Chapter 17

Electroless Plating Of Silver

N. Koura

It is frequently required to coat insulators such as glass and ceramics with

metals. Many methods are available for coating, e.g., baking, chemical vapor
deposition, ion-sputtering, and chemical plating. The chemical plating method
is very effective because the apparatus is simple, it can be done on a complex
substrate, and it is suitable for mass production. This method can be classified
into two categories: (1) the galvanic exchange deposition method, where the
potential difference between metals is utilized; and (2) the electroless plating
method, where reducing agents are used. In this chapter, only electroless
plating will be reviewed.
The silvering reaction is a well-known example of the electroless plating of
silver. This reaction was devised by Drayton (1) in 1830 and developed by Liebig
(2). This method is normally used to make mirrors. On the other hand,
electroless plating methods, which are utilized in the printed circuit industry,
have come into the limelight with the development of the electronics industry.
The electroless silver plating method (including the silvering reaction) is
important because any substance, i.e., both metals and insulators, can be coated
with silver by using this technique. Here the fundamental research and
applications of this method will be reviewed.

PLATING PROCESS
AND THE REACTION MECHANISM
The substrate pretreatment for electroless silver plating affects early stages of
the plating itself, and it plays an important role in the success of the plating
process.
The reactions that occur in the pretrestment and the plating processes are
separately summarized.

Pretreatment Process
The treatment for glass will be described first becauseelectroless silver plating is
usually carried out on glass. The plating is done soon after the pretreatment (3).
In the pretreatment process, the glass is degreased with acetone and alcohol,
44 1

442

ELECTROLESS PLATING

immersed in a SnClz solution for 1 to 2 minutes, then rinsed in warm water. A

SnCh solution has been used as the pretreatment bath for a long time (4) and is
thought to have two effects (1). Finesilver particles, which have a positivecharge
in the solution, adhere easily to the glass because the SnOz generated in the
solution from the hydrolysis of Sn" adsorbs on the surface of the glass, and the
negative charge on the surface increases. Ag' is reduced by Sn" and is then
adsorbed on the surface. Recently, the mechanism was discovered (5). The
behavior of Sn on glass was analyzed with X-ray photoelectron spectroscopy by
Pederson (6) as follows:
I
I
-Si-OH
+ SnCI; + H'O
Si-0-Sn-OH
+ 2H' + 3CI[I1
1
I

+ SnCI; -,S<
iS
'n

'Si/oH
\OH

'

+ 2H'

+ 3CI-

I21

'0

02Si-OH
-Si-OH

\I

+ SnCI;

- 0,,Si-O\
,Si-0
I

Sn + 2H' + 3CIF

[31

First, the exchange reaction of the Sn' ion occurs on the surface of the glass
according to Eqs.1-3. Then silver deposits onto the glass in the early stages of
the plating reaction, as shown in Eq. 4:

In this manner, the deposition of silver onto the pretreated glass surface is
induced early in the reaction. Then the plating reaction progresses according to
the theory stated in the next section. Geelen (7) also proposed a similar
mechanism by using the model as shown in Fig. 17.1.

Plating Reaction
It is well known that the silvering bath is highly unstable. The bath decomposes
as soon as the silvering reaction starts, and becomes muddy. Therefore it was
believed that the silvering occurs through the adhesion of silver particles with
positive charges generated in the solution ( 8 ) .With this in mind, attempts were
made to improve the silvering bath by stabilizing the fine silver particles in the
solution with a protective colloid (9). Gelatin, arabic gum, organic acids,
inorganic salts of zinc and lead, and copper sulfate were used as protective
colloid reagents.
There are many reports (10,ll) on the reaction mechanism of electroless
plating. One study states that the plating reaction progresseswith acombination
of a cathodic reduction of a cation, i.e, M"' + ne M, and an anodic oxidation of

Elecfroless Plating of Silver

443

Fig. 17.1-Model of the early stages of silver plating reaction on a glass substrate (7).

the reducing agent, Le.. R 0 + ne. In this case, it is thought that a metal ion is
cathodically reduced to metal on the surface, which is activated by a catalyst.
The above theory of electroless plating is applicable to silver plating because
silver is a metal on which an autocatalytic reaction occurs (12) as shown in Table
17.1. The concept of potential-pH diagram is very important in this theory. The
potential-pH diagrams for Ag-NH,-H:O and Ag-CN-H20 systems and various
reducingagentsareshown in Figs. 17.2,17.3,17.4andTable17.2(11,13).As the
potential of silver is very noble, as can be seen in Fig. 17.2, many reducing agents
can be used in electroless silver plating. There are 14 kinds of commercially
available reducing agents: formalin; dextrose; Rochelle salts; Rochelle salts +
silver nitrate; glyoxal; hydrazine sulfate; a boiled mixture solution of Rochelle
salts and crystallized sugar; sugar inverted by nitric acid (14); KBH, or DMAB;
aldonic acid and aldonic lactone (2,15);
cobalt ion (16); sodium sulfide (17);
triethanol amine (18); and CHrOH(CHOH),CH:OH (n = 1-6) (19).
Several examples of the reaction with representative reducing agents are
described below. Ag,O precipitation in the bath must be avoided because the
electroless silver plating is generally carried out in a basic solution. A

ELECTROLESS PLATING

444

Table 17.1
Metals Plated Autocatalytically (12)
Group

Period
3
4
5

VB

VI B

Cr

VI11
Fe
Ru

(09

co
Rh

(10

IB
Ni
Pd
Pt

Cu
Ag
Au

) = no report

complexing agent such as ammonia is added to the solution. The complex

formation reactions are thought to be as follows (14):
2AgNO3 + 2NH40H = Ag2O + 2NH4NO3 + H20

(51

AgzO + 4NH40H = 2[Ag(NH,)z]OH + 3H2O

[61

The silver plating is carried out by the reaction of the ammonia complex with
aldehyde, as in Eq. 8 (14). The electromotive force is 0.971V at pH 10.0 (20).
2[Ag(NH3)2]0H + RCHO

-.2Ag + 4NH3 + RCOOH + HzO

PI

There are many studies on the reaction with Rochelle salt as the reducing
agent. They are as follows:
2Ag(NH3); + 20H-%Ag20
3Ag20 + C406H;-

+ 20H-

+ 4NH3+ H 2 0

- 6Ag

2c204- + 3H20

4AgN03 + 4NH3+ C4H4NaK06+ H20

= 4Ag + 4NH4NOI + C3H2KNa05+ C02

[91

[lo1 (21)

Electroless flaring of Silver

Fig. 17.2-Potential-pH

445

diagram of A g - N H d b O system (13).

CHOHCOOK CHOHCOOAg boil. CHO

2AgNOi+ I
-I
-I
O2 CHO
CHOHCOONa CHOHCOOAg
+ AgJCOi + H2O + CO:

1141(14)

In Eq. 14, glyoxal (CHO-CHO) generated in the bath actsas a reducing agent.
Silver carbonate is filtered off.
The following plating reactions are reported for hydrazine (22) and
hydrazineborane (23):

- 4NHsNOi + 4NHi + Nz + 4Ag

40H- - N2H4 + B(0H)d- + 3/2H2 3Ag

4[Ag(NHi)>]NOI+ N:Hd
N,H,BHi + 3Ag'

~ 5 1
[161

The plating rates for various reducing agents are shown in Figs. 17.5-17.7

(20,24,25).
The rate for borohydride is somewhat faster than that for other

446

Fig. 17.3-Polential-pH

ELECTROLESS PLATING

diagram of Ag-CN-H,O system (13).

reagents. Moreover, hydrazine is often used in the spray method for mirror
production, as the deposition rate is fast (24).
The activation energies of the silver plating reaction for the glucose method
(26) and the Rochelle salt method are 27.1 k c a l h o l and 22.0 kcalhol,
respectively. Activation energies of electroless nickel plating for the alkane
succinic acid bath and the KBH, bath are 16.9 k c a l h o l and 9.9 kcal/mol,
respectively. These values indicate that the deposition rate for the electroless
silver plating is strongly influenced by temperature.
The polarization curves for the electroless silver plating bath that uses these
reducing agents are shown in Figs. 17.8-17.11 (21,29,30). A polarization curve
for the solution containing both silver and formalin cannot be determined,
because the solution is unstable (31).
The effect of pretreatment and the mechanism of electrolesssilver plating can
be studied from the partial anodic and cathodic polarization curves (32). Both
the partial cathodic polarization curve for a solution without Rochelle salt as the
reducing agent and the partial anodic curve for a solution without silver nitrate
are shown in Fig. 17.12. The 3,5-diiodotyrosine added bath (DIT bath), which is

Electroless Plating of Silver

447

Pn
Fig. 17.4-Potential-pH diagram of various reducing agents (11). (For Explanation of the numbers
(1) to (16), see Table 17.2)

the long-life bath described later, is used. The result for the electrode pretreated
with a SnClzsolution is shown with a solid line and that for the non-treated one is
shown with a dotted line. The difference between the partial cathodic
polarization curves in Fig. 17.12 is minimal. On the other hand, the difference
between the partial anodic polarization curves of the treated and the untreated
electrodes is clearly seen. In the case of the treated electrode, an anodic current
appears also in the range of 100-600 mV vs. SCE. At the same time, the rest
potential of the untreated electrode becomes 25 mV vs. SCE, and that of the
treated one becomes -81 mV vs. SCE. The difference in the rest potential is
attributed to the adsorption of Sn" ions on the electrode. Namely, it is thought
that the anodic current due to oxidation of the Sn-" ion flows at potentials of
100-600 mV vs. SCE. When the anodic and cathodic polarization curves for the
treated electrode are combined, a point of intersection appears at 0.02 mA/cm'
of current density. When this value of 0.02 mA/cm-' is converted to a plating rate,
the value is equivalent to 0.04 mg/cm'/30 min. This converted value is close to
the plating rate that is determined from the deposition quantity in Fig. 17.13. In
the case of the untreated electrode, the current density at the intersection is

448

ELECTROLESS PLATING

Table 17.2
Equilibrium Potential of Various Reductants (11)

No.'
1
2
3
4

5
6
7
8
9
10
11
12
13
14
15

16

Electrode
reaction
H,POI + 30H- = HPOi- + 2H:O + 2e
HPOJ- + 30H- = PO:. + 2H;O + 2e
H.POI + H.0 = H,PO; + 2H' + 2e
HIPO? + H 2 0 = H,PO, + 2H' + 2e
HIPOI + H?O = HtPO, + 2H* + 2e
HCOOH = CO. + 2H* + 2e
HCHO + H 2 0 = HCOOH + 2H* + 2e
2HCHO + 40H- = 2 H C 0 0 - + H?+ 2H.0 + 2e
HCOO- + 30H- = COi- + 2H?O + 2e
BH; + 80H- = BOI + 6H.0 + 8e
N2H; = Nz + 5H' + 4e
CN- + 20H- = CNO- + H.0 + 6e
HI = 2H' + 2e
S.0:' + 40H- = 2SO;- + 2 H 2 0 + 2e
S?Od- + 2H;O = 2S01- + 4H' + 2e
HS20; + 2H.0 = 2H?S01+ H' + 2e

Equilibrium
potential (E)
-0.31 @ 0.09 pH
0.14 @ 0.09 pH
-0.504 @ 0.06 pH
0.499 @ 0.06 pH
-0.276 (@ 0.06 pH
-0,199 (@ 0.06 pH
0.056 @ 0.06 pH
0.32 (@ 0.12 pH
0.25 (@ 0.09 pH
-0.45 @ 0.06 pH
-0.23 @ 0.075 pH
-0.13 @ 0.06 pH
0.000 @ 0.06 pH
0.56 @ 0.12 pH
-0.22 @ 0.12 pH
-0.056 @ 0.03 pH

'Numbers correspondto those in Fig. 17.4.

Fig, 17.5-Plating rates tor solutions using hydrazine ruilate, inverted sugar or Rochelle salt a8
reducing agents.

Electroless Platina nl Silver

449

. .-.... -....- --1

Fig. 17.6-Plating rates for solutions using formaline, glucose or Rochelle salt as reducing agents.

extremely small. Therefore, in the case of the DIT bath, it is thought that the
electroless silver plating reaction proceeds only on the substrate surface treated
with the SnCL solution and does not occur on the untreated surface.

Reaction in Non-Aqueous Solution

The silvering reaction in a non-aqueous solution is also reported (33). Figure
17.14 represents the reaction mechanism. A silver soap, which forms the micelle,
is stable in the solution. Since the soap adheres to the substrate surface, the
silvering reaction progresses.

Stability of the Plating Bath

It isvery important to stabilize the bath even for the electroless plating of Cu and
Ni. As stated above, the electroless silver plating bath is very unstable and
short-lived. Therefore, if the bath were made more stable, it would become more
useful. Many attempts have been made to improve the bath stability. It has been
determined that a small amount of 3-iodotyrosine or 3,5-diiodotyrosine added to
the bath works well as a stabilizer (34).

450

ELECTROLESS PLATING

Fig. 17.7-Plating ratesfor bath containing various concentrationsof KBHJ(25). Bath composition=
O.05M NaAg(CN)l, 0.10M NaCN, 0.40M NaOH, temperature 75 k2' C.

Fig. 17.8-Cathodic polarization curves lor Ag-NH1-tartaric acid solution (21). Curve 1 = 0.02M
AgNO,, 0.15M NH,. 0.1M NaOH; Curve 2 = 0.02M AgNO,, 0.15M NH,, 0.1M NaOH + tartaric acid.
Sweep rate = 0.2 Vlmin.

Electroless Plating of Silver

451

Fig. 17.9-Partial anodic polarization curves lor N?H,solution with various CN concentrations (29).
Bath composition = 6 M N:H, + 1.5M NaOH at 40" C. Curve 1 = OmM NaCN Curve 2 = 5 mM NaCN
Curve 3 = 40 mM NaCN.

Fig. 17.10-Polarization curves lor Ag-CN--N:H, solutions (29). (1): partial cathodic polarization
curve lor solution containing 0.03M AgNO,, 0.1M NaCN, and 1.OM NaOH; (2): partial anodic
polarization curve lor solution containing 6 M N:H4, 0.04M NaCN, and 1.OM NaOH; (3): total curve
(experimental) for solution containing 0.03M AgNO,, 0.01M NaCN, 6 M N:H4, and 1.OM NaOH; (3):
total curve (calculated).

452

ELECTROLESS PLATING

Fig. 17.1 1-Partial anodlc poiarlzatlon curves for various reductants (30):formaline (1,l'); BH; ion
(2, 2); ascorbic acid (3,3'); Fe" ion (4, 4).Dotted line = activated electrode; solid line = Inactive
electrode.

Fig. 17.12-Partial polarization curves for various electrodes: (1) partial cathodic polarization curve
of eiectroiesr silver platlng solullon wlthout Rochelle salt-AgNO1 (8.8 x 10.' M), ethylenediamine
(5.4 x 10.' M), DIT (4 x 10.' M), 35" C, pH 10.0; (2) partial anodic polarization curve for electroless
sllver plating solutlon wlthout silver nitrate-ethylenediamine (5.4 x 10.' M), Rochelle salt (3.5 x 10.'
M), DIT (4 x lo-' V), 35" C, p H 10.0. Solid line = Pt electrode sensitized wlth SnCh solutlon; dotted
line = PI electrode, not sensitized.

Electroless Plating of Stlver

453

Fig. 17.13-Relationship between amount of silver deposit and plating time. Bath compositlon:
AgNOI (8.8 x 10.' M),ethylenediamine (5.4 x 10.' M), Rochelle salt (3.4 x 10.' M), DIT (4 x 10.' M), p H
10.0,35" c.

