SurTec

Technical Letter 19

Hard Anodising in Practice

February 2011
Technical hard anodising is based on physical as well as chemical
processes. This complex procedure results from its various interdependent
parameters. The following describes its fundamentals and practical use.
1. Fundamentals

Fig. 1: Schematically illustrates the fundamentals (see A. W. Brace) of:

structure of anodised coating

formation of barrier layer
cell formation
orientation of layer growth

The pictures clearly illustrate the formation of pores within a hexagonal lattice (i.e. crystal
structure). