Enviralloy™ Ni 12-15

High alloy, alkaline zinc nickel process

Typical
Advantages

High cathode efficiency

Ease of use
Uniform alloy distribution
Enviralloy Ni 12-15 19/07/2005 Page 2

CONTENTS

SECTION PAGE NO.

1. Technical Advantages 3

2. Value In Use 7

3. Operating Manuals 9

4. Passivation Coatings & Top Coats 26

5. Process Conversions 43

Products and Codes for the Enviralloy Ni 12-15 System

Products Codes
Enviralloy Ni 12-15 A IP 74351
Enviralloy Ni 12-15 B IP 74352
Enviralloy Ni 12-15 C IP 74353
Enviralloy Ni 12-15 D IP 74354
Enviralloy Replenisher IP 74379
Envirowetter IP 74371

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 3

1. Technical Advantages
Enviralloy™ Ni 12-15 is an electroplating process designed to deposit a zinc-
nickel alloy containing 12-15% nickel, 85-88% zinc, on to steel substrates.
The passivated deposit is highly resistance to corrosion, providing over 1000
hrs of Neutral Salt Spray resistance from a 10 micron deposit. It is suitable for
both hexavalent and trivalent passivation treatments in clear, iridescent,
yellow and black colours. Zinc-nickel is particularly effective at preventing
corrosion in applications where repeated thermal shock or thermal cycling are
important, as the coating is not significantly affected by prolonged or repeated
heating at temperatures up to 200oC (390oF). The system can be used in
both rack (individual) and barrel (bulk) application equipment.

The Enviralloy™ Ni 12-15 system has the following principal technical

advantages:

Higher Cathode Efficiency & Plating Rate

Resulting in shorter plating time to deposit required minimum
thickness.

Uniform Alloy Distribution

Resulting in a more consistent corrosion performance.

Excellent Deposit Distribution

Resulting in lower cost to deposit minimum thickness.

Consistently High Nickel Alloy Content

Resulting in accurate compliance to specification.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 4

‘Plating Rate’
Enviralloy™ Ni 12-15
at various cathode efficiencies
(standard Hull Cell panel 1A)

70% CE 50% CE 35% CE

24
22
20
18
um per Hour

16
14
12
10
8
6
4
2
0 0.5 1 1.5 2 2.5
Amps per square decimetre

’Alloy Distribution’
Enviralloy™ Ni 12-15
at various current densities
(standard Hull Cell panel 1A)

7.5 g/l Zn 8.5 g/l Zn

14.5%

14.0%
% Ni in Alloy

13.5%

13.0%

12.5%

12.0%
0.5 1 1.5 2 2.5 3 3.5 4 4.5
Amps per square decimetre

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 5

‘Alloy Distribution’
Enviralloy™ Ni 12-15
compared to:
competitor 12% alloy (C12%) & competitor 6% alloy (C6%)
(standard Hull Cell panel 1A)

C6% C12% Enviralloy Ni 12-15

15%
14%
13%
12%
% Ni in Alloy

11%
10%
9%
8%
7%
6%
5%
0.5 1 1.5 2 2.5 3 3.5 4 4.5
Amps per square decimetre

‘Deposit Distribution’
Enviralloy™ Ni 12-15
compared to:
Acid Chloride zinc-nickel process
(standard Hull Cell panel 1A)

Acid ZnNi Enviralloy Ni 12-15

1
0.9
0.8
um per minute

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.5 1 1.5 2 2.5 3 3.5 4 4.5
Amps per square decimetre

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 6

‘Alloy Distribution’
Enviralloy™ Ni 12-15
compared to:
Acid Chloride zinc-nickel processes
(standard Hull Cell panel 1A)

Acid ZnNi Enviralloy Ni 12-15

21%
19%
17%
% Ni in Alloy

15%
13%
11%
9%
7%
5%
0.5 1 1.5 2 2.5 3 3.5 4 4.5
Amps per square decimetre

Note: The above graphs were generated from an Enviralloy™ Ni 12-15 prepared to the following standard:

Test solution
Zinc metal 8.5 g/l
Nickel metal 1.1 g/l
Ratio Zn:Ni 7.7:1
Sodium Hydroxide 110 g/l
Replenisher 10 ml/l
Part A 25 ml/l
Part B 40 ml/l
Part C 20 ml/l
Part D 6 ml/l
Wetter 0.5 ml/l
Sodium carbonate < 10 g/l
Temperature 24°C

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
 Enviralloy Ni 12-15 19/07/2005 Page 7

2. Value in Use
Process Cost Analysis
2
A comparison to deposit an average of 8um zinc-nickel on a surface area of 100m
-2 -2
meters. An average current density of 2.5 Adm (25 A/ft ) was applied. Zinc metal
and additive consumption’s were calculated and the costs compared with the
following plating systems.
Comparison with Competitor Systems

Competitor 12% Competitor 6%

Enviralloy Ni 12-15 Alloy process Alloy Process
Time 26 mins 32 mins 40 mins
Amp Hours Consumed 10.8 kAh 13.2 kAh 16.7 kAh
Zinc Consumed 5.1 kg 5.1 kg 5.4 kg
Zinc Cost unit / Kg 90 90 90
Zinc Cost 459 units 459 units 468 units
Nickel Consumed 0.74 kg 0.74 kg 0.31 kg
1
Nickel Cost unit / Kg 1009 1009 1009
Nickel Cost 746 units 746 units 312 units
Total Metal Cost 1209 units 1209 units 780 units
2
Brightener Consumed 2.2 lt 2.6 lt 2.3 lt
Brightener units / ltr 365 251 440
Brightener Cost 803 652 1012
2
Carrier Consumed 0.8 lt 3.0 lt 0.8 lt
Carrier units / ltr 455 467 973
Carrier Cost 364 1401 778
2
Booster Consumed - 3.5 lt 0.5 lt
Booster units / ltr - 275 352
Booster Cost - 962 176
2
LCD add Consumed - 1.3lt 0.7
LCD add units / ltr - 243 564
LCD add Cost - 315 395
Replenisher 0.32 lt - -
2
Ce
R op
nlseunm
isehder units / ltr 275 - -
Replenisher Cost 88 - -
Additive Cost 1,442 units 3,330 units 2,361 units
Total Cost 2,651 units 4,539 units 3,141 units
Electricity Consumed 109 kWh 134 kWh 168 kWh
Cost per 1 kWh 4.2
Cost Electricity 457 units 562 units 705 units
Total Cost 3,108 units 5,101 units 3,846 units
Material cost differences of Competitor systems…Vs Enviralloy 12-15
- + 39 % + 19 %
Data Based on:
Typical selling price of NiSO4.6H2O derived from LME price (November 2002 & MacDermid / competitor datasheets.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 8

Based on the calculations in the previous tables, to plate the reported parts,
Enviralloy 12-15 would offer the following advantages:

Versus: Competitor’s ‘High Alloy’ alkaline zinc-nickel processes

The potential to reduce plating times by a minimum of 20% to

achieve a minimum thickness
More economical when compared to a leading competitors systems
Reduction in electricity consumption to achieve an equivalent
deposit thickness
More even alloy distribution
Easier to operate

Versus: ‘Low Alloy’ metal alkaline zinc

The potential to reduce plating times by a minimum of 35% to

achieve a minimum thickness
A saving of more some 40% in system additives
Reduction in electricity consumption to achieve an equivalent
deposit thickness
Easier to operate

N.B. Low alloy zinc-nickel systems can be used to produce deposits with greater
ductility that high alloy systems, thus proving advantagous over high alloy content
deposits.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 9

3. Operating Manual

Introduction

Enviralloy™ Ni 12-15 is a high performance alkaline zinc-nickel

system that is formulated to meet market demand for zinc-nickel alloy
contents up to 15%. When used as recommended, it produces an alloy
of zinc-nickel containing 12 – 15% nickel. The deposits are semi-bright
and can be easily passivated in either trivalent or hexavalent systems.
Finishes that can be obtained range from blue/grey to black.

Please refer to the latest Enviralloy™ Ni 12-15 technical data sheet for
recommended operating parameters for this process.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 10

System requirements

There are certain plant and pre-treatment requirements that must be adopted
to ensure the successful operation of this process. This applies equally to
manual and fully automated plants:

1) Alkaline zinc-nickel plating are more susceptible to pre-treatment

faults when compared with more conventional plating systems (i.e.
cyanide zinc or cadmium) and the pre-treatment sequence must
reflect this (See Pre-treatment Section).
2) It is essential to maintain a consistent zinc concentration in the
plating solution. For alkaline zinc-nickel this is best achieved using
a suitable zinc generator. (See Zinc Generator Section)
3) The Enviralloy Ni 12-15 additives maintain the brightness,
distribution and nickel content of the zinc-nickel deposit. The level
of these additives must be maintained in the plating solution by
means of ampere-hour controlled dosing pumps. This will ensure
that a consistent finish is achieved.
4) The plating solution should be filtered. It is recommended that the
filter unit be sited in the zinc-nickel generator circuit.
5) The solution should be heated to the operating temperature after
plant shutdowns and chilled to prevent overheating whilst in
operation. Heaters should be of mild steel construction.
6) Mild agitation of the solution is recommended in order to achieve
optimum performance. Cathode rod agitation or plating solution
movement via eductors is recommended.
7) Analytical control of both the plating solution and the plated deposit
are essential for correct operation of the process. The minimum
that any potential user must have access to should be:

Volumetric analysis equipment (Zn, NaOH)

X-Ray Fluorescent spectrometer (Alloy Content, Deposit
Thickness)
Atomic Absorption or UV/VIS Spectrophotometer (Ni Content)

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 11

Cleaning

Failure to observe correct pre-treatment prior to alkaline zinc-nickel plating

can result in poor quality deposits and in extreme circumstances, imperfect
adhesion. It is important to transfer components from the final pre-treatment
stage to the zinc-nickel plating solution quickly, thereby preventing the
formation of any surface oxides. The benefits of a good pre-treatment regime
can be completely negated by allowing the parts to become oxidised just prior
to plating.

The preferred cleaning sequence is given below.

1) Soak clean
2) Anodic clean
3) Rinse X 2
4) Acid pickle (Inhibited 50% HCl or Heated H2SO4)
5) Rinse X 2
6) Anodic clean (Alkaline Deruster Salts or equivalent)
7) Rinse X 2
8) Zinc-nickel plate

The sequence has been developed to avoid contamination of the plating

solution with chlorides or oils. It also ensures the best adhesion of the zinc
deposit to steel. If you wish to use an alternative pre-treatment cycle please
confirm its suitability with your local technical manager or the global functional
group.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 12

Plating

Details of the preparation of the plating solution and basic operation are
covered fully in the Enviralloy™ Ni 12-15 Technical Data Sheet. Under
normal operation the solution should plate 16 microns average deposit
thickness per hour between 2.2 and 2.8 Adm-2. The table below outlines the
recommended ranges for the plating solution operating parameters.

Range
Parameter - Rack
Metric US
Zinc concentration 6.0 - 7.0 g/l 0.8 – 0.93 oz/gal
Nickel metal concentration 0.7 – 1.0 g/l 0.09 – 0.13 oz/gal
Zinc metal : Nickel metal ratio 6:1 to 10:1 6:1 to 10:1
Sodium hydroxide concentration 110 - 120 g/l 14.6 – 16 oz/gal
Sodium hydroxide : Zinc ratio 15:1 to 20:1 15:1 to 20:1
Replenisher concentration 10 ml/l 1%
Cathode current density 1.5 to 2.5 Adm-2 15 – 25 Aft-2
Bath temperature 20oC to 28oC 68oF to 82oF

Range
Parameter - Barrel
Metric US
Zinc-nickel concentration 7.5 - 10.5 g/l 1.0 – 1.4 oz/gal
Nickel metal concentration 0.85 – 1.3 g/l 0.11 – 0.17 oz/gal
Zinc metal : Nickel metal ratio 6.5:1 to 10:1 6.5:1 to 10:1
Sodium hydroxide concentration 110 -130 g/l 14.6 – 17 oz/gal
Sodium hydroxide : Zinc ratio 12:1 to 16:1 12:1 to 16:1
Replenisher concentration 10 ml/l 1%
Cathode current density 0.3 to 1.0 Adm-2 3 – 10 Aft-2
Bath temperature 20oC to 28oC 68oF to 82oF

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 13

Zinc
For each installation there will be an optimum zinc and nickel concentration for
operating the process. This will depend on the type of components being
processed and the way they are racked. Once this zinc concentration has
been established it should be kept to within 1g/l of this optimum value.

Generally, wherever there is the need for bright throwing power into very low
current density areas on rack installations it is necessary to operate the
process with lower zinc concentrations. For barrel plating installations where
speed and efficiency of plating is important higher concentrations of zinc (8.5
to 10.5g/l / 1.1– 1.4 oz/gal) are required. The advantages and disadvantages
of operating at lower concentrations of zinc are given in the table below.

Low Zinc - Advantages Low Zinc - Disadvantages

Improved bright throwing power Slower plating rates
Increased rack loading capability Reduced operating window
Improved deposit distribution

Sodium Hydroxide
The sodium hydroxide to zinc-nickel ratio governs the bright throwing power of
the plating solution. However, the concentration of the sodium hydroxide is
limited to a maximum of 130 g/l (17 oz/gall). This is because higher
concentrations of sodium hydroxide will hydrolyse the organic additives at an
accelerated rate. This makes solution maintenance less economical to
operate and the increased solution density (i.e. viscosity) decreases plating
efficiency. For almost all rack plants a concentration of about 110 to 120g/l
(14.6 – 16.0 oz/gall) and for barrel plants 110 to 130 g/l (14.6 – 17 oz/gall) of
sodium hydroxide should be suitable.

Nickel Metal
It is essential that the nickel metal is maintained in ratio to the total zinc
concentration in order to maintain the correct alloy deposit (& distribution) and
maintain the brightness of the deposit (particularly at low current densities).
The optimum ratio of zinc:nickel is 6:1 to 10:1 in rack and 6.5:1 to 10:1 in
barrel, depending on the deposit alloy content required. Lower ratios maintain
higher nickel deposit content. Ratios higher than 10:1 can result in LDC
burning and streaking.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 14

Cathode current density

For rack operation 1.5 to 2.5 Adm-2 (15 – 25 Aft-2) is recommended. At these
current densities the bath should be capable of producing over 0.25 microns
per minute average deposit thickness. Higher current densities (>3 Adm-2)
leads to higher plating rates, but reduced plating efficiencies. Lower current
densities give improved plating efficiencies but may lead to poorer distribution
and bright throw into low current density areas.

For barrel operation the solution efficiency is normally higher (than with rack
plating). A bath operating at 0.5 Adm-2 should plate an average of up to 0.095
microns per minute and at 0.8 Adm-2 should plate up to an average of 0.15
microns per minute.

Note: Enviralloy™ Ni 12-15 produces a tenacious organic film at the surface

during plating. Due to the nature of this film it is not recommended to interrupt
the current during the plating process. Switching off the current and then
restoring it again later may result in laminated deposits.

Rectification
Rectifiers should be 12V for rack plating and 16V for barrel plating. As for all
electroplating systems, current ripple should not be allowed to exceed 5%.

Solution temperature
It is essential to maintain a solution temperature between 20oC and 28oC
(68°F – 82°F) in order to maintain a bright deposit with good alloy distribution.
Operating at higher temperatures will result in increased consumption of
organic additives, dullness in low current density areas. Low temperature (<
20oC / 68°F) results in lowered plating efficiency, burning and poor deposit
adhesion.

For most installations this will occasionally involve the use of heaters and the
use of a refrigeration plant to cool the zinc-nickel solution whilst in production.

Zinc-Nickel Ratio Vs Alloy Composition

Alloy Composition Ratio

12-15% nickel 10:1 to 8.5:1

13-14% nickel 7:1 to 8:1

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 15

Enviralloy Ni 12-15 Additives

Under normal operation, the Enviralloy™ Ni 12-15 process employs four
maintenance additives; Part B, Part C, Part D and Replenisher.

A (IP74351)
Part A is responsible for the solubility of the nickel in the plating solution and
promote uniform nickel distribution in the plated alloy. It is generally only used
in either preparation of a new solution or during conversion from a competitors
system. If the solution is maintained as recommended, the concentration of
Part A is maintained by additions of Part C.

Part B (IP74352)
Part B is added to maintain the excellent low current density performance of
the system. It is consumed by drag out only and a recommended addition rate
is 4 – 8 litres / 25 kgs of caustic soda added to the plating solution.

Part C (IP74353)
Part C contains both the nickel metal and the correct maintenance ratio of
Part A. 1 ml/l (0.1 %) of Part C will raise the nickel content in the plating
solution by 66 ppm. It is maintained by ampere hour dosing at the rate of 7.5 –
10 litres / 10 kAh rack, and 12 – 15 litres / 10 kAh barrel. Actual rates will vary
depending on cathode efficiency, % nickel deposited and drag out. Higher
efficiency levels, drag out and % nickel deposited will consume more part C.
(See Graph 1)

Part D (IP74354)
Part D is the main brightening component and is particularly responsible for
grain refining at high current density. It is maintained by ampere hour dosing
at the rate of 1.5 – 2.5 litres / 10 kAh.

Envirozin Replenisher
This material is required to obtain a fully clear, bright deposit across the full
current density range. Low Drag out and low water quality will dictate the use
of this material. For optimum performance a newly made up bath will require
10 ml/l (1%), as the solution ages higher concentrations may be required. It is
added back to the tank in ratio with sodium hydroxide. Recommended
addition is 2 – 3 litres / 25 kgs.

