KR20130115728A - Electroless ni-w-p alloy plating solution and the method for plating using the same - Google Patents
Electroless ni-w-p alloy plating solution and the method for plating using the same Download PDFInfo
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- KR20130115728A KR20130115728A KR1020120038312A KR20120038312A KR20130115728A KR 20130115728 A KR20130115728 A KR 20130115728A KR 1020120038312 A KR1020120038312 A KR 1020120038312A KR 20120038312 A KR20120038312 A KR 20120038312A KR 20130115728 A KR20130115728 A KR 20130115728A
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1841—Multistep pretreatment with use of metal first
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
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Abstract
The present invention relates to an electroless nickel-tungsten-phosphorus alloy plating solution and a plating method using the same, and more particularly, to the corrosion resistance of various metals by electroless plating using a nickel-tungsten-phosphorus plating solution instead of a conventional electroless nickel plating solution. The present invention relates to an electroless nickel-tungsten-phosphorus alloy plating solution for forming a film capable of improving wear resistance and a plating method using the same.
The plating method using the nickel-tungsten-phosphorus alloy plating solution according to the present invention comprises a compound of nickel sulfate hexahydrate, sodium hypophosphite and sodium tungstate, and at least one of sodium citrate, glycine, ammonium sulfate and ammonium citrate It characterized in that the tungsten-containing film is formed by immersing aluminum, aluminum alloy, stainless steel (SUS), iron or iron alloy material in the electroless nickel-tungsten-phosphorus alloy plating solution further comprises.
Description
The present invention relates to an electroless nickel-tungsten-phosphorus alloy plating solution and a plating method using the same, and more particularly, to the corrosion resistance of various metals by electroless plating using a nickel-tungsten-phosphorus plating solution instead of a conventional electroless nickel plating solution. The present invention relates to an electroless nickel-tungsten-phosphorus alloy plating solution for forming a film capable of improving wear resistance and a plating method using the same.
Electroless nickel plating was the first industrially used mass use of alkali electroless nickel plating to replace the electroless copper plating of plastics.
Globally, electroless nickel plating gradually increased from 1983 to about 10% from 1984 to 1986, but stopped due to the rapid development of memory hard disks and the development of electronic components in early 1990. In recent years, geometric growth has led to a shortage of raw material supplies.
Electroless plating is divided into non-catalyzed chemical reduction plating and self-catalyzed chemical reduction plating, and electrons are not self-catalyzed, so there is a limit to thick plating, and reaction occurs simultaneously in the object and in solution, so that the plating solution can be used again. On the other hand, the latter is an electroless nickel / copper plating, which is widely used for industrial purposes, and is a self-catalyzed electroless plating method, in which the metal in the plating solution acts as a catalyst by the reducing agent, and the plating reaction is performed by other plating agents ( It can be used continuously as long as it is reduced to the surface of the metal) to form a film and metal is replenished in the plating liquid.
On the other hand, stainless steel (SUS) is used as a high corrosion resistance material, in particular, it is used in a semiconductor equipment that is repeatedly used harmful chemicals. Such stainless steel also has a problem of causing a fatal defect in the semiconductor manufacturing process by generating a large amount of particles by outgasing in the ion implantation, chlorine-based, fluorine-based environment for plasma etching during the semiconductor manufacturing process.
In order to solve this problem, a film was formed on the surface of stainless steel by electroless nickel plating or anodizing. However, since the temperature is very high, such as 600-700 ° C. or higher, during the semiconductor manufacturing process, grains such as oxide films and metals on the inner surface of the stainless steel are formed. Particles are emitted from a deep place such as a grain boundary, which also acts as a particle, resulting in a problem of deterioration of chemical resistance due to fine pinholes.
Looking at the patent document related to the plating method using nickel, KR Publication No. 10-2009-0039256 (name of the invention: nickel-phosphorus-tungsten three-way alloy electroless plating solution, electroless plating process using the same and produced by Nickel-phosphorus-tungsten tertiary alloy coating) claims for an electroless plating solution containing nickel sulfate, sodium hypophosphite, sodium tungstate and a complexing agent, KR Patent Publication No. 10-2009-0102386 The nickel-phosphorus tungsten tertiary mechanical alloy electroplating apparatus and method thereof) is a three-base alloy electroplating comprising nickel sulfate, sodium hypophosphite, sodium tungstate, a first complexing agent, a second complexing agent, a pH buffer, and an accelerator. Claims have been made for the device, but the electroless plating solution and the electroplating device described above have problems of low tungsten content and insufficient acid resistance and wear resistance.
Numerous papers and patent documents are referenced and cited throughout this specification. The disclosures of the cited papers and patent documents are incorporated herein by reference in their entirety to better understand the state of the art to which the present invention pertains and the content of the present invention.
