Wide range of applications

Nickel
High purity product

Nickel Sulfamate Sulfamate

"Nickel Sulfamate" is a highly precise and quality surface treatment chemical which utilized the
outstanding plating characteristic. We have been accepting trust of the quality for over the years.
Nickel Sulfamate bath is used for wide applications such as functional plating to following.
Electronic components : Connector, Lead frame, Chip resistor etc.
Electroforming products : Metal mask, Resin mold, Stamper, Diamond cutter etc.
Advanced technique to control plating film properties such as precision and hardness, internal stress
is required. To meet these needs, we have various products of Nickel Sulfamates and additives.

Features
1. High speed plating is possible more than general Nickel bath (Watts bath).
2. Plating bath composition is simple, so control is easy.
3. Solubility to water is large. Use by high concentration and high current is possible.
4. Influence of impurities is slight.
5. Internal stress is very small, so suitable for various electroformings.
6. Purity of our products is high, surface of the electrodeposit will be fine-grained.
7. Film properties of the electrodeposit are excellent in reproducibility under the same operating
conditions.

Type and specification

Concentration Specific gravity Fe Cu Zn Pb Co

pH
as Ni(NH2SO3)2・4H2O at 30°C max.％

60% Nickel Sulfamate Solution

> 900 g/L (60wt%) 1.50±0.02 4.7 to 5.1 0.0001 0.0001 0.0005 0.0001 －

60% Nickel Sulfamate Solution (High purity)

> 900 g/L (60wt%) 1.50±0.01 4.7 to 5.1 0.0001 0.0001 0.0001 0.0001 0.0003

65% Nickel Sulfamate Solution

> 1,014 g/L (65wt%) 1.56±0.02 4.4 to 5.0 0.0001 0.0001 0.0005 0.0001 －

1
Fe Cu Zn Pb Co
Purity pH *
max.％
Nickel Sulfamate

> 96% 3.0 0.001 0.001 0.001 0.001 －

*1 : Nickel Sulfamate 30g + Boric acid 3g + water → 100mL
Representative bath composition and operating conditions

Normal High-concentration High-speed

2
* Nickel Sulfamate 350 to 450 g/L 600 g/L 600 g/L
2
* 60% Nickel Sulfamate Solution 600 to 750 g/L 1,000 g/L 1,000 g/L
3
* Nickel Chloride 5 g/L 5 g/L 5 g/L
3
* Nickel Bromide 3 to 10 g/L － －
Boric acid 30 to 40 g/L 30 to 40 g/L 40 g/L
4
* Additives proper quantity proper quantity proper quantity
*2 ,*3 : Initial make-up using either *4 : As necessary
Bath temperature 40 to 60°C 40 to 60°C 40 to 60°C
2 2
Cathode current density 1 to 10 A/dm 1 to 45 A/dm 45 A/dm2 max.
pH 4.0 to 4.5 4.0 to 4.5 4.0
Filtration Continuous Continuous Continuous
Heating tool heat exchanger heat exchanger heat exchanger
(Ref.) Relations of
6 pH adjuster addition amount and pH

・pH control
5
Control the pH level of Nickel Sulfamate bath
4
pH

using following chemicals.

Add Sulfamic acid to decrease pH 3 Sulfamic acid
Add Nickel Carbonate to rise pH Nickel Carbonate
2
0 1 2 3 4 5 6 7
Addition amount [g/L]

Attention for control of bath

1. The bath temperature is made into less than 70 °C. Hydrolysis is caused when bath temperature
exceeds 70 °C, and formed Ammonium Sulfate deteriorates the film properties of the electrodeposit.
Not to raise temperature locally, perform liquid circulation and use a heat exchanger.
2. Nickel containing sulfur with high solubility should be used for a positive plate.
Nickel Chloride and a Nickel Bromide are used as an anode dissolving agent. When using anode
dissolving agent in large quantities, Nickel Bromide shows the lower internal stress.
3. Inorganic and organic impurities rise internal stress, become brittle electrodeposition, and worsen
film properties. Please be careful about the kinds of chemicals to use.