Envirowetter
Envirowetter is used to reduce caustic spray and lower surface tension. Lack
of wetter in the plating solution may cause pitting of the deposit.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
 Enviralloy Ni 12-15 19/07/2005 Page 16

Graph 1

18
17

= Rack Systems
16
15
14

consumption excludes drag-out

Litres of Part C per 10k A-H
13
Ni 15%

12
11
Ni 12%

10

= Barrel Systems
9
8
7
6
5
70

60

50

40

30

20

10

Bath Efficiency
%

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 17

Analysis
Enviralloy™ Ni 12-15 should be analysed frequently to determine the
concentrations of zinc, nickel and sodium hydroxide in the plating solution.

1) Zinc / Caustic can be analysed by AAS or by one of the following

volumetric methods:

Method 1a - Zinc and caustic together

Reagents
 0.1N EDTA
 N H2SO4
 BDH 1113 indicator
 EDTA indicator solution
 pH 10 buffer solution
 4% Formaldehyde solution
 Sodium cyanide

a) Take a 5ml sample of solution and dilute to 10 ml with water

b) Titrate with N H2SO4 using MacDermid 1113* indicator to a yellow end
point.
c) Concentration of NaOH g/l = mls N H2SO4 X 8
d) To this solution add 20ml of pH 10 buffer solution containing 10g/l
NaCN.
e) Add a few drops of EDTA indicator solution.
f) Add formaldehyde (4% solution) until the solution turns pink/orange
g) Titrate with 0.1N EDTA to a yellow end point.
h) Concentration of Zinc g/l = mls EDTA X 1.3
*Formulation can be obtained on request

Method 1b - Zinc

Reagents
 0.1N EDTA
 12.5 % v/v HCL
 Xylenol Orange indicator
 pH 5.5 buffer solution

a) Take a 5ml sample of solution and dilute to 50 ml with water

b) Add 5 ml of 12.5% HCL.
c) Add 20 ml of pH 5.5 buffer solution and the XO indicator.
d) Titrate with 0.1N EDTA, colour changes from red to a yellow / orange.
e) Concentration of Zinc g/l = mls EDTA X 1.3

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 18

Method 1c - Caustic

Reagents
 N HCL
 Indigo-carmine indicator

a) Take a 5ml sample of solution and dilute to 50 ml with water

b) Add Indigo-carmine indicator.
c) Titrate with N HCL, colour changes from orange to blue.
d) Concentration of caustic soda = mls HCL X 8.0

2) Nickel - Nickel can either be determined by AAS or by the method

below.

Method 2a

Reagents
 12.5 % v/v HCL
 pH 5.5 buffer solution
 20% ammonia citrate
 5% gum Arabic
 0.5% Nioxime

a) Accurately pipette 10 mls of plating solution into a 100 mls volumetric

flask. Make up to the mark with water.
b) Pipette 2 ml of this dilution into a beaker and add 2 mls of 20%
ammonia citrate solution.
c) To this solution add 5ml of 12.5% HCL and 20 ml of pH 5.5 buffer
solution. Confirm that the pH is between 4 and 6. Add a few drops of
EDTA indicator solution.
d) Add 2 ml of the gum Arabic solution, then add 2 ml of the 0.5%
Nioxime solution and dilute to 100 mls with water. Stand for 15
minutes.
e) Measure 520 nm absorbance with UV/VIS spectrophotometer.
f) Determine gm of nickel using standard nickel curve.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 19

Organic Additive Content

The effectiveness of the organic components in the plating bath is best
determined by Hull Cell testing. A stabilised power supply capable of
delivering up to 2A is required for this testing.

Hull Cell method

It is important to use the same solution temperature during Hull Cell
evaluation to ensure consistent results and subsequent interpretation. Good
panels will be essentially free of defects and of good deposit thickness and
even alloy distribution (see below). Thickness measurements are taken at
points A-C on the panel and these correspond to current densities of 4, 2 and
0.5 Adm-2 respectively for a 1A panel. The measurements of deposit thickness
and nickel content for each respective panel should be within the ranges given
below.

1A 20min

This Hull cell will give an indication of the general performance of the plating
bath. Solution temperature at 24oC

Hull Cell 1A 20min

Zinc / nickel conc. Optimum
Temperature 24oC
A:C ratio 3 to 5:1

Thickness test

A B C
x x x
um 7-9 4.5-5.5 1.5-2.5
Ni 12-15% 12-15% 12-14%

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 20

Troubleshooting

To ensure optimum performance of the Enviralloy™ Ni 12-15 process it is

essential to adhere to the following checklist.

1) Ensure good pre-treatment

2) Analyse the plating solution regularly
3) Maintain the zinc, nickel, sodium hydroxide and Replenisher
4) concentrations within the recommended limits
5) Maintain additives (where applicable) on an ampere hour basis
6) Control temperature of plating solution within the recommended
7) limits
8) Ensure good electrical contacts
9) Ensure good rack and plant maintenance

If operational difficulties arise hull cell testing is a useful tool in solving solution
problems. Details are given below of the more common type of faults
encountered in alkaline zinc-nickel baths and how to correct them.

Dull deposit appearance

1) Poor pre-treatment or oxidation/passivity of steel prior to plating.

2) Zinc and / or nickel concentrations outside the recommended limits.
Low nickel content may cause burning and grey streaks in mid CD
range.
3) Solution temperature too high. This will cause dull deposits in the
low current density area particularly.
4) Applied cathode current density too low.
5) Replenisher concentration too low. This commonly results in faint
dull streaks in the mid current density on a 1A panel. An addition of
1ml/l (0.1%) of Replenisher is generally sufficient to correct this
problem.
6) Brightener concentration too low. This may cause burning/dullness
in the high CD range.
7) Poor electrical contacts or poor rack design. It is essential that
good rack design and positive electrical contacts be maintained.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 21

Low nickel in alloy

1) Zinc and / or nickel concentrations outside the recommended limits.

2) Low level of Part A and / or B. Determine by Hull Cell whether an
addition of either Parts A or B restore the correct percentage nickel
in the deposit.
3) Low temperature.
4) Low level of Brightener. Determine by Hull Cell whether an addition
of Brightener will restore the correct percentage nickel in the
deposit.

Pitting

1) Lack of wetter. This is normally coupled with unacceptable levels of

caustic spray. An addition of up to 1ml/l should be sufficient to
eliminate this problem. If excessive amounts of wetter are being
added to the tank it is likely that oil is being dragged into the plating
solution. The source of the oil contamination should be identified
and removed.
2) Low Nickel in solution can cause burning and pitting effects in the
deposit. This can be observed on a 1A Hull cell, particularly in the
high current density areas.

Burning or nodulation

1) High zinc metal concentration. This can lead to high current density
deposit burning. The zinc nickel concentration should be restored
to within recommended levels to eliminate this problem.
2) Low temperature. Temperatures below 20oC (68°F) are not advised
and can cause adhesion problems as well as burning.
3) Low concentration of Part D. This can be observed by Hull cell
testing. It will result in excess deposit thickness of zinc in the high
current density areas of the panel. An addition of up to 5ml/l in
1ml/lt increments, (0.1%) of brightener should be sufficient to
correct the problem.
4) Applied current density too high. Measure the surface area of
components and adjust current density within range specified in the
TDS.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 22

5) High carbonate levels. Increasing concentrations of sodium

carbonate cause high current density burning. Ultimately, a low
temperature treatment or a dilution of the solution will be
necessary.
6) Zinc anodes in plating tank. Burning can occur if zinc dissolution is
carried out in the plating tank and the cages come in contact with
the anode rail or anode plates.
7) Low nickel concentration in the bath. Adjust to within recommended
range.
8) Chloride contamination. If level has risen above 4 g/l then a either a
dilution or replacement of the solution should be considered

Poor adhesion

1) Poor pre-treatment. Please refer to the section on pre-treatment.

2) Low solution temperature. This lowers the efficiency of zinc-nickel
deposition and increases the tendency to burning. Slower initial
propagation, which occurs at low temperature, can cause poor
adhesion.
3) Current interruption. If the current has been very low or switched off
and subsequently raised back to recommended plating current
density poor adhesion or lamination will occur within the deposit.
4) Chloride contamination. If the level has risen above 4 g/l then a
either a dilution or replacement of the solution should be
considered

Low plating rate

1) Low metal concentration. As the zinc concentration is reduced from

optimum, the plating efficiency decreases. It is important to
maintain the correct zinc metal content of the bath (and of course
the Zn:Ni ratio) to obtain optimum performance.
2) Low temperature. As mentioned above efficiency reduces as
temperature is lowered.
3) Overdose. An overdose of Part A,B,D or Replenisher in the solution
will reduce plating efficiency. Reducing additions of the particular
additive by 50 to 100% until the plating rate is restored will correct
this problem.
4) High carbonate. As sodium carbonate builds up in the solution to
above 75g/l (10 oz/gall) plating efficiency reduces gradually.
Periodic low temperature treatments to remove carbonate are
advisable.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 23

Zinc Generator System

It is recommended that the zinc concentration in the Enviralloy Ni 12-15
system be maintained by use of a zinc generator. A zinc generator consists of
a steel tank (some 10 – 20% volume of the plating solution) in which steel
cages containing balls (or domes) are suspended. The zinc generator greatly
simplifies control of the zinc metal concentration and makes maintenance of
the anode material easier. The generator tank must be constructed of mild
steel. A suitable arrangement is described below, although different variations
are possible depending on individual circumstances.

Typical Layout Diagram

Ideally, the plating solution is gravity fed to the generator via an overflow on
the plating tank. It flows through the generator, which contains zinc balls held
within mild steel cages. It is recommended that the steel cages are not de-
scaled before immersion into the solution, as the presence of iron oxide
promotes the dissolution of zinc metal. The solution is then pumped back to
the process tank via a filter. The filter is located on the return side of the
generator in order to filter out any large particles of un-dissolved zinc. An
overflow tank is incorporated into the system to allow drainage of the
generator during shutdown periods or when the concentration of zinc metal
has become too high.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 24

Many methods have been tried to maintain a consistent dissolution rate of the
zinc in the generator tank. Most focus on changing the area of zinc in contact
with the circulating electrolyte. Cages containing the zinc domes, fixed on a
pulley that can be lowered or raised and valves to control the solution level
are the most popular. However, for simplicity manually adjusting the zinc
dome volumes is the most common approach.

Insoluble Anodes
Insoluble anodes used in the plating tank should be made of pure nickel.
Nickel sheet is ideal for this. Nickel plated steel can be used (min. 25um Ni),
but will degrade quicker than pure nickel and can give inferior deposit
throwing power. Bolting them to submersed nickel or nickel plated steel (i.e.
not copper) anode rails is recommended to make the best electrical contact.
Suitable dimensions for the nickel anodes could be 150 – 250 mm (6 – 10”)
wide, the depth will depend on the components being processed.

Zinc anodes in the process tank are not recommended because:

They can polarise at current densities above 1.5 Adm-2 (15 Aft-2).
They can cause roughness in the plating solution.
Control of the zinc metal concentration is more difficult

Zinc Generator Volume

It is not possible to predict the exact dissolution rate of zinc-nickel metal in the
Enviralloy Ni solutions. This is because many factors influence the rate at
which the zinc metal dissolves. These factors include; the concentration of
sodium hydroxide, complexant, temperature, zinc to steel cage area ratio,
plant loading, solution flow and agitation etc.

The major factor when estimating zinc generator size is the plant loading.
Experience has shown that generator volumes are usually between 10 – 20%
of that of the plating solution, the larger percentage values being used for
barrel installations. As the Enviralloy™ Ni 12-15 operates at approximately
60% cathode efficiency, 0.7 kgs (1.6 lb) of zinc will need to be generated for
each 1,000 Ah passed.