In the case of the existing electroless nickel plating solution, the particles are discharged from a deep place such as an oxide film on the inner surface, grain boundary of a metal, etc. in a very high temperature environment such as a semiconductor manufacturing process and the like, and thus, fine pinholes or the like. The problem that the chemical resistance falls by this was found, and earnestly researched in order to solve it.
As a result, when the plating solution is manufactured by combining nickel-tungsten-phosphorus and a series of complexing agents in an optimum ratio, corrosion resistance, abrasion resistance, and hardness are improved, thereby preventing discoloration or staining of the plated film on the metal surface. The present invention has been completed by discovering that it can be maintained in a stable state.
Accordingly, it is an object of the present invention to provide a plating solution for electroless nickel-tungsten-phosphorus.
It is also an object of the present invention to provide a method for plating aluminum, stainless and iron using the electroless nickel-tungsten-phosphorus plating solution.
Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.
The present invention provides an electroless plating solution.
In the case of the existing electroless nickel plating solution, the particles are discharged from a deep place such as an oxide film on the inner surface, grain boundary of a metal, etc. in a very high temperature environment such as a semiconductor manufacturing process and the like, and thus, fine pinholes or the like. The problem that the chemical resistance falls by this was found, and earnestly researched in order to solve it.
As a result, when the plating solution is manufactured by combining nickel-tungsten-phosphorus and a series of complexing agents in an optimum ratio, corrosion resistance, abrasion resistance, and hardness are improved, thereby preventing discoloration or staining of the plated film on the metal surface. It was confirmed that it could be kept in a stable state.
According to one aspect of the invention, the invention provides an electroless nickel-tungsten-phosphorus alloy plating solution comprising: (a) nickel sulfate hexahydrate (NiSO 4 6H 2 O) as a metal salt 30-50 g / Lt ; (b) 50-100 g / Lt tungsten alloy source selected from the group consisting of sodium tungstate (Na 2 WO 4 2H 2 O), oxide of tungstate, tungsten chloride and carbonyl tungsten chloride; (c) 30-50 g / Lt sodium hypophosphite (NaH 2 PO 2 H 2 O) as reducing agent; And (d) 50-100 g / Lt sodium citrate (Na 3 C 6 H 5 O 7 H 2 O), ammonium sulfate ((Na 4 ) 2 SO 4 ) 100-130 g / Lt, sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) 50-100 g / Lt and ammonium sulfate ((Na 4 ) 2 SO 4 ) 100-130 g / Lt, sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) 50 -100 g / Lt, ammonium sulfate ((Na 4 ) 2 SO 4 ) 100-130 g / Lt and glycine (HNCHCOOH) 30-50 g / Lt and sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) A complexing agent selected from the group comprising 50-100 g / Lt and 150-230 g / Lt ammonium citrate ((Na 4 ) 2 HC 6 H 5 O 7 ).
According to an embodiment included in the present invention, the present invention may include nickel sulfate hexahydrate (NiSO 4 6H 2 O) as a metal salt, preferably 30-50 g / Lt.
If the nickel sulfate hexahydrate is contained in less than 30 g / Lt, the plating power for aluminum, stainless and iron, etc. may be reduced, and if it contains more than 50 g / Lt, it may not contain a sufficient amount of tungsten, sufficient to the inside of the film There is a problem that it cannot contain a positive amount of tungsten.
According to a preferred embodiment of the present invention, the tungsten alloy source may preferably be selected from the group comprising sodium tungstate (Na 2 WO 4 2H 2 O), oxide of tungstate, tungsten chloride and carbonyl tungsten chloride, More preferably, it may be sodium tungstate or oxide of tungstate, and most preferably sodium tungstate.
According to a preferred embodiment of the present invention, the sodium tungsten may preferably comprise 1-100 g / Lt, more preferably 10-100 g / Lt, most preferably 50-100 g / Lt may contain. The amount of sodium tungsten is very important in the case that the plating film contains a large amount of tungsten, which can greatly increase the corrosion resistance and wear resistance of the plating.
When the content of the contained tungsten sodium is less than 50 g / Lt, the content of tungsten included in the plating is not enough to improve the corrosion resistance and abrasion resistance of the plating, and when it exceeds 100 g / Lt, the content of tungsten included in the plating is significant This is because the quality of the plating can be lowered if it contains more tungsten than necessary.
According to an embodiment included in the present invention, the present invention may include sodium hypophosphite (NaH 2 PO 2 H 2 O) as a reducing agent.
According to a preferred embodiment of the invention, the sodium hypophosphite as the reducing agent may preferably comprise 1-50 g / Lt, more preferably 10-50 g / Lt, most preferably 30- 50 g / Lt.
Sodium hypophosphite as the reducing agent serves to control the plating rate, when containing less than 30 g / Lt sodium hypophosphite has a problem that the plating rate is slow, when containing more than 50 g / Lt There is also a problem in that the addition of sodium hypophosphite is not significant and the plating rate is significantly increased.
