원방법을 개발하게 된 것으로 이하 본 발명 실시예에 의하여 상세히 설명한다.The inventors have developed the present method after many years of research and will be described in detail by the following examples.

Cu(NO3)2, Cu(H2PO4)2, CuSO4등을 등도금원으로 Cu 2-lOg/l와 NaH2PO4, NaPO3, Zn(H2PO4)2, Mn(H2PO4)2등의 제1인산염 2-10g/l와 환원제로서 호르마린 1-2g/l 및 산화제로서 NaN03, NaNO2등의 질산염 0.3-1g/l로 조성된 산성용액(pH 2-3)을 처리용액으로 하여 탈산 탈지된 깨끗한 철소지를 처리 용액에 침지 처리하면 철소지표면에 Cu 도금막이 먼저 형성되고 동시에 Cu 도금막위에 불용성의 제2 및 제3인산염화성피막이 단일처리 용액에서 단일공정으로 형성하게 되는 것이다.Cu (NO 3 ) 2 , Cu (H 2 PO 4 ) 2 , CuSO 4, etc. as a plating source, Cu 2-lOg / l, NaH 2 PO 4 , NaPO 3 , Zn (H 2 PO 4 ) 2 , Mn (H Acid solution (pH 2-) composed of 2-10 g / l of primary phosphate such as 2 PO 4 ) 2 and 1-2 g / l of homomarine as reducing agent and 0.3-1 g / l of nitrate such as NaN0 3 and NaNO 2 as oxidizing agent 3) As a treatment solution, when the deoxidized and clean degreasing iron material is immersed in the treatment solution, a Cu plated film is formed on the surface of the iron plate first, and at the same time, an insoluble second and tertiary phosphate coating film is formed on the Cu plated film in a single treatment solution. It is formed by the process.

본원의 작용효과를 설명하면, 처리용액 중에 함유된 Cu 이온은 인산염피막제로서 첨가된 Na, Mn, Zn 동금속이온 보다도 전기화학적순위(K,Na,Mg,Al,Mn,Zn,Cr,Fe,Cd‥‥Cu)가 가장 낮고 따라서 Cu 이온은 이들 금속이온을 이기고 철소지를 침식하여 Fe와 치환하여 철소지면에 Cu를 석출하게 된다.In describing the effect of the present application, Cu ions contained in the treatment solution were electrochemically higher than those of Na, Mn, and Zn copper metal ions added as phosphate coating agents (K, Na, Mg, Al, Mn, Zn, Cr, Fe, Cd .... Cu) is the lowest, and thus Cu ions overcome these metal ions, erode the iron material, replace it with Fe, and precipitate Cu on the iron surface.

이때 환전세인 호르마린은 액중의 Cu 이온의 환원력(Fe와의 치환력)을 조장하여 철소지와의 치환반응을 촉진하여 도금이 촉진되며 한편 Na, Mn, Zn 등 금속은 Fe 보다 전기화학적 순위가 높아 Fe 소지를 치환할 수는 없으며 어느 정도의 Cu 화학도금이 진행되면 철소지와의 치환이 억제 둔화되고 액 중의 나머지 Cu 이온과 치환용출된 Fe 이온은 제1인산염의 금속 M와의 치환가 산화제에 의한 피막화성반응이 촉진되어 다음 식에 의하여 방청, 내식효과가 좋고 내구성 및 하도성이 좋은 불용성인 제2 또는 제3인산염을 형성하게 되는 것이다.At this time, the currency exchange Hormarin promotes the plating reaction by promoting the reduction reaction of Cu ions in the liquid (substituting with Fe) and promoting the substitution reaction with iron, while metals such as Na, Mn, and Zn have higher electrochemical rankings than Fe. It is not possible to substitute the Fe base, and when the Cu chemical plating is carried out to some extent, the substitution with the iron base is suppressed and the remaining Cu ions and the substituted eluted Fe ions in the solution are substituted with the metal M of the first phosphate. The chemical reaction is promoted to form an insoluble second or triphosphate having good rust resistance and corrosion resistance and good durability and coating properties by the following equation.

Cu+M(H2PO4)2+1/2O2→CuHPO4+MHPO4+H20Cu + M (H 2 PO 4 ) 2 + 1 / 2O 2 → CuHPO 4 + MHPO 4 + H 2 0

Fe+M(H2PO4)2+1/2O2→FeHPO4+MHPO4+H2OFe + M (H 2 PO 4 ) 2 + 1 / 2O 2 → FeHPO 4 + MHPO 4 + H 2 O

(M=Na, Mn, Zn 등)(M = Na, Mn, Zn, etc.)