The Enviralloy™ Ni 12-15 process has been proven to be more efficient than
other alkaline zinc-nickel plating systems. The cathode efficiency will have a
direct impact on the ability of any existing generator to maintain a stable zinc
concentration. Therefore, we recommend that the zinc generator is evaluated
as part of a plant audit, to ensure that there is sufficient capacity to increase
the dissolution of metal.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 25

4. Passivation Systems & Top Coats

Feature Benefit
Deposit contains between 12-15% Accepts both hexavalent and trivalent
nickel passivates
Process developed for use with Ideally suited to meet new End of Life
TriPass™ passivation systems Vehicle (ELV) directives
Even passivation films Improved corrosion protection

The purpose of conversion coatings is simply to protect zinc-nickel deposits

from corrosion. Environments likely to produce conditions where corrosion can
be accelerated include air and sea shipping, long-term storage in humid
environments and severe environments like coastal regions. Conversion
coatings increase the resistance of zinc-nickel and plated coatings against
these types of corrosion, thus considerably extending component life.

Traditionally, conversion coatings were based on hexavalent chromium

compounds. However, new legislation and corporate policies are beginning to
restrict use of hexavalent chrome compounds due to toxicity and difficulty in
recycling. The primary driver for hexavalent chrome is the EEC legislation
‘End of Life Vehicle’ directive (or ELV).

In order to passivate zinc-nickel deposits with systems free of hexavalent

chrome compounds, the alloy must contain a minimum of 12% nickel. The
Enviralloy Ni 12-15 will give a consistent alloy distribution at or above this
percentage and therefore are ideal for trivalent passivation. These new light
iridescent TriPass™ coatings give conversion coatings whose performance
can exceed the protection offered by traditional hexavalent films and are
exceptionally resistant to thermal shock treatment.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 26

Enviralloy Ni 12-15 has been developed to work synergistically with the

MacDermid trivalent TriPass™ processes to give high anti-corrosion
performance coatings without the use of hexavalent based compounds.

Passivate Corrosion
Film type MacDermid Passivate
Type Resistance
Blue/Grey Trivalent Up to 200 TriPass ELV 3000
Iridescent Trivalent > 200 TriPass ELV 2000
Black Trivalent > 200 TriBlack
Yellow Hexavalent > 200 Iridite 880
Black Hexavalent > 200 Iridite 990
*Time to ‘white rust’ for rack passivated work. Spec. ASTM B117, no thermal shock treatment

A suitable trivalent passivation sequence for the plated zinc-nickel coating

from the Enviralloy Ni 12-15 process would be as follows:

1) Zinc-nickel plate – minimum 5 microns

2) Rinse X 2
3) Passivation
4) Rinse X 2
5) Topcoat (optional)
6) Oven dry (< 70oC)

A suitable sequence for the TriBlack process over a zinc-nickel coating from
the Enviralloy Ni 12-15 process would be as follows:

1) Zinc-nickel plate – minimum of 8um

2) Rinse X 2
3) Activate in 0.5% Hydrochloric acid
4) Rinse
5) 1st dip - TriBlack, 10 – 20 seconds
6) Drain off or centrifuge (1 – 2 minutes)
7) Cure 5 – 10 minutes at 80 – 100°C
8) 2nd dip - TriBlack, 10 – 20 seconds
9) Drain off or centrifuge (1 – 2 minutes)
10) Final cure 10 minutes at 80 – 100°C

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 27

A suitable hexavalent passivation sequence for the plated zinc-nickel coating

from the Enviralloy Ni 12-15 process would be as follows:
1) Zinc-nickel plate – minimum 5 microns
2) Rinse X 2
3) Passivation
4) Rinse X 2
5) Fixer solution
6) Rinse and Topcoat (optional step)
7) Oven dry (< 70oC)

Enviralloy Ni 12-15 produces a uniform zinc-nickel deposit, which is easy to

passivate. Using the correct passivate to meet a given standard, the
Enviralloy Ni 12-15 process can give improved resistance to red rust over
competitor processes, particularly on complex and difficult to plate
components. The following guide highlights the MacDermid preferred range of
passivates and topcoats.

Trivalent based passivation systems

Where high corrosion performance is required from a trivalent passivate,
TriPass ELV 2000 or 3000 are recommended. The achievable corrosion
performance is similar to traditional yellow hexavalent passivates before any
thermal shock is applied. However, the protection obtained after thermal
shock is superior to hexavalent systems making it suitable for use in
environments where high temperatures are regularly encountered (i.e. engine
compartments / brake callipers).

These processes are simple to make up and operate and can be used in both
rack and barrel applications.

TriPass ELV 2000 TriPass ELV 3000

Colour Iridescent Blue / grey
Concentration 80 – 100 ml/l 100 ml/l
pH 1.8 – 2.2 2.3 – 2.5
Temperature 60 – 70°C 40 - 55°C
Immersion Time 60 – 120 sec. 30 - 60 secs

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 28

During use the concentration of the TriPass solution will decrease and the pH
will increase. The passivate is maintained by regular additions of the
applicable TriPass concentrate. Accurate control of the pH is essential to
ensure the process operates successfully. The pH should be maintained by
additions of concentrated nitric acid. The nitric acid and TriPass concentrate
can be pre-mixed for auto dosing purposes.

Suitable additions could be per 100 m2 of treated surface area:

TriPass ELV 2000

70% nitric acid To maintain pH

TriPass ELV 2000 0.15 – 0.3 litres

TriPass ELV 3000

70% nitric acid 0.5 – 2.1 litres

TriPass 3000 0.5 – 2.1 litres

Trivalent Black System (Dip-Spin)

Where a high corrosion resistant black coating is required from a trivalent
passivate, TriBlack is recommended. This process is an all-in-one black
trivalent passivation and sealant process. The TriBlack solution contains no
hexavalent chromium compounds and is therefore suitable to meet the new
End of Life Vehicle directives.

The passivated film contains a unique mixture of inorganic and organic

compounds which provides exceptional corrosion protection. The film also
incorporates an integral lubricant which is designed to meet specifications
requiring coefficient of friction properties between 0.12 – 0.18. This material
should always be tested under the conditions for which it is intended.