According to an embodiment included in the present invention, the present invention may include sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) as a complexing agent, and the content may preferably include 1-100 g / Lt. More preferably 20-100 g / Lt, most preferably 50-100 g / Lt.
It is very important that the present invention may include 50-100 g / Lt of sodium citrate as a complexing agent. This is because when 50-100 g / Lt of sodium citrate is used as the complexing agent, up to 25% of tungsten is included in the plating to maximize the acid and wear resistance of the plating.
If sodium citrate is included as less than 50 g / Lt as the complexing agent, even if sodium citrate is used as a complexing agent, there is a problem that the high level of tungsten may not be included in the plating, and sodium citrate is included in excess of 100 g / Lt. This is because the tungsten content cannot be significantly increased compared to the amount of sodium citrate added.
According to an embodiment included in the present invention, the present invention may include ammonium sulfate ((Na 4 ) 2 SO 4 ) as a complexing agent, and the content may preferably include 1-130 g / Lt, more preferably Preferably 50-130 g / Lt, most preferably 100-130 g / Lt.
When the ammonium sulfate is included as a complexing agent in the present invention, the complexing function and pH buffering ability are strong, and the film formed by using the same includes tungsten of up to 15% and has excellent acid resistance.
According to an embodiment included in the present invention, the present invention provides 50-100 g / Lt of sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) and ammonium sulfate ((Na 4 ) 2 SO 4 ) as a complexing agent. And 130 g / Lt.
In the present invention, when the sodium citrate and ammonium sulfate are used as the complexing agent, the tungsten content is lower than that of the plating solution using sodium citrate, but the pH buffering ability is high, and the life of the plating solution is long. The film formed using the plating liquid contains up to 20% of tungsten and is excellent in acid resistance.
According to an embodiment included in the present invention, the present invention is a complexing agent sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) 50-100 g / Lt, ammonium sulfate ((Na 4 ) 2 SO 4 ) 100- 130 g / Lt and glycine (HNCHCOOH) 30-50 g / Lt.
In the present invention, when sodium citrate, ammonium sulfate, and glycine are used as complexing agents, the tungsten content is lower than that of the other plating solutions, but the pH buffering ability is high, and the content of the components forming the plating solution is small. to provide.
According to an embodiment included in the present invention, the present invention provides 50-100 g / Lt of sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) and ammonium citrate ((Na 4 ) 2 HC 6 H 5 O as a complexing agent. 7 ) 150-230 g / Lt.
50-100 g / Lt of the sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) and ammonium citrate ((Na 4 ) 2 HC 6 H 5 O 7 ) as a complexing agent in the present invention 150-230 g / Lt It is very important to include. This is because, in the case of including the complexing agent, the content of tungsten is drastically lower than in the case of using the other complexing agents described above, but the plating solution exhibits the highest pH stability, and the life of the plating solution can be dramatically improved. .
The present invention provides the advantage that the complexing agent in the above-mentioned category can be freely selected according to the purpose and use of the plating.
According to a preferred embodiment of the present invention, the plating solution may further include a pH adjuster selected from the group consisting of caustic soda (NaOH), aqueous ammonia (NH 4 OH) and sulfuric acid (H 2 SO 4 ), but is not limited thereto. It is free to choose a pH adjusting agent commonly used in the art.
According to another aspect of the present invention, the present invention provides a method for plating aluminum or an aluminum alloy using an electroless nickel-tungsten-phosphorus alloy plating solution comprising the following steps:
(a) degrease to remove contaminants present on the aluminum or aluminum alloy surface;
(b) etching the aluminum or aluminum alloy from which the contaminants of step (a) have been removed to remove the non-conductive aluminum oxide film present on the surface of the aluminum or aluminum alloy;
(c) neutralizing the etched aluminum or aluminum alloy of step (b) with a chemical comprising nitric acid or sulfuric acid to remove smites remaining on the aluminum or aluminum surface;
(d) performing twice the gating treatment on the aluminum or aluminum alloy from which the smat of step (c) is removed; And
(e) immersing the twice zincated aluminum or aluminum alloy of step (d) in the electroless nickel-tungsten-phosphorus alloy plating solution according to any one of the preceding claims to form a tungsten-containing film. Steps.
According to a preferred embodiment of the present invention, the double gating process is to immerse aluminum or aluminum alloy in an alkaline solution in which zinc oxide is dissolved in thick sodium hydroxide, which is commonly used to form a zinc layer on the surface of aluminum or aluminum alloy, It is immersed in a nitric acid solution to dissolve the zinc layer, and then again immersed aluminum or aluminum alloy in an alkali solution in which zinc oxide is dissolved to form a zinc layer.
As described above in the present invention, the double gating process is a very important component. This is because a uniform zinc layer is formed in the second zinc gating treatment than in the first zinc gating treatment, so that a dense and uniform film can be obtained during electroless nickel-tungsten-phosphorus alloy plating.