Example of performance
Please refer to the following data about Nickel Sulfamate plating and precision electroforming.
In addition, the operating conditions are as follows.
Nickel Sulfamate 250 to 650 g/L
Nickel Bromide 5 g/L
Boric acid 30 g/L
PITLESS S 5 mL/L
pH 4.0
Bath temperature 50±1 °C
Agitation Mild agitation, Cathode locker
Current density 5 A/dm2
1. Nickel Sulfamate concentration and internal stress, hardness

Fig.1 Relations of Concentration and

1000 Internal stress

Internal Stress [kg/cm2]

Internal stress shows the minimum at Nickel
800
Sulfamate ( Ni(NH2SO3)2・4H2O) concentration of
× 650g/L
450 g/L (Figs 1 and 2). 600 ○ 550g/L
Hardness shows the minimum between 350 to ◆ 250g/L
400 □ 350g/L
450 g/L (Fig. 3).
△ 450g/L
200
0 10 20 30 40
Time [minutes]

Fig.2 Relations of Concentration, Fig.3 Relations of Concentration

plating thickness and Internal Stress and Hardness
1000 350
Internal Stress[kg/cm2]

Hardness（HV)
800 2μm 300
5μm
600 11μm 250

400 200

200 150
200 400 600 800 200 400 600 800
Concentration of Nickel Sulfamate [g/L] Concentration of Nickel Sulfamate [g/L]

2. Cathode current density and internal stress, hardness

Initial internal stress rises with cathode current density rises. And internal stress becomes stable with
plating film becomes thicker(Fig 4). Hardness decreases with cathode current density rises(Fig 5).

When performing electroforming etc., cathode current density is set up low at the early stage, and if it
rises to predetermined cathode current density, the effect of the prevention from exfoliation under plating
or the crack prevention at the time of a mold release can be expected.

Fig.4 Relations of Current dencity Fig.5 Relations of Current density

and Internal Stress and Hardness
1200 350
Internal Stress [kg/cm2]

1000
Hardness（HV)

300
800
250
600 8A/dm2
6A/dm2
400 4A/dm2 200
2A/dm2
200 150
0 10 20 30 40 0 2 4 6 8 10
Time [minutes] Current density [A/dm2]
3. Anode dissolving agent and internal stress, hardness
Nickel Chloride and a Nickel Bromide are used as an anode dissolving agent of Nickel Sulfamate bath.
The influence that those chemicals give in plating film properties are as follows.
In low concentrations, internal stress is almost equivalent at addition of Nickel Chloride and addition of
Fig.6 Relations of NiCl2 addition amount Nickel Bromide (Figs 6 and 7). However, to
and Internal Stress dissolve an anode reasonably and to stabilize a
1200
Internal Stress [kg/cm2]

bath, it is necessary to make concentration of an

1000 anode dissolving agent higher. At the high
800 concentration, addition of Nickel Bromide shows
20g/L
600 15g/L the lower internal stress than addition of Nickel
10g/L Chloride.
400 5g/L
0g/L Hardness is almost equivalent at addition of
200 Nickel Chloride and addition of Nickel Bromide
0 10 20 30 40
(Fig 8).
Time [minutes]
Fig.7 Relations of NiBr2 addition amount Fig.8 Relations of Anode dissolving agents
and Internal Stress and Hardness
1200 350
Internal Stress [kg/cm2]

Nickel Chloride
1000
Hardness（HV)
300 Nickel Bromide
800
20g/L 250
600 15g/L
10g/L
5g/L 200
400
0g/L
200 150
0 10 20 30 40 0 5 10 15 20
Time [minutes] Concentration [g/L]

4. Ammonium ion concentration and internal stress, hardness

By hydrolysis, Sulfamic acid generates Ammonium ion (NH4+) and a Sulfate ion (SO42-).
NH2SO3－ + H2O → NH4+ + SO42－
These ions degrade plating film properties. Internal stress becomes highest between 2 to 4 g/L of
NH4+ concentration (Fig 9). Hardness rises with NH4+ concentration increase (Fig 10) and becomes the
brittle film. Appearance becomes the rough gray plating film.
Fig.9 Relations of NH4+, Plating thickness
and Internal Stress Fig.10 Relations of NH4+ and Hardness
700 350
Internal Stress [kg/cm2]

600
Hardness（HV)

300
500
6μｍ
250
400 12μｍ
23μｍ
200
300

200 150
0 2 4 6 8 10 0 2 4 6 8 10
Concentration of NH4+ [g/L] Concentration of NH4+ [g/L]

In order to suppress hydrolysis, please work on condition of the following.