TriBlack Part A 500 ml/l

TriBlack Part B 150 ml/l
DI water to 1 litre
Immersion time 10 – 20 seconds
Temperature 20 – 30°C
Curing schedule 5 – 10 minutes at 80 – 100°C (metal temperature)

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 29

TriBlack Application By Dip Spin

In order to get good even colouration and full coverage it is important to
control application conditions.

TriBlack is usually used at a concentration of 50-80 % concentration of part A.

The working tank should be maintained at 15-30 degrees C in normal
operation. The higher the concentration used the thicker the final layer will be.
For large scale production where there is more tendency for items to have
restricted drainage during spinning it is normal to use a concentration level of
50 %. The TriBlack concentration should be maintained at the same level from
day to day. This can be done by maintaining the working level of TriBlack with
TriBlack A &B at the initial makeup concentration. This concentration can then
be checked periodically by measuring total solids or chromium content by the
methods provided. Bathside viscosity checks using a B2 flowcup can also be
useful to give a quick rough check on concentration.

After dipping excess TriBlack is then spun off in the basket. Due to the effects
of centrifugal force a large diameter basket should be spun at a lower speed
than a small basket to achieve the same effect. As a general guideline a spin
speed of 200 linear metres is recommended. To avoid unnecessary damage
during this process a slow ramp up to final speed of 10-20 seconds can be
used. A spin time at final speed of 20-40 seconds is normally sufficient and for
larger loads it is common to use a forward and reverse step to make sure that
excesses are removed from the centre of the load.

The basket is approximately half filled for the process. Overfilling makes it
difficult to avoid thread fill and sticking together whilst very low loadings lead
to low coating thickness and unnecessary damage.

Generally it will be found that some parts have a greater tendency to trap
excess coating than others so it may be necessary to vary the above
parameters occasionally to maintain good results. To maintain the required
corrosion resistance and cosmetic finish a double coating will normally be
required.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 30

TriBlack Troubleshooting Guide

Problem Possible causes

Basket underfilled
Grey or patchy black finish Spin speed too fast
Low TriBlack concentration
Spin speed too slow
Too thick, drips or thread fill Basket overfilled
High TriBlack concentration
Basket overfilled
Work sticks together Extra spinning or reverse step needed
High TriBlack concentration

Hexavalent Passivation Systems

Where high corrosion performance is required from a hexavalent passivate
(chromate), Iridite 880 or 990 are recommended. These processes are simple
to make up and operate and can be used in both rack and barrel applications.
They have been developed to work synergistically with the Enviralloy Ni 12-
15 system. After passivation, either a fixer or suitable topcoat is advisable (or
both).

Iridite 880 Iridite 990

Colour Iridescent Black
Concentration Part ‘A’ 100 – 120 g/l 140 – 160 ml/l
Concentration Part ‘B’ 140 – 160 ml/l
pH 1.4 – 1.6 0.5 – 0.65
Temperature 35 – 50°C 20 – 25°C
Immersion Time 30 – 60 sec. 110 - 120 secs

Chrome content in passivates

In order to determine the level of total chromium contained within a
passivation film, the deposit and passivate layer are stripped in dilute mineral
acid and the total chromium concentration is measured by Atomic Absorption.
In order to ascertain the chromate level a second technique, X-ray
Photoelectron Spectroscopy* (XPS), is employed. This method allows the
ratio of Cr(III) to Cr(VI) in a passivate film to be estimated.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 31

Comparison of chromium concentrations using chemical analysis

method
Type of passivate Thickness in nm Total Cr* mg/m-2
Yellow 250 – 500 200 - 460
Black 250 – 1000 1000 - 1800

Peak fit data showing Cr(III) concentrations relative to Cr(VI) based on

XPS spectra of various passivate films.
Passivate Film Cr(III) as Cr(OH)3 Cr(III) as Cr2O3 Cr(VI)
Yellow 23% 36% 41%
Black 55% 22% 22%

The above results show that there is both hexavalent and trivalent chromium
species present in hexavalent chromium based passivates. The amounts /
ratios will vary depending on the type of passivate used, the proprietary
process employed and the operating parameters utilised. Also the methods for
the detection used (for these compounds) do have limitations and are
therefore recommended for qualitative analysis only. The concentration of
chromium within a passivation film is also dependent on immersion time,
solution concentration, pH, and temperature and contamination levels.
Therefore, the above table should be used as a reference guide only.

* Ref: Lionel Thiery, Galvanotechnik, page 3373.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 32

Chrome (VI) content in trivalent based passivates

It is recognised that under certain conditions trivalent passivation films can
generate or contain small amounts of hexavalent chromium. These levels are
at the limits of detection with current analytical equipment and are orders of
magnitude lower than any traditional hexavalent chromate film.

Typical Hexavalent Chrome Content of Trivalent passivate films

Total Cr Leachable % Leachable

content mg/m2 Cr(VI) mg/m-2 Cr(VI) to total Cr
Iridescent type 100 – 180 <0.06 0.03 – 0.06 %
Blue type 35 - 45 <0.03 0.07 – 0.09 %

GMW-3034
General Motors have recognised the need to eliminate hexavalent chromium and
have issued specification GMW-3034 as a method of detecting its presence in
passivate films. This specification details the dissolution of the passivate film and the
detection of any residual hexavalent chrome compounds using 1,5-diphenyl
carbizide. 1,5-diphenyl carbizide produces a red coloured complex in the presence
Cr (VI) compounds. These can then be measured by UV/vis spectroscopy. This
specification is a go / no-go test with the maximum allowable limit of hexavalent
chrome compounds at 0.1 mg/m-2 of passivated area.

GMW-3034 test on the Trivalent based passivates

Deposit Pass or Fail
Hexavalent Yellow Fail
Peroxide based trivalent Iridescent Fail
GMW-3034 Standard Comparative standard
Trivalent (TriPass ELV 2000, 3000) Pass

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 33

Relationship between Passivation Colour, Type and Alloy Content

Due to the variation in nickel content of zinc-nickel deposit, passivation
processes may produce variable results in terms of film formation, thickness,
colour and corrosion performance. It is therefore important to establish the
correct operating conditions for alloy composition and passivation process to
ensure consistent performance results.