According to another aspect of the present invention, the present invention provides a method for plating stainless steel (SUS) using an electroless nickel-tungsten-phosphorus alloy plating solution comprising the following steps:
(a) degreasing and electrolytic degreasing to remove contaminants present on the surface of stainless steel;
(b) performing a nickel strike on the stainless steel from which the contaminants of step (a) are removed by a nickel chloride bath; And
(c) immersing the stainless steel subjected to the nickel strike of step (b) in the electroless nickel-tungsten-phosphorus alloy plating solution according to any one of claims 1 and 2 to form a tungsten-containing film.
In the present invention, it is very important to carry out the nickel strike in step (b). This is because the adhesion of the coating film to the stainless steel surface can be made very good through the nickel strike process.
According to another aspect of the present invention, the present invention provides a method for plating iron or iron alloy using an electroless nickel-tungsten-phosphorus alloy plating solution comprising the following steps:
(a) removing contaminants present on the surface of the iron or iron alloy by degreasing and electrolytic degreasing;
(b) activating the surface by immersing the iron or iron alloy from which the contaminant of step (a) is removed in an acidic solution to remove the oxide film remaining on the surface or the oxide film produced by electrolytic degreasing;
(c) immersing the surface of the step (c) activated iron or iron alloy in an electroless nickel plating solution to form a primary film; And
(d) immersing the iron or iron alloy having the primary coating of step (c) in the electroless nickel-tungsten-phosphorus alloy plating solution according to any one of the preceding claims to form a secondary coating containing tungsten. Steps.
According to a preferred embodiment of the present invention, the plating method is a pH of the plating liquid is 6-12, the temperature of the plating liquid may be carried out at 50-100 ℃ conditions.
According to a preferred embodiment of the present invention, the coating may preferably be formed to a thickness of 0.5-200 μm.
According to a preferred embodiment of the present invention, the coating may preferably include 3-25% of tungsten, but according to the purpose and use of the plating solution to control the type and content of the complexing agent to control the tungsten content contained in the coating It can be as described above.
The features and advantages of the present invention are summarized as follows:
(Iii) The present invention provides an electroless nickel-tungsten-phosphorus alloy plating solution comprising: (a) nickel sulfate hexahydrate (NiSO 4 6H 2 O) 30-50 g / Lt as a metal salt; (b) 50-100 g / Lt tungsten alloy source selected from the group consisting of sodium tungstate (Na 2 WO 4 2H 2 O), oxide of tungstate, tungsten chloride and carbonyl tungsten chloride; (c) 30-50 g / Lt sodium hypophosphite (NaH 2 PO 2 H 2 O) as reducing agent; And (d) 50-100 g / Lt sodium citrate (Na 3 C 6 H 5 O 7 H 2 O), ammonium sulfate ((Na 4 ) 2 SO 4 ) 100-130 g / Lt, sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) 50-100 g / Lt and ammonium sulfate ((Na 4 ) 2 SO 4 ) 100-130 g / Lt, sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) 50 -100 g / Lt, ammonium sulfate ((Na 4 ) 2 SO 4 ) 100-130 g / Lt and glycine (HNCHCOOH) 30-50 g / Lt and sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) A complexing agent selected from the group comprising 50-100 g / Lt and 150-230 g / Lt ammonium citrate ((Na 4 ) 2 HC 6 H 5 O 7 ).
(Ii) The film formed by using the electroless nickel-tungsten-phosphorus alloy plating solution of the present invention is improved in corrosion resistance, abrasion resistance, hardness, etc., compared to a film formed by a conventional electroless nickel plating solution, and thus discoloration of the film plated on the metal surface; It is effective to prevent the phenomenon of staining to maintain the plating state in a stable state.
(Iii) The electroless nickel-tungsten-phosphorus alloy plating solution of the present invention has an effect of dramatically reducing particle phenomena due to outgassing in the semiconductor process due to improved pinhole reduction, chemical resistance, and thermal stability.
(Iii) The electroless nickel-tungsten-phosphorus alloy plating solution of the present invention provides an advantage of producing a nickel-tungsten-phosphorus plating solution of various properties to suit the purpose by controlling the type and amount of the complexing agent to be added.
1 is a flow chart showing a process of plating aluminum or an aluminum alloy using a nickel-tungsten-phosphorus alloy plating solution according to the present invention.
Figure 2 is a flow chart showing a process for plating a stainless steel (SUS) using a nickel-tungsten-phosphorus alloy plating solution according to the present invention.
3 is a flow chart showing a process of plating iron or iron alloy using a nickel-tungsten-phosphorus alloy plating solution according to the present invention.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not to be construed as limiting the scope of the present invention. It will be self-evident.
Example
Throughout this specification, "%" used to denote the concentration of a particular substance is intended to include solids / solids (wt / wt), solid / liquid (wt / The liquid / liquid is (vol / vol)%.
