Presentatie Robin Furneaux, TSC PDF

surface critical
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products
New technologies for

colour anodizing
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Issues driving change
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Energy
➢ Anodizing has the reputation of being energy-intensive
➢ Electrochemical oxidation
➢ Hot water sealing
Waste
➢ Etching can produce large quantities of waste
Appearance
➢ “Checkerboard” panels on buildings
➢ Metallurgical non-uniformities
Car wash fluids

➢ Anodized aluminium has insufficient resistance to high pH
2 © TSC Surface Critical Products Ltd tsc Extrusion Surface Finishing Course
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Long life and recovery etches
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Long life etch

➢ Rate of dissolution of metallic aluminium equals the rate of loss of solution
aluminium by drag-out into the rinse
➢ Aluminium sequestrant to keep aluminium in solution, eg sodium gluconate
➢ High aluminium concentration in solution gives the very matt appearance
required by the European market
➢ High levels of waste sludge from etch rinse.
Recovery etch
➢ Precipitation of aluminium hydroxide by seeding and temperature modulation
➢ No additives in etch solution because crystallizer would remove them
➢ Low aluminium concentration means that the finish can be insufficiently matt for
the European market
➢ Aluminium hydroxide by-product that can sometimes be sold.
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Shot or sand blasting
Reduce the need for chemical etching
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Blasting with steel shot or sand in

compressed air
➢ stainless not mild steel, otherwise rust or
corrosion
➢ cleans off staining, corrosion products
➢ removes the surface features, eg die lines,
pick-up, weld lines, etc
➢ requires subsequent brief alkaline-etch to
achieve satin finish
Finer abrasives such as alumina or glass

beads in air or water
➢ uniform cleanliness and fine finish
➢ media consumption of brittle materials can
be high – high costs
Shot blasting machine and

effect on surface appearance
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Acid etching
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North American anodizers are using acid etching

in solutions based on ammonium bifluoride
(NH4HF2) at about 45°C.
➢ Fluoride forms soluble complexes with Al3+ thus
maintaining a high dissolution rate.
➢ Produces a rougher surface for less metal
removal than with caustic etching.
➢ Less sensitive to alloy variations and can be
better at removing die lines, hot spots and
streaking.
➢ Less metal dissolution means less waste - a
precipitate that contains (NH4)3AlF6.
➢ Usually followed by a brief caustic etch to
produce the appearance wanted by the
customer.
➢ OH&S issues with acidic fluoride solutions
Acid etch bath
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Acid etching versus alkaline etching
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Comparison showing that acid etching gives lower (and more consistent) gloss
at low levels of metal removal for different AA 6063 alloy variants. There is
further gloss reduction after anodising.
160 AA 6360
caustic etch
120
60° gloss
80
40 acid etch
data includes
AA 6360 N. Parson et al. Aluminum
0 Anodizers Council Conf.
0 20 40 60 80 100 Montreal, 2010.
Metal removal (g/m2)
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Extent of streaking after etching
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10 min NaOH 180 s acid etch
N. Parson et al. Aluminum

Anodizers Council Conf.
Montreal, 2010.
60 s acid etch + 20 s NaOH 180 s acid etch + 40 s NaOH

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Checkerboard
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Different finishes can

produce interesting
contrasts – not like
checkerboard panels
http://www.jamesandtaylor.co.uk/
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Designs and signs
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Combining masks or photo-

resists with chemical milling
and anodizing can produce a
range of decorative effects.
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Mechanically-textured surfaces
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Both extrusion and rolling processes can Pattern rolling - brushed

produce textured surfaces which can have stainless steel look-alike
their own unique aesthetic appeal, hide
surface blemishes or mimic other materials
Decorative extrusions
www.aluminiumdesign.net
10
Digital printing surface critical
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Print onto unsealed anodized aluminium

Printing capabilities
➢ Maximum print area: 2000 x 3000 mm
➢ Resolution: 2880 x 2880 dpi
Seal after printing
J-A Mantel, ESTAL Congress, Toledo, 22/9/17
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Examples of interference colours
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Munk Alu Spectral colours
Examples of Anolok 2 colours
Examples of Henkel
Spectrocolor 2000
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Aurora®
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Aurora® was commercialized in Japan in the 1990s using a variant of Anolok 2.

➢ clear, pastel colours such as blue, green, yellow, orange and pink
➢ no longer in production.
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Optical model
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A model predicts interference colours

100
based on the morphology of the anodic
oxidation coating and the optical
volume fraction of tin in thin film (%)

properties of tin and the coating material.
It has been verified by using electron
microscopy.
The model shows that colour is very 50
sensitive to morphological differences,
which might explain the low rate of
exploitation of the technology.
actual colour of sample

0
100 250 300 450
thickness of thin, interference film (nm)
I De Graeve et al, ASST 2009, Leiden colours predicted by the optical model
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Wasted energy during anodizing
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Poor throwing power can lead to a variation of 4 to 8µm over load with 20µm
coating thickness.
The current concentrates at edges and corners. And it is lower within box
sections. Higher current density leads to thicker anodic coating.
Throwing power is also affected by solution chemistry
-ve +ve
thick
thin thick thin
thick
a load of extrusions a cathode and a box section
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Reduce excess thickness
See chart below
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➢ Low current density is most important in controlling thickness spread

➢ High acid temperature is beneficial (compare brown and blue)
➢ Questionable whether acid concentration is significant (compare green and blue)
30
165 g/l, 25°C acid
Percentage spread on 22µm
25 220 g/l, 20°C acid
165 g/l, 20°C acid
thick coatings 20
A lower current
density saves energy 15
because less energy
is wasted on excess 10
thickness
5
0
1.0 1.5 2.0
Anodizing current density (A/dm2)
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Reduce excess power consumption
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A lower current density saves power because of the lower anodizing voltage.
However, higher acid temperature or concentration can degrade the quality of
the anodic coating by producing a “soft film”.
Temperatures above 25
20°C or
165 g/l, 25°C acid
Anodizing voltage (V) 220 g/l, 20°C acid
concentrations
165 g/l, 20°C acid
above 200g/l are not 20
recommended for
applications where
soft films are to be
avoided. 15
10
1.0 1.5 2.0
Anodizing current density (A/dm2)
Surface abrasion tests and “soft films”
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“Soft films” are believed to be more susceptible to degradation by weathering. If

the outer few micrometres are too soft, unacceptable changes can occur within
months of weathering.
Referee test - abrasive wheel (ISO 8251) - wear index < 1.4
12
Production control test
- manual test with 10
abrasive paper 8
hardness
(Mohs’s principle)
6
Anodic oxidation
coating must not be 4
scratched by glass 2
0
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n iam
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Anodizing and weathering
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AA 6063 flat bar extrusion anodized in 165 g/l sulfuric acid to produce coatings
25 µm thick and sealed in de-ionized water at 98 °C for 50 min.
Weathering for 6 months at Banbury, UK (rural).
Anodizing conditions Abrasive wheel Weathering

test (4.9 N) performance
Current Temperature Time Wear index
A/dm2 °C min
1.5 16 50 0.5 Original good clear
anodized finish
1.5 20 50 1.0 Slight chalking but
satisfactory appearance
1.5 22 50 1.2 Slight chalking but
satisfactory appearance
1.5 25 55 1.5 More severe chalking
1.2 25 70 1.9 Very heavy chalking
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How to reduce anodizing energy consumption
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o Low current densities

o High anodizing bath temperatures
o Effective means of dissipating heat from aluminium surfaces to
prevent soft films
 Oxalic acid additions to anodizing bath reduces coating dissolution

but acid regeneration processes might be difficult
 Pulse anodizing allows heat dissipation during “off” periods but
extends anodizing time
 Flow eductors to agitate the anodizing bath but pumping costs are
high
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Oxalic acid
8
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Oxalic acid can reduce the dissolution

of anodic oxidation coatings in sulfuric
acid enabling good quality coatings to
be produced in slightly warmer baths.
thickness reduction, µm
6 0 g/l
Many proprietary additives are probably
oxalic acid or similar organic acids.
Thickness reduction caused by an

abrasive wear test applied to 20 µm
10 g/l
coatings produced in 170 g/l H2SO4
15g/l
at 20°C with additions of 0 to 15g/l
2 5g/l
oxalic acid
0
P G Sheasby et al, “The Surface Treatment and Finishing 100 300 500
of Aluminium and its Alloys”, 2001
number of double strokes
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Heat dissipation using flow eductors
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Heat dissipation in the acid can be improved by using flow eductors instead
of air agitation
➢ venturi effect to jet acid within anodizing bath
➢ better agitation
➢ higher conductivity because there are no air bubbles
➢ reduced mist emissions
Flow eductor
Recirculated
solution
Reduction in orifice size

allows entrainment of
surrounding solution
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Sealing
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What is sealing?
“Treatment of anodic oxidation coatings on aluminium, applied after anodizing to
reduce the porosity and absorption capacity of the coating, including but not
limited to hydrothermal sealing and cold sealing.” Thus, this includes:-
➢ Hot water
➢ Steam
➢ Cold sealing
➢ Medium temperature
➢ And many other potential methods
The problem with sealing