이와 같이 본 발명은 철강재에 무전해 화학도금과 동시에 제2 및 제3인산염화성피막의 형성을 간단히 디핑하는 단일공정으로 찬성되는 이점이 있고 또 본 발명에 사용되는 처리용액은 화학적으로 대단히 안정되어 처리액을 단위상품으로 일반 화공상회에서 시판할 수도 있어 누구나 손쉽게 구하여 사용할 수 있는 이점이 있는 것이다.As such, the present invention has the advantage of being a simple process of simply dipping the formation of the second and third phosphate conversion coatings at the same time as electroless chemical plating on steel materials, and the treatment solution used in the present invention is chemically very stable and treated. The amount can be marketed as a unit commodity in the general chemical industry has the advantage that anyone can easily obtain and use.

이하 처리용액의 수지한정에 대하여 기술한다.Hereinafter, the resin limitation of the treatment solution will be described.

CUCU

Cu는 구리도금형성 성분으로서 Cu(NO3)2, Cu(H2PO4)2, CuSO4등을 첨가되며 2g/l 이하에서는 Cu 이온농도가 희박하여 철소지면에 형성되는 Cu 도금이 불균일하게 되고 한편 10g/l 이상에서는 Cu 이온량이 과다해 철소지면에 형성된 Cu 도금이 적동색으로 되어 색상이 깨끗치 못하며 따라서 Cu 함량을 2-lOg/l로 정한다.Cu is added Cu (NO 3 ) 2 , Cu (H 2 PO 4 ) 2 , CuSO 4, etc. as the copper plating forming component, and at 2g / l or less, Cu ion concentration is thin, resulting in uneven plating of Cu formed on the surface of iron. On the other hand, at 10 g / l or more, the amount of Cu ions is excessive, and the Cu plating formed on the iron surface becomes reddish-colored, so that the color is not clean. Therefore, the Cu content is set to 2-lOg / l.

제1인산염Monophosphate

제1인산염으로서 NaH2PO4, NaP03, Zn(H2P04)2, Mn(H2PO4)2등이 인산염피막의 형성제로서 첨가되며 2g/l 이하에서는 인산염피막 형성속도가 느리고, 한편 10g/l 이상에서는 형성된 인산염피막이 거칠어 페인트 등의 도장 시 표면이 평할치 못하므로 고첨가 범위를 2-10g/l로 정한다.As the first phosphate, NaH 2 PO 4 , NaP0 3 , Zn (H 2 P0 4 ) 2 , Mn (H 2 PO 4 ) 2, etc. are added as a phosphate coating agent, and at 2 g / l or less, the rate of phosphate coating is slow. On the other hand, at 10g / l or more, the formed phosphate film is rough, so that the surface is not flat when the paint is applied, so the high addition range is set to 2-10g / l.

환원제(호르마린)Reducing Agent (Hormarin)

인산염피막 처리에 있어 환원제로 호르마린을 첨가하는 것은 잘 알려진 바로 1g/l 이하에서는 환원력이 약하고 한편 2g/l 이상에서는 냄새가 심하며 위생상 해롭고 작업에 지장이 있으므로 그 범위를 1-2g/l로 정한다.It is well known that the addition of hormones as a reducing agent in the treatment of phosphate coatings is known to have a low reducing power below 1 g / l, odors above 2 g / l, harmful to hygiene, and troublesome work. Decide

산화제Oxidant

NaNO2, NaNO3등 질산염으로 첨가되며 액 중에서 분해하여 발생기 산소를 발생하여 인산염 형성반응을 현저히 촉진하는 효과가 있으며 0.3g/l 이하에서는 인산염 형성반응이 느리고 한편 1g/l 이상에서는 Fe 소지면을 부동태로 하여 동도금 및 인산염피막 생성을 조해한다. 따라서 그 범위를 0.3-1g/l로 정한다.It is added as nitrates such as NaNO 2 and NaNO 3 , and it is effective to accelerate the phosphate formation reaction by generating generator oxygen by decomposing in the liquid.The phosphate formation reaction is slow at 0.3g / l or less, while the passivation of Fe surface is more than 1g / l. The copper plating and phosphate coating production is promoted. Therefore, the range is set to 0.3-1 g / l.

PHPH

용액의 상성도를 PH 2 이하로 한 경우는 Fe소지면의 침식반응(치환반응)이 과다하여 Cu도금피막형성이 길어지고 결정성피막으로 되며 PH 3 이상에서는 Fe 소지면과의 침식반응이 약하여 피막의 밀착성이 불량하게 된다. 따라서 그 범위를 PH 2-3으로 정한다.If the solution has a pH of less than or equal to PH 2, the erosion reaction (substitution reaction) of the Fe surface becomes excessive, resulting in the formation of a Cu-plated film and the formation of a crystalline film. The adhesion becomes poor. Therefore, the range is set to PH 2-3.