The electroless nickel-tungsten-phosphorus alloy plating solution according to the present invention is composed of a compound of nickel sulfate hexahydrate, sodium hypophosphite and sodium tungstate, further comprising any one or more of sodium citrate, glycine, ammonium sulfate and ammonium citrate. It is characterized by comprising.
In addition, the plating method using an electroless nickel-tungsten-phosphorus alloy plating solution according to the present invention for achieving the above object is composed of a compound of nickel sulfate hexahydrate, sodium hypophosphite and sodium tungstate, sodium citrate, glycine Immersing an aluminum, aluminum alloy, SUS, iron or iron alloy material in an electroless nickel-tungsten-phosphorus alloy plating solution further comprising at least one of ammonium sulfate and ammonium citrate to form a tungsten-containing film. It features.
The present invention relates to an electroless nickel-tungsten-phosphorus alloy plating solution for forming a tungsten-containing film on a metal surface of aluminum, aluminum alloy, stainless steel (SUS), iron or iron alloy material, and a plating method using the same. Instead of a plating process using an electroless nickel plating solution, which is conventionally performed, a metal material to be plated is immersed in an electroless nickel-tungsten-phosphorus alloy plating solution to form a film containing tongsten on the surface of the metal material.
To this end, in the present invention, a plating solution is prepared using the chemicals listed in Table 1 below. Although Table 1 shows that tungsten is contained in sodium tungstate, tungsten can be provided from any one of tungsten oxide, tungsten chloride and carbonyl tungsten chloride in addition.
(g / Lt)
Ni-WP Plating
Na 2 WO 4 2H 2 O
pH: 6-12
Thickness: 0.5-100μm
W alloy rate: 3-25%
NiSO 4 6H 2 O
NaH 2 PO 2 H 2 O
Na 3 C 6 H 5 O 7 H 2 O
HNCHCOOH
(Na 4 ) 2 SO 4
(Na 4 ) 2 HC 6 H 5 O 7
Plating solutions can be prepared in a number of ways, including compounds of nickel sulfate hexahydrate (b), sodium tungstate (a) and sodium hypophosphite (c) by default, in addition to sodium citrate (d) and glycine ( e), ammonium sulfate (f) and ammonium citrate (g) further. Sodium hypophosphite (c) is a reducing agent according to the amount of the plating rate is adjusted. Sodium citrate (d) and ammonium citrate (g) are used as complexing agents, which affect the adhesion of the coating.
Looking at the composition and manufacturing method of the plating solution is as follows. Herein, the amount of chemicals used in the plating solution follows the composition ranges described in Table 1 above.
Example 1: Preparation of nickel-tungsten-phosphorus plating solution
Example 1-1: Preparation of Plating Solution (1)
Sodium citrate (d) was dissolved in a first container containing the required amount of pure water, sodium tungstate (a) was added to dissolve, and nickel sulfate hexahydrate (b) was completely dissolved therein. Sodium hypophosphite (c), a reducing agent, was placed in a second vessel containing the required amount of pure water to completely dissolve it. The plating solution 1 was prepared by gradually adding the solution of the second vessel while stirring the solution of the first vessel.
The plating solution 1 thus prepared maintained a high and stable tungsten content, and the film formed using the same contained up to 25% tungsten and had excellent acid resistance.
Example 1-2: Preparation of Plating Solution (2)
Ammonium sulfate (f) was dissolved in a first container containing the required amount of pure water, sodium tungstate (a) was added to dissolve it, and nickel sulfate hexahydrate (b) was completely dissolved therein. Sodium hypophosphite (c), a reducing agent, was placed in a second vessel containing the required amount of pure water to completely dissolve it. The plating solution 2 was prepared by gradually adding the solution of the second vessel while stirring the solution of the first vessel.
The plating solution 2 prepared in this way had a strong complexing function and a pH buffering capacity, and the film formed using this contained up to 15% of tungsten and had excellent scratch resistance.
Example 1-3: Preparation of Plating Solution (3)
Sodium citrate (d) is dissolved in a first container containing the necessary amount of pure water, ammonium sulfate (f) is dissolved therein, sodium tungstate (a) is dissolved therein, and nickel sulfate hexahydrate (b) is dissolved therein. ) Was completely dissolved. Sodium hypophosphite (c), a reducing agent, was placed in a second vessel containing the required amount of pure water to completely dissolve it. The plating solution 3 was prepared by gradually adding the solution of the second vessel while stirring the solution of the first vessel.
The plating solution 3 thus prepared has a lower tungsten content than other plating solutions, but has a strong pH buffering force and a long service life. The film formed using the plating liquid 3 contained up to 20% of tungsten and was excellent in scratch resistance.
