JPS62177199A - Dispersion plating liquid - Google Patents

Abstract

PURPOSE:To simplify the composition of a dispersion plating liq. and to facilitate the control of the composition as well as to reduce the cost of materials by adding ammonium chloride at a specified concn. to the plating liq. prepd. by suspending a dispersible material in a nickel sulfamate soln. as a base without adding nickel chloride used generally in the plating liq. CONSTITUTION:Ammonium chloride is added by 5-50g/l, preferably 20-40g/l to a dispersion plating liq. prepd. by suspending a dispersible material such as hard and fine SiC particles in a nickel sulfamate soln. as a base without adding nickel chloride used generally in the plating liq. A plated film of an Ni-P alloy contg. dispersed SiC formed with the resulting dispersion plating liq. has a strong matrix, the hardness of the plated film is increased and the control of the composition of the plating liq. is facilitated.

Description

[Detailed description of the invention] a. Industrial application field The present invention relates to a dispersion plating solution with improved coating properties.

b. Surface treatment using the conventional technology dispersion plating method involves forming a film composed of eutectoid fine particles and a metal matrix on the base metal.
This is a method of imparting new properties to metal surfaces.

The eutectoid fine particles used in this method include silicon carbide (Si
C), alumina (A1.Oyu), silicon nitride (SiJa)
, hard fine particles such as diamond (C), and boron nitride (
BN).

There are lubricating particles such as sericite and Teflon.

By various combinations of these eutectoid fine particles and the metal matrix, a dispersion plating film having properties such as wear resistance, lubricity, heat resistance, and corrosion resistance can be formed on the base metal.

The wear resistance, lubricity, and other properties achieved by the dispersion plating film, which are more than the problems that the C0 invention aims to solve, are not due to the metal matrix itself that constitutes the dispersion plating film, but to the eutectoid metal matrix itself. The metal matrix only plays an auxiliary role. In particular, N1-P-5iC, N1-P-AIyOz+ with wear resistance and heat resistance
In dispersion plating coatings such as N1-P-5iJ4+ or N1-P-diamond, SiC.

It is necessary to configure the metal matrix so that the functions of hard fine particles such as ^1□Oj+ 5iJ4 or diamond can be fully exhibited.

However, if the N1-P alloy matrix does not have sufficient hardness, or if the hardness of Malinox deteriorates in high-temperature cloud surroundings, the fine particles protruding from the matrix surface and eutectoid will not disperse. Due to the surface pressure exerted by the member on the other side of the plated membrane, the plated membrane is buried in the matrix.

Therefore, from a macroscopic perspective, the surface of the dispersion plating film is no different from a surface made of only a single metal matrix, and the problem arises that the functions of the eutectoid fine particles are not exhibited at all.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to solve the problems of the prior art and to provide a dispersion plating solution having an improved composition.

d. Means for Solving the Problems In order to solve the above-mentioned problems, the present invention provides a generally used dispersion plating solution which is based on a nickel sulfamate solution and has a dispersion agent added thereto. In addition to omitting the addition of nickel chloride that is normally used, ammonium chloride is added at 5 to 50 g/7! , preferably 20-40g/
It was added at a ratio of 14:1.

Hereinafter, the present invention will be explained in detail with reference to the drawings.

N l+ Cu as a metal matrix for dispersion plating
+Ni-Co, N1-P, or Zn are used, but the most used is Ni matrix, and among these, N1-P has a certain degree of heat resistance.
Alloy matrices are often used. And this N1-
As the nickel bath for forming the P alloy matrix, a nickel sulfamate bath is advantageous because it can provide a relatively high current density and has high productivity.

An example of a commonly used composition of this nickel sulfamate bath is shown in Table 1.

Table 1 Nickel sulfamate solution (Ni(S(h ・N
Hz)t・4Lf)): 500 (g/
7!11 Nickel chloride (NiC1□・61120
): 15 Boric acid
(I(ffBOri:
45〃P compound (1'): o,
i~4.2〃Silicon carbide (SiC): 100
~150 In this nickel sulfamate bath, the problem that occurs in the management of the acid bath is that nickel sulfamate decomposes and ammonium sulfate is produced as a by-product due to low Pl+, bath temperature of 7oC or more, or local heating.

As shown in the following formula, both the ammonium ion (NH, ゝ) and the 6N 1m ion (SO, ``-'') constituting ammonium sulfate become factors that have an adverse effect on the plating solution.

SO, l-N11z-10HzONHa' + SO
4'' - As a result, the internal stress (electrodeposition stress) of the plating solution becomes high, and the plating film becomes brittle, and eventually the plating solution becomes unusable.

The present inventors focused on the fact that the plating film becomes brittle due to the presence of NIl,' ions in this plating solution. If the plating film becomes hard,
In the present invention, in particular, NIl,' ions are added to the nickel sulfamate bath shown in Table 1 to form a hard plating film.

In the present invention, ammonium chloride: NIl, CI, for example, was used as the NH4'' ion to be added.
If the amount of If a Cl added to the plating solution is too large, the action as a so-called impurity will increase, which is not preferable.

Furthermore, in the present invention, the composition of the nickel sulfamate bath is improved by the following method in addition to the addition of NH and CI.

That is, looking at the role of the composition constituting the plating solution, first, nickel sulfamate replenishes most of the nickel ions. Nickel chloride also replenishes nickel ions and promotes anodic dissolution. Furthermore, the newly added ammonium chloride has the additional effect of improving the hardness of the plating film as described above and promoting anodic dissolution. Therefore, the present invention focuses on the effect of ammonium chloride to promote dissolution of IWIJi and attempts to replace the effect of nickel chloride, thereby omitting the addition of nickel chloride and improving the bath composition. be. The supply of nickel ions is based on sulfamic acid nifgal.

e. Example First, Table 2 shows an example of the plating solution according to the present invention.

Table 2 (Chemical name) (Concentration) S37 amino acid difluoride solution: 5
00 (g/l>boric acid
: 45 Hypophosphorous acid
io, 6 ammonium chloride
:35# silicon carbide :100-150#
Satucharin Soda: 3 When considering the amount of NIl and CI added in such a plating solution according to the present invention, it was found that if the amount added is large, the action as so-called impurities becomes large for the plating solution. Undesirable. Figure 1 shows the old 1. This figure shows changes in the internal stress (or electrodeposition stress) and hardness of the plating solution with respect to the concentration of Cl, that is, the amount added. According to this figure, in the case of the plating solution according to the present invention (see Table 2), N
The internal stress value for It 4 CI 'jar degree is nickel chloride (15
Compared to the plating solution containing plating solution (indicated by g/1) (as shown in the above), the values were slightly lower over the entire concentration, which is a good result.

On the other hand, if we look at the effect of hardness on the amount of NH and CI added, if the amount added is small, we cannot expect much improvement in the hardness of the plating film (see the hardness curve in Figure 1). , the amount of N II aCI added in the nickel sulfamate bath was 5 to 50 g/1.

The appropriate amount is preferably 20 to 40 g/f.

In addition, in the plating solution according to the present invention, the anodic dissolution efficiency was sufficiently maintained due to the anodic dissolution function of ammonium chloride, and similar problems did not occur.

As described above, hard fine particles such as SiC are suspended in a nickel sulfamate solution, and N II , C
N1-P-Si obtained by adding I and omitting the conventionally used nickel chloride
The C-dispersed nifkelurin alloy plating film has a strong matrix, and the hardness of the film is further increased.

Therefore, the plating film obtained by the plating solution according to the present invention, which has a simplified composition, retains the SiC particles even against the surface pressure of the mating material facing it.

It can be kept protruding from the surface of the plastic.

FIG. 2 shows a comparison between the plating film obtained using the plating solution according to the present invention shown in Table 2 and that obtained using the conventional plating solution shown in Table 1, that is, the relationship between the hardness of the two depending on the heat treatment temperature. shows. As is clear from the figure, the plating film obtained using the plating solution according to the present invention shows a much higher value, indicating that the addition of Nll4CI has a great effect on improving the plating film. That is, Ni
A sulfamino acid nickel bath was used in which 1, CI was added at a rate of 35 g/12 times, and SiC was added to this bath.
The plating film obtained from the plating solution in which the .

Table 3 shows an example of another plating solution of the present invention.

Table 3 (Chemical name) (Concentration) Nickel sulfamate solution 5
00 (g/1) boric acid
45 Sodium hypophosphite l Ammonium chloride
35〃Silicon carbide 100-150〃
Saccharin soda 3 Figure 3 shows the relationship between the plating film formed with the plating solution shown in Table 3 and the plating film formed with the conventional plating solution shown in Table 1, compared in the same manner as in Fig. 2. show. As in the case of FIG. 2, it can be seen that the plating film formed by the plating solution according to the present invention is superior to the conventional one.

Table 4 shows still other examples of plating solutions of the present invention.

Table 4 (Drug name) Nifkel sulfamate γ &
500 (g/l-)
Acid 45 Ammonium chloride 35 Silicon carbide
100-150〃 Satucharin Soda 3〃The relationship between the plating film formed with the plating solution shown in this Table 4 and the plating film formed with the plating solution with the conventional composition excluding the P compound from the above Table 1 is as follows. Figure 4 shows the results of the same comparison as in Figure 2.The plating film formed with this plating solution according to the present invention has a micropinkers hardness of about 620 at room temperature.
(lIIIv).

The maximum hardness was about 690 (l1mν).

f4 Effects of the Invention As described above, according to the dispersion plating solution according to the present invention, a predetermined amount of ammonium chloride is added to the dispersion plating solution which is based on a nickel sulfamate solution and has a dispersion material suspended therein, and a predetermined amount of ammonium chloride is added. By omitting the addition of dichloride and kel, which was previously used, it is possible to reduce the cost of plating materials, simplify the composition of the plating solution and make it easier to manage.Moreover, the coating has high hardness, wear resistance, and heat resistance. A dispersion plating film with excellent properties and lubrication resistance can be obtained.

[Brief explanation of drawings]

Figure 1 is a diagram showing the relationship between NHACl a degree, internal stress, and plating film hardness in a dispersion plating solution, and Figures 2-
FIG. 4 is a diagram showing a comparison of the hardness of a plating film formed with the dispersion plating solution according to the present invention and the hardness of a plating film formed with a conventional dispersion plating solution at each heat treatment temperature. Patent Applicant Suzuki Motor Co., Ltd. Agent Patent Attorney Hisao Okuyama (and 2 others) Value in (μm) -
---1 Conventional method heat treatment temperature (lhr) Figure 3 O-111 According to the present invention ---1 Conventional method heat treatment temperature (Ihr) Figure 4 0--1 Uninvented method・---1 Conventional method heat treatment temperature (Ihr) Procedural amendment (Own ship May 23, 1988; 1 Director General of the Patent Office Michibe Uga 1, Indication of the case Patent Application No. 19311 of 1988) 2. Name of the invention Dispersion plating solution 3. Relationship with the case of the person making the amendment Patent applicant name (20B) Suzuki Motor Co., Ltd. 4. Agent 107 (and 2 others) 5. Contents of the amendment subject to the amendment 1 ) "Improvement of plating film" in the third line from the bottom of page 9 of the specification is corrected to "improvement of hardness of plating film". 2) Same, page 12, line 4, “lubrication resistance” was changed to “lubricity”
I am corrected. 3) Correct Figure 1 as shown in the attached drawing.

Claims (1)

[Claims] In a dispersion plating solution in which a dispersant is suspended in a nickel sulfamate solution, the addition of nickel chloride normally used in the plating solution is omitted, and ammonium chloride is added in an amount of 5 to 50 g/l, preferably 20 to 40 g/l. A dispersion plating solution, characterized in that the dispersion plating solution is added at a ratio of 1.