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Trivalent Chrome Systems

POP seminar USA


October 2014

Confidential – for authorized use only

Lammert de Boer
Global Director – Decorative Coatings
Agenda

• Trichrome demand
• Overview
• The state of art on Decorative Trichrome
• MacDermid OEM selling focus
• Corrosion Resistance
• Specifications and Approvals
• Colour Ranges
• Benefits

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Trivalent Chrome - Demand

• Why is the market moving towards trivalent


chrome…
– REACh - Registration, Evaluation, Authorisation and
restriction of Chemicals
– SVHC’s - Substance of Very High Concern
– T1 “Corporate Compliance” programs
– Pressures on OEM to go “GREEN”
– Increased Colour and Styling options
– Technical performance and Specific
– The Trichrome technology is now mature
– Many competitors are promoting it
Trivalent processes – An overview

Two distinctive types of systems


• Chloride type
• Sulphate type
Time line
• 1970’s
• Chloride systems introduced
• Graphite anodes
• Introduction of original Envirochrome sulphate system
• Anode boxes to prevent oxidation of CrIII
1990’s
• Twilite Sulphate based system
• Dark chrome deposit
• Dimensionally stable anodes (DSA)
• Much easier to use and facilitates wider adoption of process
2003
• TriMac Sulphate based system
2010
• Starlite Sulphate based system
• Darker chromium colours for automotive use

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Process comparison
Sulphate based system Chloride based system
• Lighter colour • Higher plating speed
• Easier process control • Cheaper anode system
• Higher corrosion • Longer life anodes
resistance • Higher resistance to
• No cooling required metallic contamination
• Liquid maintenance
additives

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Yellow/Green Zone Yellow/Red Zone
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TriMac RM™

1.5 Twilite™

1
Macrome CL3™

Envirochrome™ 0.5

-2.0 -1.5 -1.0 -0.5 0.5 1.0 1.5 2.0

TriMacIII™
-0.5

Std. Hex
-1.0

-1.5

Blue/Green Zone -2.0 Blue/Red Zone

Luminosity 62.5 75 87.5 100


TriMac RM Hex Chrome
Envirochrome
Twilite
TriMacIII 6
Macrome CL3
Trivalent - State of the Art

• MacDermid
Sulphate Systems
– TriMacIII, TriMac RM, Twilite, Starlite
• High Purity Chromium Deposits
• Highest Performance
• Fewest Competitors
• MMO anodes
• Best in Class Product

TriMac III TriMac RM Twilite Starlite


Trivalent - State of the Art
• MacDermid
Chloride Systems
– Macrome CL3, Galaxy
• Fastest Speed
• Higher Alloy Content (Fe, Ni)
• Graphite anodes
• Passivation required

Macrome CL3 Galaxy


Advanced Trivalent Systems

• TriMacIII
– Sulphate Based
– Ultra white deposit, closest to Hex colour
– Excellent CASS 60+ hrs
– Excellent NSS, 240+ hrs
– Passes “VW” PV 4017 Russian Mud test
– Very stable colour, zero Fe
– Ion Exchange Mandatory
Advanced Trivalent Systems

• Twilite
– Sulphate Based
– Mid-Dark Colour
– Highest performance in ALL testing
– CASS, NSS, Russian Mud – Nissan + VW
– Colour in Blue/Green range
– Contains Sulphur for colour and performance
– Additives make darker colour
– Ion Exchange Mandatory
– Consistently passes all OEM requirements
Advanced Trivalent Systems

• Starlite
– Sulphate Based
– Contains an additive as colour control agent
– Highest performance in ALL testing
– Contains Sulphur for colour and performance
– Ion Exchange Mandatory
Advanced Trivalent Systems

• Macrome CL3
– Bright chloride trivalent system
– High plating rate
– Graphite anodes
– Passes Nissan Russian Mud test
Trivalent - Corrosion Performance
Process CASS Russian Mud Russian NSS Notes
(Nissan) Mud
(hrs) (hrs)
(Porsche)

Hex – MP 80+ 48 Fail 240 Hex

Hex – MC 48 max. 336 Pass 120 Hex

TriMacIII 80+ 72 Pass 240 Tri-Sul

Twilite 80+ 336 Pass 240 Tri-Sul

Starlite 48-72 72 Fail 240 Tri-Sul

Macrome
72+* 336 Fail 240 Tri-Cl
CL3

*using hexavalent passivate


MRD North America CASS Testing

TriMac III Hex • Cycles both use triple


Semi-Bright Nickel 20 – 25 µm 20 – 25 µm nickel (semi-bright,
Bright Nickel 10 -12 µm 10 -12 µm bright, microporous
Microporous Nickel 1 – 2 µm 1 – 2 µm nickel), and differ only in
Trivalent Chrome 0.3-0.4 µm the chrome layer.
Hexavalent Chrome 0.3 - 0.4 µm