Example 1-4: Preparation of Plating Solution (4)
Sodium citrate (d) is dissolved in a first container containing the required amount of pure water, and ammonium sulfate (f) and glycine (e) are dissolved therein. Nickel hexahydrate (b) was completely dissolved. Sodium hypophosphite (c), a reducing agent, was placed in a second vessel containing the required amount of pure water to completely dissolve it. The plating solution 4 was prepared by gradually adding the solution of the second vessel while stirring the solution of the first vessel.
The plating solution 4 thus prepared also had a lower tungsten content than other plating solutions, but had a strong pH buffering power, and had a small lifespan due to a small change in the content of the plating solution. The film formed using this had good acid resistance.
Example 1-5: Preparation of Plating Solution (5)
Sodium citrate (d) is dissolved in a first container containing the required amount of pure water, and ammonium citrate (g) is dissolved therein. Sodium tungstate (a) is added thereto and dissolved therein, followed by nickel sulfate hexahydrate (b). ) Was completely dissolved. Sodium hypophosphite (c), a reducing agent, was placed in a second vessel containing the required amount of pure water to completely dissolve it. The plating solution 5 was prepared by gradually adding the solution of the second vessel while stirring the solution of the first vessel.
The plating solution 5 thus prepared had a low plating rate and a low tungsten content, but had high stability of the plating solution. The film formed using this contained 3-5% of tungsten and had good acid resistance.
The plating solution may contain a pH adjuster for adjusting the acidity of the plating solution to pH 6-12, wherein any one of caustic soda (NaOH), aqueous ammonia (NH 4 OH) and sulfuric acid (H 2 SO 4 ) Can be used.
Conclusion: Quality Characteristics by Kinds of Complexing Agent
The quality of the nickel-tungsten-phosphorus plating liquids disclosed in Examples 1-1 to 1-5 and the products produced by the plating liquids prepared in the compositions shown in Table 1 were investigated. The evaluation items were tungsten content, pH buffering power, plating solution life and acid resistance, and were marked as very good (+++), good (+++), good (++) and normal (+) according to the quality of the plating solution and the finished product. (See Table 2 below).
In Example 1-1 prepared by adding only sodium citrate (d) as a complexing agent, the tungsten content was very excellent at 20-25%, and the acid resistance was also excellent. However, the pH buffering capacity and life span of the plating solution were found to be satisfactory.
In Example 1-2 prepared by adding only ammonium sulfate (f) as a complexing agent, the tungsten content was 10-15%, and the acid resistance was also good. The pH buffering capacity was good, but the plating solution life was good.
In Example 1-3 prepared by adding sodium citrate (d) and ammonium sulfate (f) as a complexing agent, the tungsten content was 15-20%, and the acid resistance was very good. pH buffering capacity was good and plating solution life was excellent.
In Example 1-4 prepared by adding sodium citrate (d), ammonium sulfate (f) and glycine (e) as a complexing agent, the tungsten content was 5-10%, and the acid resistance was good. The pH buffering ability was excellent and the plating solution life was also excellent.
In the case of Example 1-5 prepared by adding sodium citrate (d) and ammonium citrate (g) as a complexing agent, tungsten content was a normal level of 3-5%, and acid resistance was good. pH buffering capacity and plating solution life were found to be very good.
Example 1-1
++++
(Example 1-2)
+
(Example 1-3)
+++
(Example 1-4)
+
Example 1-5
+
(+ + + +: Very good, + + +: excellent, + +: good, +: normal)
As can be seen from the results of Table 2, in the case of preparing a plating solution that requires particularly high acid resistance and wear resistance characteristics, the plating solution may be prepared using the composition of Example 1-1, which requires high pH buffering power and plating solution life. When preparing a plating solution, it will be preferable to prepare the plating solution with the composition of Example 1-5. On the other hand, in the case of the plating solution prepared in Examples 1-3, the overall quality was found to be the best.
In conclusion, when the plating solution is prepared using the composition of the present invention, it may be possible to prepare a nickel-tungsten-phosphorus plating solution suitable for desired quality characteristics.
Example 2: plating process for each metal material using nickel-tungsten-phosphorus plating solution
Hereinafter, a plating process performed for each metal material will be described in detail with reference to the accompanying drawings.
Example 2-1: Aluminum Plating Process Using Nickel-Tungsten-Phosphorus Plating Solution
1 is a flowchart showing a process of plating aluminum or an aluminum alloy using a nickel-tungsten-phosphorus alloy plating solution according to the present invention.
Contaminants (mainly organic substances) such as fats and oils, buffing abrasives and the like existing on the surface of aluminum or aluminum alloys were removed by degrease.
Next, the non-conductive aluminum oxide film present on the surface of the aluminum or aluminum alloy is evenly corroded to remove the oxide present on the surface by etching and then remove the smut remaining on the surface of the aluminum or aluminum alloy. In order to remove it, neutralization with chemicals such as nitric acid or sulfuric acid completely removed foreign substances on the surface of aluminum or aluminum alloy.
