CrO3 alternatives in decorative and

functional plating
25.01.2017
 CrO3 alternatives

Decorative plating
Chrome plating
Etching of plastics
Functional plating

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 Decorative chrome plating from trivalent
Chrome electrolyte

End use sector

Automobile
Trims, emblems… plating on plastics
Building
Door handles, furnitures, door hinges : steel, zamak
base material
Cosmetics
Perfume caps
Sanitary fittings
Shower heads & holders : plating on plastics, on zamak,
or brass

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 Decorative chrome plating from trivalent
Chrome electrolyte

Required properties
Aspect : colour (L*a*b* values as close as possible to CrVI
reference)

Corrosion resistance properties

Neutral Salt Spray Test (ISO 9227)
CASS test (ISO 9227)
Russian Mud (NISSAN NES M 4063…)
Specific tests
PV 1073 A & B : Chrome and Nickel corrosion

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 Aspect of chrome deposits

Colour
Measured by spectrocolorimeter
Results expressed in the CIE L*a*b* color space

L* ( 0 ÷ 100 ) a* ( - 60 ÷ + 60 ) b* ( - 60 ÷ + 60 )
(Black ÷ White) (Green ÷ Red) (Blue ÷ Yellow)

TRISTAR 300 (chloride) 78 ÷ 80 -0.1 ÷ 0 0.5 ÷ 1

TRISTAR 300 AF serie

(sulphate) 82 ÷ 84 -0.6 ÷ 0 -0,2 ÷ 0,5

CHROME 200 (CrO3) 82 ÷ 84 -0.6 ÷ 0.2 -0.5 ÷ 0.5

Table N°3 : Colour of different Chrome deposits (CIE

L*a*b* coordinates)

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 Corrosion resistance of trivalent
chrome vs hexavalent systems

CrVI reference TRISTAR 300 serie TRISTAR 300 AF

(Cl- based) + post serie (SO42- based)
treatment + post treatment
NSST (ISO 9227) 480h wo stains 480 hours wo stains 480 hours wo stains
CASS test (ISO 72 hours 48 hours on 48 hours on
9227) microporous Ni microporous Ni
72 hours on STRATA
Russian Mud (NES Doesn’t pass 96 h Pass 96 hours Doesn’t pass 96 h
M 4063)
PV 1073 A Doesn’t pass Pass Doesn’t pass
PV 1073 B Doesn’t pass Doesn’t pass Doesn’t pass

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 POP Sequence-TRISTAR: Acid Copper
thru Drying

Acid Sulphur Micro-

Bright Nickel
Rinse Porous

Rinse

Rinse

Rinse
Copper Free Nickel CRYSTAL
CUBRAC CRITERION Nickel
103
2900 SB 100 CRITERION
MP 250
Rinse

Rinse

Rinse

Rinse

Rinse

Rinse
TRISTAR POST
300 Dry
TREATMENT

Max 2 more steps than for CrVI

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 CrO3 alternatives

Decorative plating
Chrome plating
Etching of plastics
Functional plating

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 Plating On Plastics with Non Chrome
Etch
CrVI etching mechanism
Cr6+ Cr3+ Pd colloid EN

Acc.
B AS
Substrate ABS After Etching After After After EN
CrO3/H2SO4 Neutralization Catalyst ~10 min, ~30°C
10-15 min, ~68°C 1 min, ~45°C 2-3 min, ~30°C

Before etching After low CrVI Etch After high CrVI Etch
Bare material ~80 g/L CrO3 ~400 g/L CrO3
ABS – SEM picture – before and after etching

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 Plating On Plastics with Non Chrome
Etch
CrO3 based etch versus non CrO3 etch on ABS
COMPARISON OF THE ETCHED SURFACE BY SEM

Surface structure after etching with SILKEN Bond and Cr VI etch

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 Adaptation in an existing line

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 Oxidation cell

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 Adhesion

Peeling test 90° following ASTM B533-85 (2004) in Newton per 25 mm width of strip
peeled
Peeling strength highlights the adhesion of the metallic layers on the plastic surface.
Parts are 2.5 cm wide and measurement was done in OEM labs.