The graphic details below show how the alloy content of Enviralloy Ni 12-15
should be controlled in order to obtain the desired passivation colour.

Iridite Hexavalent Passivates

TriPass Trivalent Passivates

Work within the following ranges for specific colours:

Hexavalent Yellow Passivation up to 13% nickel
Hexavlent Black Passivation over 13% nickel
Clear Trivalent Passivation up to 12.5% nickel
Iridescent Trivalent Passivation over 12.5% nickel
Black Trivalent Coating Any nickel content using TriBlack (dip-spin)

The most cosmetically attractive clear finish can be obtained by using TriPass
ELV 2000 under the following conditions.

Make Up 10% v/v

Temperature 30 – 40 oC
pH 2.5 – 3.0
Immersion 30 – 60 seconds

Shorter immersion times are better for higher alloy contents.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 34

Topcoats & Seals

Although it has long been recognised that conversion coatings on sacrificial
deposits increase their performance considerably, today’s coating
specifications often require performance levels which exceed the limits of the
conversion coatings detailed above. The principal improvements required by
these ever more demanding specifications are:

Better corrosion protection (usually defined as improved resistance

to Neutral Salt Spray, ASTM B117 or by cyclic corrosion methods)
Improved resistance to thermal shock test
Specific torque and tension requirements
Improved contact corrosion performance
Improving coating aesthetics

In order to achieve the various criteria outlined above with minimal cost increase,
topcoats (or final finishes) are now commonly applied to passivated coatings. These
can be inorganic, organic or a mixture of both (organo-mineral). The majority of these
topcoats are aqueous solutions applied by single stage dips incorporated into
conventional electroplating lines or as the final stage in mechanical plating.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 35

Torque and Tension Control

The use of torque (turning or twisting force) has long been associated with
methods of tightening and inspecting bolts. The object of tightening bolts is to
achieve a minimum tension (straight pull), not torque, in the bolts.

As a nut and bolt are tightened the components to be fastened are clamped
together. The thread angle in the bolt converts the force applied into tension
(or stretch) in the bolt shank. The amount of the tension created in the bolt is
critical, because when a bolt is tensioned correctly it is working at its optimum
efficiency and will resist coming undone. However, if the tension is too low
the nut could vibrate or work loose. If the tension is too high (over-stretched),
the bolt could break. Therefore, it is important to have these figures available
so that the end product will be safe, efficient and economical.

There is a relationship between torque and tension, but it is highly variable

and must be used with caution. The variables in the torque-tension
relationship include lubrication, thread fit, the use of a washer and the tension
in the bolt. The torque used to tighten a bolt is consumed by overcoming the
friction between nut and washer (about 60%), overcoming the friction between
bolt thread and nut threads (about 30%), and providing energy to elongate the
bolt (about 10%). Tests have indicated that torque-tension relationships for
structural bolts easily vary by as much as 40%.

Specifications do not permit the use of any tabulated torque or calculated

torque for either installation or inspection. Installation and inspection torque’s
must be determined or set using Skidmore-Wilhelm (or similar) devices to
establish actual tension, then determine the torque. A basic equation to
estimate the torque-tension relationship is:

T = 0.0167 x P x D
Where
T = torque (foot-pounds)
P = bolt tension (pounds)
D = bolt diameter (inches)

The value of 0.0167, called the nut factor, is a traditional industry average. It
can range as low as 0.01 for well-lubricated assemblies and can exceed 0.025
for dry or rusty fasteners.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 36

Torque – Tension relationships of zinc-nickel plated fasteners

Zinc-nickel alloy plated deposits generally exhibit unpredictable torque/tension
relationships.

Furthermore, zinc-nickel deposits have a significantly higher coefficient

of friction than either zinc or other zinc based alloys.

This means that applying conventional post plating lubricants will give a higher
CoE than expected. Also the CoE spread or range is usually wider than
anticipated. Friction control lubricants should therefore be chosen and tested
carefully when zinc-nickel is specified.

In order to give predictable relationships MacDermid recommend the following

lubricant types:

Lubricant suspension - i.e. Torque ‘n’ Tension control fluids

Organic Coating with lubricant Suspension - i.e. Maculube 9775

Torque ‘n’ Tension Control Fluids

Torque ‘n’ Tension Control Fluid MPE 1186 is formulated to apply a dry
lubricating film to machined parts, especially threaded fasteners which have
been protected from corrosion by sacrificial or barrier coatings like zinc-nickel
electroplating. The objective of this lubricant is to decrease the coefficient of
friction of coated parts and to control the induced tension obtained with a
given tightening torque.
Torque ‘n’ Tension Control Fluids 11 or 15 will also increase the corrosion
protection of a plated layer. These products are generally applied off line
using dip-spin or curtain wash process equipment. Application of Torque ‘n’
Tension Control Fluids requires the parts to be free of oils.
Torque ‘n’ Tension Control Fluid / UV Fluid can be used as received or diluted
with water. Torque ‘n’ Tension Control Fluids 11 or 15 are generally used as
received. The concentration that is required will depend on several factors, the
quantitative importance of which cannot be determined in advance for each
individual application.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com
Enviralloy Ni 12-15 19/07/2005 Page 37

The following methods of application can be used:

1) Dipping parts in solution using perforated or screened baskets then

drying on a belt or spin dryer.
2) Cascade or Curtain Coater in which the parts pass through a
running cascade of lubricant on a belt or conveyor then on to a
drying stage.
3) Spraying the solution on the parts in liberal volumes using
equipment such as a parts or dunk washer, then drying.

MacDermid plc, Palmer Street, Bordesley, Birmingham B9 4EU

International Telephone: + 44 (0) 121 606 8100 Fax: + 44 (0) 121 606 8300 Sales Order Fax: + 44 (0) 121 766 6883
www.macdermid.com