Then, double gating is performed to uniformly form a film to be formed on the surface of the aluminum or aluminum alloy and to improve adhesion.
In the double gating process, aluminum or aluminum alloy is immersed in an alkali solution in which zinc oxide is dissolved in thick sodium hydroxide, which is commonly used to form a zinc layer on the surface of aluminum or aluminum alloy, and the zinc layer is immersed in a nitric acid solution. After dissolving, aluminum or an aluminum alloy is again immersed in an alkali solution in which zinc oxide is dissolved, thereby forming a zinc layer. The reason for this double jincate treatment is to obtain a dense and uniform film during electroless nickel-tungsten-phosphorus alloy plating since a uniform zinc layer is formed in the second jincate process than in the first jincate process. to be.
Thereafter, aluminum or an aluminum alloy in which a zinc layer was formed was immersed in the electroless nickel-tungsten-phosphorus alloy plating solution according to the present invention to form a film including tungsten. At this time, pH of the plating liquid was 6-12, and the temperature of the plating liquid was 50-100 degreeC. In addition, the thickness of the film formed on the surface of aluminum or aluminum alloy was 0.5-100 micrometers, and the tungsten alloy rate was 3-25% in the film.
Here, before the aluminum or aluminum alloy in which the zinc layer is formed is immersed in the electroless nickel-tungsten-phosphorus alloy plating liquid, a film may be formed primarily by immersing in a conventional electroless nickel plating liquid which is commonly used. At this time, the thickness of the film formed on the surface of aluminum or an aluminum alloy was 0.5-200 micrometers.
Next, the aluminum or aluminum alloy immersed in the electroless nickel-tungsten-phosphorus alloy plating solution was taken out, poured into a washing tank using pure water (H 2 O), washed with water, and dried.
Example 2-2: Nickel-tungsten-phosphorus plating solution Stainless steel Plating process
2 is a flowchart illustrating a process of plating stainless steel (SUS) using a nickel-tungsten-phosphorus alloy plating solution according to the present invention.
Contaminants present on the surface of stainless steel were removed by degreasing and electrolytic degreasing.
Next, stainless steel was immersed in an acid solution to remove the oxide film remaining on the surface or the oxide film produced by electrolytic degreasing to activate the surface, and nickel strike was immediately performed by a nickel chloride bath. The reason for the nickel strike treatment on the surface of the stainless steel is to improve the adhesion of the coating plated on the surface of the stainless steel.
Then, stainless steel was immersed in the electroless nickel-tungsten-phosphorus alloy plating solution according to the present invention to form a film containing tungsten. At this time, pH of the plating liquid was 6-12, and the temperature of the plating liquid was 50-100 degreeC. Moreover, the thickness of the film formed on the surface of stainless steel was 3-100 micrometers, and the alloy rate of tungsten in the film was 3-25%.
Next, the stainless steel immersed in the electroless nickel-tungsten-phosphorus alloy plating solution was taken out, poured into a washing tank using pure water (H 2 O), washed with water, and dried.
Example 2-3: iron or iron alloy plating process using a nickel-tungsten-phosphorus plating solution
3 is a flowchart illustrating a process of plating iron or an iron alloy using a nickel-tungsten-phosphorus alloy plating solution according to the present invention.
Contaminants present on the surface of iron or iron alloys were removed by degreasing and electrolytic degreasing.
Subsequently, iron or iron alloy was immersed in an acid solution to remove the oxide film produced by the trioxide film or electrolytic degreasing remaining on the surface to activate the surface.
Next, iron or an iron alloy was immersed in the electroless nickel-tungsten-phosphorus alloy plating solution according to the present invention to form a film containing tungsten. At this time, pH of the plating liquid was 6-12, and the temperature of the plating liquid was 50-100 degreeC. Moreover, the thickness of the film formed on the surface of iron or iron alloy was 0.5-100 micrometers, and the alloy rate of tungsten in the film was 3-25%.
Here, before the iron or the iron alloy is immersed in the electroless nickel-tungsten-phosphorus alloy plating liquid, the film may be primarily formed by immersing it in a commonly used electroless nickel plating liquid. At this time, the thickness of the film formed on the surface of iron or iron alloy was 3-200 μm.
Next, the iron or iron alloy immersed in the electroless nickel-tungsten-phosphorus alloy plating solution was taken out, poured into a washing tank using pure water (H 2 O), washed with water, and dried.
The tungsten-containing film formed by the above embodiments has excellent hardness and wear resistance at the same time as the film formed by general electroless nickel plating, and has corrosion resistance and chemical resistance of 10 times or more, and resistance even at temperatures around 300 ° C. Has thermal stability that does not change. In addition, due to the vacancy of tungsten in the coating, the fine pinhole phenomenon of the surface is reduced, so that it has excellent salt spray and chemical resistance.
