JPS5950194A - Method for plating aluminum, aluminum alloy, magnesium, magnesium alloy, zinc or zinc alloy - Google Patents

Abstract

PURPOSE:To form uniform Cu plating with high adhesive strength, by cleaning the surface of a material, forming a Zn or Zn alloy film by a Zn substitution method, and carrying out electroplating in a copper cyanide plating soln. contg. water soluble silicate. CONSTITUTION:The surface of a material such as Al, an Al alloy, Mg, an Mg alloy, Zn, or a Zn alloy is cleaned, and a Zn or Zn alloy film is formed on the surface of the material by a Zn substitution method. Electroplating is then carried out to the surface on which Zn or Zn alloy film is formed, or the cleaned surface of Zn or Zn alloy in a copper cyanide plating soln. contg. <=50g/l water soluble silicate to form Cu plating. Sodium ortho- or metasilicate, potassium ortho- or metasilicate, ammonium ortho- or metasilicate or the like is used as the water soluble silicate.

Description

[Detailed description of the invention]

The present invention relates to a method for plating aluminum, aluminum alloys, magnesium, magnesium alloys, or zinc, zinc alloys. Aluminum, aluminum alloy (J]
It is light, yet has enough strength to attack, and also has excellent conductivity, so it can be used for various construction materials, materials, electronic equipment, etc. It is often used for mold parts, electrical equipment 1'il (+4, etc.) Also, zinc, zinc alloy (hereinafter abbreviated as zinc-based alloy) t, t
M-tight casting is possible, and the above various types (:'-Fushi 1 Te■ Material 471
However, the surface of the alloy is covered with a strong filtration film in the atmosphere, and the electrical contact resistance is extremely low.
- Mouth: It has the disadvantage that it is difficult to attach half 1-11 to the surface of the mouth. Also, this oxidation degree %IL. 11 (Also has the disadvantage of worsening heat resistance. In order to eliminate these defects, and also () - from the decorative point of view, Conventionally, electroplating was performed on these metal grains and alloys at a rate of tJ per 1 m.
1 The following method has been tested. 0 Aluminum alloy, magnesium alloy; Material, →
Dessert Sakaki water washing → pickling → water washing → 111 (lead substitution - tru, that pond) It plating, no electroplating 0 zinc alloy; Material → descaling → water washing → pickling → water washing → cyanization Copper IH plating → water washing → nickel, the pond's flu gas M) is applied, no vat Fl'l' plating However, using the conventional cyan system plating bath, the silver tlf is noticed, By removing degreasing, water washing, pickling, water washing, and iff fn substitution treatment, aluminum alloys, magnesium alloys, and magnesium alloys with a zinc It9 film formed on the material surface (first part 1! When the surface of a zinc-based alloy material is immersed in a cyanide r4 electroplating bath, the zinc coating on the material surface or r, J: I + [lead-based alloy Since the surface undergoes a substitution reaction with cyanide f1.! and the components in the plating bath, the surface of the plating material is exposed to the irradiation of [4 It, J Be? τ1ri electric current of plating, close contact t', l: 1:

[
Iyl-na:, ql of Ru゛'J'/j'F'IC
There was no warm skin. In the valley C, - Te, of... d) with - [nickel chrono NXIL 'I'u+, gold, 9 barbs, platinum, etc. performed early f'tt.
((Plating, no plating? Tj l'lY W) Plating skin that is damaged by about 1-1?'J) 111 Even worse, non-uniformity, and the incidence of defective products was high. The inventor of the present invention has uniformly applied copper, nickel, or other plating to the bare surface of an aluminum alloy, a magnesium alloy, or a zinc alloy. As a result, I completed the present invention by obtaining the following knowledge! 1 to t bu ξ. 11 and 91) By substitution method, wave N2 is applied to aluminum alloy, magnesium alloy element +1 side; 1 ■ Lead or v, ■
, 11 [(The thickness of the lead alloy film L is very thin, (+,
(Chips at about 15 to 05 μm. Furthermore, zinc itself σ)
Because the tendency to become older is more dog-like than the normal one, the above-mentioned elementary school]
11i of the surface. Lead or rt,, r + ff lead alloy film, tyu, sub-G) non-alloy -4E +1 side is immersed in a scraping bath,
For a short time, Jm usually elutes within several tens of seconds. l.The main component of copper plating bath is cupric cyanide,
If soluble silicic acid (-acid 11+ is included, zinc 1i!! film of zinc or zinc alloy obtained by the conversion method or the A'f surface of the zinc-based alloy substrate will be the interface of the silicic acid 1 story ion monologue. It is preserved by physicochemical behavior and does not elute into the plating bath, and by plating 9 drops into the plating bath, it can be used whether it is a barrel method or a hook method. , it is possible to always perform copper plating with good uniform adhesion, and furthermore, in the subsequent nickel and other plating processes, the plating is applied with good and uniform adhesion. The water-soluble silicate takes a special solution structure in water and exhibits unique behavior at the interface with F'l.
It is known that this behavior has a masking effect and a cleaning effect (・ru), but this behavior can be actively applied to IIt plating to improve The present invention was completed based on new knowledge that was useful for adjusting the surface behavior throughout the day.In other words, the gist of the present invention is to apply V,
1. Purify the filial surface 5. - (+lIj f in Table 1N+1
iI It1. In the case of L7, E, i'lli ship non-alloys, which have a zinc alloy coating and a zinc alloy coating, the above pretreatment is performed and the surface of the material is dissolved in water. Sexuality n'9. Copper was plated in a cyanide 4 plating bath with AK, nickel, chromium, copper, semi-11J1 gold, Silver, platinum, etc. 1. I'J'i plating 71 tons of plating
IB 9) (accommodates theory. The aluminum-based alloys used in the present invention include general aluminum plate materials, 1.1 materials (1σ)+1, duralumin, and other aluminum alloys. -5i series (silmin etc.), AI-) (u series, AI-MV series, A7-yy-s
i series, hl-au-s1 series (Rautaur etc.), kl-
Alloy materials such as Ou-MV-Ni (Y alloy, etc.) are shown. Magnesium alloys include MV-AA'-Mu and MP-
-Zu-Mu series, M5'-Zu-Zr series and other alloys are shown. 11i P:' I-based alloys include alloys such as general pure zinc 4° (in addition to Zu-/1-Gu-), 4P-based, and Zu-A/based. The treatment process and zinc replacement method for materials are generally as follows: 0 Aluminum alloy (water washing) → Cyan system, copper alloy plating → Water washing → Depletion process Zinc 1d replacement treatment bath and conditions; Water fat Sodium chloride, 120-500 V/1 Zinc oxide 20-l 00 f//13 Second chloride
Iron 1~41/l Lotusel salt lO~50 F/'111i11
n? Sodium 0-2flnnl! Every time
20-25°C Immersion time 30-120 seconds O Magnesium alloy degreasing - → Water washing → 11-inch washing → Water washing → Zinc ti'i exchange treatment →
Wash with water → cyan f1. ((1, θ same alloy?〆7ji-) Ki-tei water i'1.-st? (Step starved lead replacement treatment 11 [I bath and conditions; Zinc sulfate 3 jl ~ 451-/1 birophosphoric acid Sodium, 1.20~2], Oy/('. Sodium fluoride 57/l Sodium carbonate 5 y/l wet bap
(68-75°C Immersion time 5-10 minutes 0 Zinc-based alloy degreasing → water washing → r1 cycle washing → water washing → cyanide silk plating → water washing → next step Composition and electroplating conditions of the cyanide copper plating bath according to the present invention is the first step cyanide in the following 1111 -@
25-100g/l Sodium cyanide 35-1
50g/l sodium carbonate C) ~ J, 0 (