[실시예]EXAMPLE

Figure kpo00001
Figure kpo00001

와 같은 조성의 처리용액을 조제하여 이 처리용액에 깨끗한 쇠못을 1분간 침지하여 적색의 Cu 도금층상에 인산염화성피막이 형성된 피복층을 얻고 물에 세척하여 건조하였다.A treatment solution of the same composition was prepared, and a clean iron nail was immersed in this treatment solution for 1 minute to obtain a coating layer having a phosphate coating on a red Cu plating layer, and washed with water and dried.

이 못을 국립시험원에서 시험한 걸과는 300℃에서 5분간 가열 후 공냉한 결과 균열 또는 부풀음이 없는 매우 밀착성이 좋고 견고하고 방청, 내식성이 우수하고 도장성 및 내구성이 우수하였다.The nails tested at the National Laboratory were air cooled after heating at 300 ° C for 5 minutes, and were very good in adhesion and firmness without cracking or swelling, and were excellent in corrosion resistance, corrosion resistance, paintability and durability.

본원방법을 철관 온돌사관에 실시한 바 열전도성이 좋고 방청 내식성이 좋아 구리관에 손색없는 온돌배관을 염가로 시공할 수 있었다.The present method was applied to the iron pipe ondol pipe, so that the thermal conductivity was good and the corrosion resistance of the rust was good.

본 발명에 있어서 Cu원으로서 Cu(H2PO4)2를 사용하는 경우는 Cu 도금원으로뿐 아니라 인산염피막화성제로서도 작용하게 되어 인산염피막으로서 CuHPO4또는 Cu3(PO4)2로 되고 Cu와의 친화성으로 일층 견고한 밀착성 화성피막을 형성하는 것이다.In the present invention, when Cu (H 2 PO 4 ) 2 is used as the Cu source, Cu (H 2 PO 4 ) 2 acts not only as a Cu plating source but also as a phosphate coating agent, thereby forming CuHPO 4 or Cu 3 (PO 4 ) 2 as Cu phosphate coating. The affinity with and forms a firmer adhesion film.

이상과 같은 본 발명은 철강소지에 구리의 무전해 도금과 인산염화성피막을 동시에 간단히 한 공정에 의하여 형성할 수 있는 매우 산업적으로 유효한 발명인 것이다.The present invention as described above is a very industrially effective invention capable of simultaneously forming an electroless plating of copper and a phosphate coating on a steel substrate by a simple process.

Claims (2)

구리이온원으로서 Cu(NO3)2, Cu(H2P04)2, CuSO4와 인산염피막제로서 NaH2PO4, NaP03, Zn(H2PO4)2, Mn(H2PO4)2등의 제1인산염, 과 환원제로서 호르마린 및 산화제로서 NaNO3, NaNO2등으로 조성된 산성 처리용액에 철강소지를 디핑함으로서 철강 소지면에 구리 화학도금과 동시에 불용성인 제2, 제3인산염피막을 형성함을 특징으로 한 구리도금과 인산염피막을 동시에 형성하는 방법.Cu (NO 3 ) 2 , Cu (H 2 P0 4 ) 2 , CuSO 4 as a copper ion source and NaH 2 PO 4 , NaP0 3 , Zn (H 2 PO 4 ) 2 , Mn (H 2 PO 4 ) as a phosphate coating agent Second and third phosphate coatings which are insoluble at the same time as copper chemical plating on steel substrates by dipping steel substrates into acidic treatment solutions composed of primary phosphates such as 2 , and supermarines as reducing agents and NaNO 3 and NaNO 2 as oxidizing agents. Forming a copper plating and a phosphate coating simultaneously. 제1항에 있어서 처리용액은 Cu 2-lOg/l, 호르마린 1-2g/l, 제1인산염 2-lOg/l, 산화제 0.3-1g/l로 되는 철강소지에 구리도금과 동시에 인산염 피막을 형성하는 방법.The process solution according to claim 1, wherein the treatment solution is coated with copper and simultaneously with a phosphate coating on steel substrates made of Cu 2-lOg / l, Hormarin 1-2g / l, monophosphate 2-lOg / l, and oxidant 0.3-1g / l. How to form.
KR1019880001696A 1988-02-15 1988-02-15 Method to make a phosphate film with a copper coating on steel substrates KR900005843B1 (en)

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