10 10
24 hr CASS Rating
• No significant
10 9
48 hr CASS Rating
performance difference
72 hr CASS Rating 9 9 in trivalent chrome vs.
Average CASS Rating 9.7 9.3 hex chrome in CASS
testing.
Trivalent – Thickness

Coating Exterior Interior


Microns Microns

Trivalent Chrome 0.25 to 0.45 0.25 to 0.45


Micro Porous 1-3 Recommended but not essential

Bright Ni 10 10
Hi Sulphur (optional) 1-2 not required

Semi Bright Ni 15 7.5


Copper 20 25
Trivalent Cr – STEP (Optimum)

Coating STEP

Millivolts (mV)

MP to Bright Ni > -30

Bright Ni to Hi Sulphur (optional) > 20

SB to Bright Ni > 100


Trivalent Cr – Pores (Optimum)

Coating Pore Count

“Active” Pores per cm2

Micro Porous 15,000 – 50,000

Higher pore count results in hazy deposits and loss of cosmetic appearance.
Pore counts up to 70,000 can improve corrosion performance.
Below 10,000 pore count has no significant beneficial effect.
OEM Specifications for Twilite
OEM Satin Product Twilite Specification Color Designation Color L* Color A* Color B Gloss Level
Bright Twilite GS 97017 Shadow Bright Motor Sport Package 67- 69 0.3 2.7 - 2.9 Bright

M Satin Lite + M Satin Fine Twilite GS 97017 Cerium Grey Motor Sport Package 58 - 61 0.4 - 0.8 4.7-6.1 TBD
Bright Twilite CM612 Brunito Lucido 62.5 – 64.5 0.4-0.6 3.8-4.6 Bright

NiMac M-Satin Star + M Satib Fine Twilite CM615 Brunito Satinato Leggero 60.5 - 62.5 0.4-0.5 3.8-4.4 12.5 – 14.5
NiMac M-Satin Star Twilite SZN Liquid Titanium Chrome 64.5 – 67.5 0.3-0.6 2.8-3.3 23 - 25
Bright Twilite SZS Light Black Chrome 64.5 – 67.5 0.3-0.6 2.8-3.3 Bright

NiMac M-Satin Star Twilite PS12600 Light Black Chrome 64.5 – 67.5 0.3-0.6 2.8-3.3 23 - 25
M-Satin Star Twilite SM 911 Smoked Satin 68.3 0.3 2.9 TBD
Bright Twilite SM 5166 Dark Chrome 62.5 – 64.5 0.4-0.6 3.8-4.6 Bright

SatinKote Pearl Twilite PB0029/172V Illudium 172V Waiting for release of master sample
Bright Twilite PB0025/215V Obsidian 70.0 - 71.6 0.3 3.3 Bright

Bright Twilite NH-763X Dark Chrome 62.5 - 64.5 0.6 4.5 - 5.0 Bright

Hyundai /Kia Bright Twilite ? No Color designation NA NA NA Bright


Bright Twilite X61A Dark Chrome 62.5 - 64.5 0.6 4.5 - 5.0 Bright

PSA Bright Twilite FVB-M001 Smoked Chrome 63.5 - 65.5 0.4-0.5 3.5-4 Bright
Bright Twilite 11CR03 Smoked Chrome 61 - 67 0.4 - 0.9 3.6 - 4.7 Bright
NiMac M-Satin Star Twilite 21CR11 Satin, Smoked Chrome No sample available

VW Bright Twilite TBD TBD 67 - 69 0.3 2.7 - 2.9 Bright


Benefits of Trivalent Chrome systems (1)

1. Non-carcinogenic
• Trivalent is the most stable form, which is why it is less
reactive
• Trivalent chromium cannot traverse cell membranes*
• This is the reasoning behind the claims of harmlessness of
trivalent chromium in the context of human and animal genes and
tissue

2. Low chrome concentrations


• Typically a MacDermid system will contain between 10 – 20
g/l as chrome metal
• Hexavalent systems typically contain 250 g/l as CrO3
• Equivalent to some 125 g/l as chrome metal
*Source – Chromium plating in the German Electroplating industry – ZVO, October 2003

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Benefits of Trivalent Chrome systems (2)

3. PFOS-free wetter package

4. Superior deposit distribution

5. No chrome blows around holes

6. Free from burning at high current densities

7. Free from whitewashing

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Questions?

Thank You
www.macdermid.com/industrial

www.fashionfinishes.com

www.qklad.com

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