Fig. 17.14-Silvering reaction mechanism from nonaqueoussolution (32).

The bath conditions are as follows:

Silver nitrate 3 x 10.' M
Rochelle salt 3.5 x 10.' M
pH 10.0-10.5

Ethylenediamine 1.8 x 10.' M

3,5-diiodotyrosine 4 x 10.' M
Temperature 35-40' C

It was found that the plating rate and the bath stability were greatly affected by
the pH of the bath, therefore the factorsaffecting the bath pH werestudied (34).
The bath pH was found to change with the addition of silver nitrate. The change

454

ELECTROLESS PLATING

was remarkable at pH values <10.5. The complex formation between silver ion
and ethylenediamine (en) is believed to be as follows:
+ 2H'
Ag' + 2Hz0+ 2en 2 [Ag(OH)2en2]-

1171

The equilibrium consideration of this reaction shows that the bath pH must
change with concentrations of Ag' and ethylenediamine. On the other hand,
even with the stable bath (DIT bath), the plating reaction almost stopped after24
hours and the pH of the bath dropped. It was thought that the pH change
strongly affected the life of the bath, because a slight drop in the bath pH
reduced the plating ratesignificantly, as seen in Fig. 17.15. When a bath of small
temporal change was used (Table 17.3),the same plating quantity was obtained
even after 24 hours. The life of this bath increased to one week by adjusting the
bath pH occasionally.
The life of the DIT bath was also studied from partial polarization curves (32).
As seen in Fig. 17.16, the DIT controls the cathodic reaction. This effect may
contribute to the bath stability. Moreover, the temporal changes of rest potential
and bath pH were measured for the DIT bath (Fig. 17.17a),for the bath without
Rochelle salt (Fig. 17.17b), and for the bath without silver nitrate (Fig. 17.17~).
Those pH values remained unchanged. In the case of Fig. 17.17b, the rest
potential moved to a noble potential and the color of the solution gradually
changed from colorless to yellow. The color change suggested that the fine

Fig. 17.15-Electrolars plating rate of silver as a function of bath pH: AgNO, (2.9 x 10.' M),
ethylenediamine (1.8 x lo:* M), Rochelle salt (3.5 x lo-* M), 3,5-dilodotyroslne (4 x 10.' M), 35' C.

Elecfroless Plating of Silver

455

Table 17.3
Deposit Thickness as a Function
Of Bath pH and Plating Time

Bath'

pH

Deposit
thlckness,
rng/crn'

Initial

9 97

0 115

After 24 hr

995

0 092

Silver
content,
Qh

96 0

Bath composition A g N 0 3 (8 8 x 10 ' M), Ethylenediamine

(5 4 x 10 ' M) Rochelle salt (3 5 x 10 ' M), 3,5-diIodotyrosine
(4 x 10 ' M), temperature 35O C

EImV vs SCE
Fig. 17.16-Effects of various additiveson the partial cathodic polarizationcurve for the Pt electrode
in electroless silver plating solutlon without Rochelle salt. Bath cornposition:AgNOt (8.8 x 10 ' M),
ethylenediamine (5.4 x 10 M), pH 10.0,35" C. (1) Noaddltive; (2) DIT (4 x 10.' M); (3) KI (4 x 10.' M).

'

silver particles were growing in the bath (35). Based upon the theory of Vaskelis
(36) concerning the electrode potential and the particle size in an electrolyte, it
was also believed that the potential becomes noble when the particle size
increases. The temporal changes for the non-additive bath (Fig. 17.17b), the
KI-added bath, and the DIT bath (Fig. 17.17a) were 2.1, 1.9, and 1.1 mV per 24
hours, respectively. From these facts, it can be stated that DIT restricts the
reaction at the electrode surface by controlling the partial cathodic reaction, and
stabilizes the bath by controlling the growth of fine silver particles in the
solution.