l Y/lJ water soluble t・[dred salt ~□ ri
11 Sl' / 14 pH], (+-■1.8 Temperature 40 to 65°C In the present invention 11"
A new ingredient in the cyanide bath.
Water-soluble fa to be blended: water-soluble fa, sodium chloride and metal chloride, potassium chloride and potassium chloride, ammonium ammonium, etc.
It will be done. When water-soluble silicic acid (/
'! If it is -713 or more, the plated surface becomes dirty and current efficiency deteriorates, which is not preferable. According to the method of the present invention, it is possible to uniformly and uniformly loosen plating such as silk, nickel, and other materials on the surface of materials such as aluminum alloys, magnesium alloys, and salivary lead alloys, and to remove defects in the plating. Incidence rate V" is extremely low. Next, practical aspects of the present invention will be explained using practical examples, but the present invention is not limited by these. Example 1 An ordinary aluminum plate with a thickness of 1B is 5 Q m x 10
Remove the small piece of aluminum that was cut into 1'7i L, washed with water, (washed with water, then washed with water, 1)
1 ■ dlj @itei′tF,. Processing (so-called zinc-[lJ1!! logic) line 19 7'C
It was. Next, the obtained zincate solution 1 aluminum piece was subjected to the following copper anhydride plating bath: III '--
Copper electroplating is performed using the 411 method under the conditions described in R and F)
Ta. Cyanide frx-copper 35g/7' Sodium cyanide 51 'I/IJ Ortho Kei 69 Natriuno, 5';//1 Sodium carbonate 5
0f/1fpHIl, (1 temperature 50 C 1 [T, flow density IK J-A / (1m
! Further, the resulting copper electroplated aluminum pieces were washed with water and plated with nickel using the 1B method. Nickel electroplating sets 1 and 1 are shown below. Sulfuric acid nickel 24 (lj//lI' nickel 45 Y//borous 30
W/1 Zatsukarin 111-/1 plI 4.5 Temperature: 50°C Current density: 2A/dm' Plating time: 2 minutes Cut two pieces from the obtained nickel-plated aluminum pieces, bring both surfaces into close contact, Half Ill at °C (
I went to Jke. After soldering both parts, I pulled them in a direction perpendicular to the soldering surface and peeled them off.
? i+ Ittt semi-1.11 surface), the exposure of nickel plated surface, copper plated surface, and aluminum base surface was not criticized. Comparative Example 1 A small aluminum piece similar to that used in Example 1 was subjected to degreasing → water washing → pickling → water washing → zincate treatment in the same manner as in Example 1. The same copper electroplating bath as used in Example 1 was used in Example 1 except for the addition of ortho-acid sodium. Copper plating was performed on the aluminum small piece. 711 et al.
, I'I-+'1 is itwoku, Muraga 73mera Jllfuku) 11 incidence is 15% Moari, V!・：An-ness is also 1：
t 7' in IJr, C in ). i (7) (!f
et Jl, Ta copper i1. <・(Plated aluminum Uno, small pieces each 71,411 pieces, 113 times nickel m <j
T-plated. The resulting nickel-plated aluminum pieces had uneven surfaces and bud adhesion, so a tensile test was conducted in the same manner as in Example 1 using a semi-ITI f=J of 1i. By the way, the peeling M'4 iii tt was on the aluminum surface of the J rim. ', +41. IIi Example 2 Aluminum Uno, alloy plate (Cu4..0%, sit. 2K, M rl (), 6?i%
MS' (1,696, evening", fit:
A A! ) into a 5 x 20 x 1 chip. Don't buy this chip! : IKa Example 1 was washed one by one, treated with zincate, and the following composition σ】6' issue + (+,
4th step: Plating was carried out using a barrel method using a plating bath of 1. Cyanide fr(-cut 3(1y/1 Sodium cyanide 40!/7'Metal ℃・r Shun Potassium
■o yiit1=I I+b Sodium 40
iV/dpH1+1.5 ; ]ui I(J
4 5 ℃1if 1jlj iil, n11IF'4'W I(!:
0. 5 A/dm fin when plating 2
After washing with water for 10 minutes, 11L nickel plating was carried out using the barrel method at a nL current density of 5 A/dm' using the bath composition and conditions shown in Example 1. Riki's aluminum chips are 1 chip 1 (i
, '4 is plated with good uniformity and good adhesion.
A tensile test was performed on the surface according to Example 1, and the peeled surface was V + 11. Comparative Example 2 Copper plating that was similar to Example 2 Pour ℃ ℃ acid potassium into the bath (except for...
The aluminum alloy chip was cleaned under the same conditions as in step 2, copper electroplated, and then nickel ttt
<・(Me・One look two lines car.
1, non-uniform '+': '? :
'M 11: The incidence rate has reached 202. Actual strength IX・11Ki (11 tensile test performed for the first time) 7 rollers, peeled surface t, j f (i plating surface - base surface No, tsuta. Example magnesyrano alloy plate (A12. 'i?6,Z