(1) Bath temperature : 70 °C or lower, (2) Avoid local heating, (3) pH4.0 or higher
By the work of bath temperature 50 °C and pH 4.0 or higher, the increases in NH4+ and SO42- are very
few.
5. Bath temperature and internal stress, hardness
Internal stress decreases with a temperature rise (Fig.11).
Hardness is stable from low temperature to 50°C. If temperature reaches 50 °C or more, hardness will
rise (Fig.12).
Fig.12 Relations of Temperature
Fig.11 Relations of Temperature
and Hardness
1000 and Internal Stress 350
Internal Stress [kg/cm2]

800 Current density 2A/dm2

300

Hardness（HV)
600
250
400
200
200

0 150
20 30 40 50 60 70 20 30 40 50 60 70
Temperature [℃] Temperature [℃]

6. Effect of NSF-E (Additive agent only for Nickel Sulfamate)

Fig.13 Relations of NSF-E addition amount

If NSF-E is used, a plating film will become the and Internal Stress
0
hardness of 500 HV or more with compressive
Internal Stress [kg/cm2]

-100 5μm 10μm

stress (Fig.13).
-200
-300
-400
-500
-600
2 4 6 8
Concentration [mL/L]

7. Cobalt salt additives (to rise hardness)

In order to rise the hardness of plating film, Cobalt salt may be added to a Nickel Sulfamate plating
bath. Usually, Cobalt Sulfamate is added. In this case, the Cobalt content in the plating solution is
desirable to around 10%. Higher Cobalt content is accompanied by higher internal stress and lower
hardness. Please keep in mind that a crack may occur(Fig.14).

Fig.14 Properties of the Nickel- Cobalt alloy plating

Internal Stress/10 [kg/cm2]

600 100
Co content in the film

500 80
Hardness(HV)

400 Hardness
60
[%]

300
Co content in the film 40
200
（Right axis ）
100 Internal Stress 20

0 0
0 2 4 6 8 10 12 14 16 18 20
Co content of a plating solution Co/(Ni+Co) [%]
8. Pit Prevention additive (PITLESS S)

Fig.15 Relations of PITLESS S

addition amount and surface tension
100

Surface tension[mN/m]
80
Surface tension influences generating of a pit.
PITLESS S can prevent pit generating(Fig 15). 60

40

20

0
0 5 10 15 20
Addition amount of PITLESS S [mL/L]

Other Sulfamic salt

50% Cobalt Sulfamate Solution Co(NH2SO3)2・4H2O

50% Lithium Sulfamate Solution LiNH2SO3
50% Manganese Sulfamate Solution Mn(NH2SO3)2・4H2O
40% Ferrous Sulfamate Solution Fe(NH2SO3)2・5H2O (Order Production)
35% Indium Sulfamate Solution In(NH2SO3)3 (Order Production)
40% Copper Sulfamate Solution Cu(NH2SO3)2・2H2O (Order Production)
In addition, we have “NSF series” only for Nickel Sulfamate additive agent and " NIKKA NONTACK "
mold releasing agent for electroforming.

Applications

1. Electronic component : Connector, Lead frame, Chip resistor etc.

2. Electroforming products : Metal mask, Resin mold, Stamper, Diamond cutter etc.

NIHON KAGAKU SANGYO CO., LTD. Sales Agent

h t t p : / / w w w. n i h o n ka g a k u s a n g yo . c o . j p/
Head Office: 2-20-5 Shitaya, Taito-ku, Tokyo 110-0004
Phone: +81-3-3876-3135 Fax: +81-3-3876-0559
Osaka Branch:
1-23-10 Uemachi, Chuo-ku, Osaka 540-0005
Nagoya Branch:
2-16-13 Shinsakae, Naka-ku, Nagoya 460-0007
December 2014