456

ELECTROLESS PLATING

Flg. 17.17-Change 01 rest potentialand bath pH wlth plating time. Bath composition: (a) AgNOl(8.8
x 10 M), ethylenediamine(5.4 x 10 M). DIT (4 x lO-M);(b) AgNO, (8.8 x 10 M),ethylenediamine
(5.4 x I O - M), Rochelle salt (3.5 x 10. M), DIT (4 x 10. M); (c) ethylenediamlne (5.4 x 10. M),
Rochelle salt (3.5 x 10 M), DIT (4 x 10. M).

Other stabilizers reported include: metal ions (Cu, Ni+, Co, Zn,) (37);
Na-2,3-mercaptopropane sulfonate (NaBH4, N2H4,CN-system bath) (38);
cystine, cysteine, dimethyldithio carbamate, NaSCN (NzH4, NH, bath) (39);
RCONHR (e.g., dodecylammonium acetate), [AgN03, (NH4)1Fe(SOJ)Z,
Fe(NO,),, citric acid system bath] (40), and CaO (41).

PLATED FILM
There are many reports about the characteristics and the protective nature of the
plated film that is obtained by the silvering method.
Dense plating is obtained by using glucose and formalin as the reducing
agent. The X-ray diffraction pattern for the chemical plating method (the
silvering method) is similar to those of a metal silver plate and a silver film
obtained by the vapor deposition method as shown in Fig. 17.18 (42) and Table
17.4 (20). The diffraction pattern changes slightly with different reductants (Fig.
17.19). Etching and sensitizing during pretreatment are important in order to
obtain good adherent plating (43).

Electroless Plating of Silver

457

The thickness of the coated silver film was measured by quantitative analysis
with KSCN (44), the p r a y method (454, and the iodine-ring method (46). The
plated silver film was usually protected by a polymer film such as lacquer.
Multiple platings of Cu or Ni improve durability (14).

PRACTICE OF ELECTROLESS SILVER PLATING

Bath Composition
The immersion and the spray methods are known as the commercialized
electroless silver plating technique. As it is impossible to review all reports with
respect to the bath composition for the immersion method, some typical
examples are presented in this chapter. ( A and B denote a silver ion solution and
a reducing agent solution, respectively.)

Fig. 17.18-X-ray dllfractlon patterns 01 various silver films (42). (a) Ag IIlm obtalned by chemlcai
platlng (thickness-1000 angstroms); (b) Metal Ag flim (thlckness-1 mm); (c) Ag film obtained by
vapor deposition method (thickness-1 000 angstroms).

ELECTROLESS PLATING

458

Table 17.4
X-ray Diffraction Patterns
Of Various Sllver Fllms
lntensitv
Plane
Metal Ag Chemical Vapor
orientation
fiim
plating deposition
(111)

(200)
(220)

100

40
25

100
41

23

100

13.5

Glucose method (47)

Although the operation is complex, a good plating is obtained.
A: Silver nitrate 3.5g, ammonia solution proper quantity, water60 mL, sodium
hydroxide solution 2.5 g/100 mL.
B: Glucose 45 g, tartaric acid 4 g, water 1 L, alcohol 100 mL.
Rochelle salt method (48)
Because handling Rochelle salt is easy, this method is widely used.
A: Silver nitrate 454 g, ammonia solution 355 mL, water 5.45 L.
B: Rochelle salt: 1590 g, Epsom salt 114 g, water 3.64L.
Distilled water of 3.61 L is added to the mixture of A (256mL) and B (256mL)
solutions.
Formaldehyde method (1)
The deposition rate is fast, but a cloudy film is obtained or peeling occurs.
A: Silver nitrate 20 g, ammonia solution proper quantity, water 1 L.
B: Formaldehyde 40 mL, water 200 mL.
A and B are mixed at the ratio of 5 1 .
Hydrazine method (48)
This is used for the spray method.
A: Silver nitrate 114 g, ammonia solution 227 mL.
B: Hydrazine sulfate 42.5g, ammonia solution 45.5 mL.
A and B are diluted to 4.55 L and mixed in a ratio of 1:l.
Organic borane method (49)
The plating rate is very fast.
A: N ~ [ A s ( C N ) 1.83
~ ] g/L, NaCN 1.0g/L, NaOH 0.75 g/L.
B: DMAB (dimethylamine borane) 2.0 g/L.