I)1. , 09g, MnO, 2%, balance MP) in 5. X
20 x J gate rh chip ((I made it. This chip f i)'! '4 The 1111 place (cleaned as soon as possible, then the next zinc replacement treatment) 4 soaked in 111 solution 11k. Zinc sulfate 40 ¥/1 Sodium bilorin 180111 Sodium fluoride 52/l Sodium charcoal 5y//l Flooding degree 7()℃ Purifying time 5 minutes Wash with water and use the flooding bath shown in Example 2. ~・
A 4-meter test was carried out using the barrel method under the same conditions. 1
! ) washed copper-plated magnesium alloy chips with water,
Nickel electroplating was performed using the same bath composition and conditions as in Actual Example 2. The r+I nickel plated chip is the chip l II!
The uniformity of l fl;'i was 1) and the density was also good (. When soldering was conducted a tensile test, it was found that the peeling surface was half 11, indicating excellent adhesion.Comparative Example 3 Magnesium alloy chips were pretreated under the same conditions as in Example 3 except for using potassium metasilicate in the copper electroplating bath, and copper electroplating was performed using a barrel method. The blistering rate of the cap-plated magnesium alloy chip reached 3526.Next, it was washed with water and subjected to nickel-11 plating under the same bath conditions as in Example 3.Nickel-plated chip #1 Fuku h occurrence rate is 469d, and the surface condition of each chip is also very good, uniform and adhesion 1'
I thought of 1. Execution 1' = 111, 1'< + (Tensile test was conducted) Peeling gate I# surface & -1... Plating surface - Barley J111, t9770't+) J was very poor. Example A74. l'6, Qu ],, 0
'X, M! 7 11. 0 5 5115
, Yu Q ('tlζzn's N lead die-casting product case (25X l O x 5, thickness l, Q rr
w+)? , said r)iJ b,l! p un H,
Barrel method available! Electroplating was carried out using the method shown in Example 2. Also, the nickel-plated product showed no blistering at all. In addition, when I soldered the same as Example IKQ and tested the pull-out test, I found that
The peeled surface is half Il1), '7j? ; Ya'i sex L
It was L Yuft. Comparative Example 4 In the copper plating bath used in Example 2, remove metallurgy, remove acid potassium, and remove all ingredients except !-7. Copper and nickel plating was applied to the new die-cast crystal case 7. The nickel-plated product 4526 blistered, and '
Jt”Wt was non-uniform.F<il, occurred (・
I11' 1st example Tbe' (Jitehan11)
When a tensile test was performed on 1 fr poppy, the adhesion was I/'
, [It was very bad that the NlJ H4 was bare-copper-plated. For patent purposes (1 person Tokyo Plating Co., Ltd. Patent Attorney Asano Fyo Tsukasa thousand grains if:, f'j Il-11t January 1, 1957 () 7'Ml ↑Ying' [r Director Aki Kazuo Waka ITsu] 6 small fl° display 1981 '1°? Revised de 1 (1st (i 1 n 54
Kano 2. Name of the invention Aluminum, aluminum alloy, magnesium, magnesium alloy or [1. Method for plating lead and zinc alloys 3. Relationship with the case of the person making the amendment Patent applicant address: Shimome M2, Meguro-ku, Tokyo. Ding ``113 No. 7 Name Tokyo Plating Co., Ltd. ・ 41 generation 1 (1 (person) 103 spontaneous correction n leopard 1t ilE imitation of the invention 07, f
(Li correct object (1) Detailed li' of the invention in the specification and Akira's (8, Contents of amendment (1) Particulars page 6, line 14 I 8 cross-Mu series moss 1A counterfeit-MTl-name ,] and!H' !l (Zuro. (2) Akii 11 effect (Shiro page F3 line 1' M
A l -M uJJ'(1'M/'!-A 5L
-M n, ij and n+1E. (3) Akira, page 1111116, line F2 r'Mg-Zu
-Mu system, M tLz tlz rq J %I
' M g z n-Mn system, Mg-Zn-Zr and full' ilE. (4) Details page 7, 2 lines [Z u-AI-cu
-M g ;R% Z u” 9- J J [zn
-Ai -+3u-Mg system, 7. n-A liberal arts,” he corrected.

Claims (1)

[Claims] (1) Clean the surface of aluminum, aluminum alloy, magnesium, magnesium alloy, zinc, zinc alloy, and then apply 1F to the material surface by zinc substitution method.
A lead or zinc alloy film is formed on the surface of the material or the surface of the material is treated with purified zinc or river (on the surface of the lead alloy material, water-soluble cyanide (containing acid salts) is applied in a copper plating solution. Electroplating is energized, f) A method to avoid rust plating on the iJ marking material surface (2)
)! f! ? tt'r 11? Item 1: Electroless plating of nickel, chromium, bar, semi-11J, gold, silver, and platinum (method of strengthening air plating)