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 Plating on plastics with non chrome
etch
Rack plating
Conventional system : CrVI acts as a poison and prevents rack
metallization
Non chrome etch system : specific rack conditioner* prevents
electroless Nickel reduction on the racks

Bi injected parts
Beta site test
Beta site test : 18 months of production in pilot line * Patent pending
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 CrO3 alternatives

Decorative plating
Chrome plating
Etching of plastics
Functional plating

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 CONTEXT

Hard Chrome = use of hexavalent chomium

 For decorative appearance
 For functional aspect (hardness, thickness, 
mechanical properties and corrosion)

∎ Industrial context

 Chrome industry = 5000 to 10000 employees in France

 Hex Chrome use will be submitted to authorization
 According REACH regulation EC N° 1907/2006
 From September 2017
Research project at the IRT‐M2P in order to develop an alternative to CrVI
process based on CrIII electrolyte 

HCTC Project → « Hard Chrome by Trivalent Chromium »

16
 PROJECT HCTC : « HARD CHROME BY
TRIVALENT CHROMIUM »

∎General information
 Project duration: 48 months since Feb 2014
 17 partners: 15 industrial and 2 laboratories
 Total budget: ≈ 3.35 million euros
 Multi‐scales : 40 liters to 800 liters

∎ Project’s goals

 Develop an alternative from a REACH compliant CrIII based electrolyte
 Understanding of the deposition mechanisms from a CrIII electrolyte
 Evaluation of ageing of CrIII electrolyte
 Coatings characterization in comparison to those of the deposits obtained from CrVI

17
 SUBSTRATE

• Substrates
– Representative of the final use

15CDV6 coupons
(quenched and tempered
steel) 15CDV6 & XC 48
Mechanical strength : 980 to steel cylinders
1180 MPa 18
 COATING CHARACTERIZATION

Fatigue tests (rotative bending) ISO 1143:2010

15 CDV 6 (Moore type) samples
Frequency : 50 Hz
Stress vs Number of cycles until 1E+07 cycles without complete failure
900

800

15CDV6
Better fatigue
700 behaviour than
hex Chrome
Stress (MPa)

600
CrIII + Th T 4h at 200°C

500

19
400

CrVI + ThT 4h at 200°C

300
1E+04 1E+05 1E+06 1E+07
Number of cycles 18
 OVERVIEW OF THE COMPARATIVE PROPERTIES

HEXAVALENT  TRIVALENT HARD 
CHROME CHROME
Ability to plate high  Yes Yes (up to 400 µm 
thickness tested)
Structure Micro cracked Presence of through
cracks – Increase with
heat treatment – Last 
developments : low and 
thin cracks even after
thermal treatment
Hardness Decreases with Increases with
temperature temperature
Fatigue Good Superior to Hex Chrome
Wear resistance Good Comparable to Hex
Chrome

Corrosion protection Medium Superior to Hex Chrome 

with a Ni underlayer
20
 CONCLUSIONS
 Bath is very stable:
 2 x 40 Liters : Coventya and Utinam : > 1000 Ah/L
 600 Liters (IRT M2P) – 20 months of use > 130 Ah/L
 800 Liters (Safran Turbomeca) – 6 months of use 50 Ah/L

 Comparison with CrVI on low Carbon steel :

 Optimization of electrolysis conditions
 Fatigue on steel : Confirmation of the superior behaviour of CrIII vs
CrVI
 Hardness : Yes
 Deposition rate : Yes
 Abrasion : Yes
 Adhesion : Improvement of adhesion and through cracks even after
thermal treatment
 Corrosion : No (but yes with Ni layer)

 Simple parts (as automotive shock absorber) to be coated and

characterized
 Specific rectifier required
 Pre treatment sequence : substrate dependent 21
 Conclusion
Alternatives to CrO3 in decorative chrome plating
Chrome plating electrolyte
Anti corrosion properties are achieved with chloride based electrolytes
Aspect is close to CrVI with sulfate based electrolytes
Systems are in production phase since 3 years for automotive exterior
parts
Etching of plastics
Permanganate based systems enable to obtain consistent results on
ABS, ABS/PC parts
Bi components treatment in beta test

Alternatives to CrO3 in functional chrome plating

Trivalent chrome with dedicated operating parameters
Representative parts to be plated first semester 2017

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