Electroless Plating of Silver

459

Fig. 17.19-X-ray dlffrrction patterns of the silvering films obtained by using (a) glucose, (b)
formaline, and (c) Ag powder (325 mesh) as reductants (20).

Aldonic acid and lactone methods (15)

The deposition rate is fast. The yield of silver is very high.
A: Ag(NH1)2'5 x lo-' M, NaOH 4.0 x lo-' M.
B: 8-gluconolactone 0.5-2.0 x lo-' M.

In the silvering method, the silver ion solution and the reducing agent solution
are prepared separately, then combined just before plating. In order to prepare
the silver ion solution with ammonia as a complexing agent, a black-brown
precipitate is produced upon addition of ammonia solution to a silver nitrate
solution; then the ammonia solution is added until this precipitate almost
dissolves. This solution is dark brown and clear. Reducing agents are prepared
by the specific methods.
In the spray method, various guns have been devised (50). For example, the
gun may have two tubes. The silver ion solution and the reducing agent are
sprayed separately, and mixed on the substrate.
Other distinctive baths are as follows: long life bath (34); good adherence (51)
or high speed (52); for semiconductors (53); mixture of silver and copper ions
(54); for substrate pretreated by hydrazine or dextrine (55); for plating on Si (56);

460

ELECTROLESS PLATING

Table 17.5
Effects of Chemical and Mechanical"
Etching on Adhesion Strength
Ot Electroless Copper Platingh
Adhesion
strength,
g/4 mm'

Chemical
etchant
None
HCI (20 wt.

Oh),

100" C, 15 rnin

NaOH(lOwt.o/o).lOOo C . 1 5 m i n

499.4
(613.2)dx
501.8
(467.9)
498.3

(750.0)
NaOH (lOwt. %) + NaCl(10wt. O h )
100' C. 15 rnin

780.2

(933.0)

'Mechanical etching (AllO, powder treatment): alumina

powder (0.5 wt. O b ) ; ultrasonic agitation lor 15 min.
'Undercoated with Ag (0.05 pm) by electroless plating.
'L-type tensile strength.
'( ) = with mechanical etching.
'When Ag was not undercoated, the value was 206.0.

with cyanides of the platinum group (57); electrolyzed Rochelle salt solution
(58).
The displacement plating method is usually used in order to electroless-plate
Ag on metals (59). For example, the bath composition for Ag plating on a Cu
alloy consists of silver nitrate (7.5 g/L), sodium thiosulfate (105 g/L) and
ammonia (75.0 g/L). There are many other reports (60).

Applications
There are applications for electroless silver plating in many fields. They are
broadly divided into two categories:
1. Optics and decoration.
2. Electrical conductivity or for undercoating prior to other plating.

A good example of the first category is a mirror. There are many reports about
this process (61). The second application makes the best use of the
characteristics of electroless silver plating, including silvering, which is used for
all insulators because the plated layer has electrical conductivity. For example,
the plating is used as an undercoating (62) for electroless gold plating, for Ag
plating on ceramics, for Sn-Pb alloy plating (63), and electrolytic plating (64).
When electroless plated silver was used as the undercoating on 96 percent
A1203 ceramics, an improvement in the adhesion of copper plating on the
ceramics was obtained (32). SEM photographs confirmed that electroless silver

E/ectro/ess Plating of Silver

461

plating was useful in obtaining smooth and uniform electroless copper plating.
Furthermore, the adhesion was greatly increased by etching the ceramics by
both mechanical and chemical techniques, as shown in Table 17.5.
In other cases, silver plating on ceramics is used for SEM measurement of the
surface (65). The plating is also used for quantitative analysis of trace arsenic
(66), for determination of the pore diameter of a membrane (67), and for
recovery of mercury.

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