Claims (8)
(a) 30-50 g / Lt of nickel sulfate hexahydrate (NiSO 4 6H 2 O) as a metal salt;
(b) 50-100 g / Lt tungsten alloy source selected from the group consisting of sodium tungstate (Na 2 WO 4 2H 2 O), oxide of tungstate, tungsten chloride and carbonyl tungsten chloride;
(c) 30-50 g / Lt sodium hypophosphite (NaH 2 PO 2 H 2 O) as reducing agent; And
(d) sodium citrate (Na 3 C 6 H 5 0 7 H 2 0) 50-100 g / Lt,
Ammonium sulfate ((Na 4) 2 SO 4) 100-130 g / Lt,
50-100 g / Lt sodium citrate (Na3C6H5O7H2O) and 100-130 g / Lt ammonium sulfate ((Na4) 2SO4),
Sodium citrate (Na3C6H5O7H2O) 50-100 g / Lt, ammonium sulfate ((Na4) 2SO4) 100-130 g / Lt and glycine (HNCHCOOH) 30-50 g / Lt and
Complexing agent selected from the group comprising 50-100 g / Lt of sodium citrate (Na 3 C 6 H 5 O 7 H 2 O) and 150-230 g / Lt of ammonium citrate ((Na 4) 2 HC 6 H 5 O 7).
The plating solution is an electroless nickel-tungsten-phosphorous alloy plating solution, characterized in that further comprises a pH adjuster selected from the group consisting of caustic soda (NaOH), aqueous ammonia (NH 4 OH) and sulfuric acid (H 2 SO 4 ).
(a) degrease to remove contaminants present on the aluminum or aluminum alloy surface;
(b) etching the aluminum or aluminum alloy from which the contaminants of step (a) have been removed to remove the non-conductive aluminum oxide film present on the surface of the aluminum or aluminum alloy;
(c) neutralizing the etched aluminum or aluminum alloy of step (b) with a chemical comprising nitric acid or sulfuric acid to remove smites remaining on the aluminum or aluminum surface;
(d) performing twice the gating treatment on the aluminum or aluminum alloy from which the smat of step (c) is removed; And
(e) immersing the twice zincated aluminum or aluminum alloy of step (d) in the electroless nickel-tungsten-phosphorus alloy plating solution according to any one of the preceding claims to form a tungsten-containing film. Steps.
(a) degreasing and electrolytic degreasing to remove contaminants present on the surface of stainless steel;
(b) performing a nickel strike on the stainless steel from which the contaminants of step (a) are removed by a nickel chloride bath; And
(c) immersing the stainless steel subjected to the nickel strike of step (b) in the electroless nickel-tungsten-phosphorus alloy plating solution according to any one of claims 1 and 2 to form a tungsten-containing film.
(a) removing contaminants present on the surface of the iron or iron alloy by degreasing and electrolytic degreasing;
(b) activating the surface by immersing the iron or iron alloy from which the contaminant of step (a) is removed in an acidic solution to remove the oxide film remaining on the surface or the oxide film produced by electrolytic degreasing;
(c) immersing the surface of the step (c) activated iron or iron alloy in an electroless nickel plating solution to form a primary film; And
(d) immersing the iron or iron alloy having the primary coating of step (c) in the electroless nickel-tungsten-phosphorus alloy plating solution according to any one of the preceding claims to form a secondary coating containing tungsten. Steps.
The plating method is a plating method, characterized in that the pH of the plating solution is 6-12, the temperature of the plating solution is carried out at 50-100 ℃ conditions.
The coating is characterized in that the plating is formed to a thickness of 0.5-200 μm.
The coating method comprises a tungsten of 3-25%.
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| KR20160090771A (en) | 2015-01-21 | 2016-08-01 | 티씨에스(주) | Method for tungsten alloy plating with and product plated with tungsten alloy |
| KR101645676B1 (en) * | 2015-03-24 | 2016-08-04 | 김대수 | Tungsten-nickel-molybdenum alloy electroless plating solution and plating method using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20160090771A (en) | 2015-01-21 | 2016-08-01 | 티씨에스(주) | Method for tungsten alloy plating with and product plated with tungsten alloy |
| KR101645676B1 (en) * | 2015-03-24 | 2016-08-04 | 김대수 | Tungsten-nickel-molybdenum alloy electroless plating solution and plating method using the same |
| CN105951062A (en) * | 2016-05-23 | 2016-09-21 | 河海大学 | Nano-sized-WC-strengthened Ni-W-P composite coating and plating process thereof |
| CN105951062B (en) * | 2016-05-23 | 2018-07-31 | 河海大学 | Nano-carbide enhances Ni-W-P composite deposites and its plating technology |
| CN109423670A (en) * | 2017-08-21 | 2019-03-05 | 珠海市椿田机械科技有限公司 | The preparation method and its electroplate liquid of track copper bar plating nickel on surface tungsten phosphorus alloy |
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