➢ Hot water (≥ 96 °C) and steam have high energy consumption
➢ Formulations based on nickel salts might be controlled because of OH&S and
environmental issues
➢ Anodized aluminium has poor alkali resistance if conventional sealing methods are
used
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General Motors requirements
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GMW 14665 – 3rd edition, 1st November 2016

This specification covers basic requirements for anodic coatings
on aluminum and aluminum alloys.
An issue is resistance to car wash fluids.
Exterior Applications.
➢ Class A – Extreme alkaline resistance to pH 13.5. For Class A, a
supplemental coating is mandatory. Exterior coloured anodized
parts are required to be Class A
➢ Class B – High alkaline resistance to pH 13.0.
X
➢ Class C – Alkaline resistance to pH 12.0. This performance level
X
may be usable in emerging markets or other areas where
environments are known to be mild.
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Examples of approaches to alkali resistance
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Sol-gel method
➢ Silica coating needs high temperature curing
Siloxane glass (Japanese)

➢ Alkoxysiloxane coating dried at room temperature
Silicate treatment applied to unsealed anodized aluminium

➢ Two-stage with drying after each at 160 °C for 10 min
1. Sodium silicate solution at 60 °C for 5 min
2. Fluorozirconic acid solution at 25 °C for 5 min
Silicate treatment applied to sealed anodized aluminium
➢ Sodium silicate solution at 60 °C for 2 min, and dried at room temperature
 The prospect of nickel-free cold sealing

 Sealing methods that provide good alkali resistance might be suitable for
outdoor architectural applications.
 But how do we test product quality?
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Tests for sealing quality
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Referee test
Mass loss (ISO 3210) - immersion in
hot chromic / phosphoric acids
➢ Tests the chemical resistance to
particular acids that do not mimic any
service environment
➢ Developed ca. 1970 for hot water
sealing only
Production control tests

Admittance measurements (ISO 2931)
➢ Measures a property related to the
porosity of the whole thickness of the
coating
Dye absorption (ISO 2143)

Electrical analogue of anodic coating used in
➢ Assesses the absorption capacity of
the development of the admittance test: pores
the coating surface
R1; cell walls C0, R0; barrier layer C2, R2
Hoar et al, Proc Conf on Anodising Aluminium, ADA, London, 1962.
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Test requirements
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CrO3/H3PO4 Nitric acid Maximum mass

Sealing methods
mass loss test* predip loss (mg/dm2)
AAMA 611 All no 40
ISO 7599 yes and no
Only hot and cold
BS 3987
sealing 30
DIN 17611 yes
Qualanod All
The application of the mass loss test is inconsistent.

Can we be confident in its applicability to new sealing methods in the future?
* Qualanod and ISO are introducing a chrome-free mass loss test using H3PO4 alone.
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Summary
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Trends for the future

➢ Reduced use of alkaline etching
➢ More novel design technologies rather than new colouring
methods
➢ Technology to reduce anodizing electrical-energy consumption
➢ Silicate-based cold sealing processes
➢ Re-evaluation of product quality control tests

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surface critical

New technologies for

Car wash fluids

Long life etch

Blasting with steel shot or sand in

Finer abrasives such as alumina or glass

Shot blasting machine and

North American anodizers are using acid etching

Acid etch bath

10 min NaOH 180 s acid etch

N. Parson et al. Aluminum

60 s acid etch + 20 s NaOH 180 s acid etch + 40 s NaOH

Different finishes can

Combining masks or photo-

Both extrusion and rolling processes can Pattern rolling - brushed

Print onto unsealed anodized aluminium

Seal after printing

J-A Mantel, ESTAL Congress, Toledo, 22/9/17

Munk Alu Spectral colours

Examples of Anolok 2 colours

Aurora® was commercialized in Japan in the 1990s using a variant of Anolok 2.

A model predicts interference colours

volume fraction of tin in thin film (%)

actual colour of sample

thin thick thin

➢ Low current density is most important in controlling thickness spread

“Soft films” are believed to be more susceptible to degradation by weathering. If

Anodizing conditions Abrasive wheel Weathering

o Low current densities

 Oxalic acid additions to anodizing bath reduces coating dissolution

Oxalic acid can reduce the dissolution

Thickness reduction caused by an

Reduction in orifice size

The problem with sealing

GMW 14665 – 3rd edition, 1st November 2016

Siloxane glass (Japanese)

Silicate treatment applied to unsealed anodized aluminium

 The prospect of nickel-free cold sealing

Production control tests

Dye absorption (ISO 2143)

Hoar et al, Proc Conf on Anodising Aluminium, ADA, London, 1962.

CrO3/H3PO4 Nitric acid Maximum mass

The application of the mass loss test is inconsistent.

Trends for the future

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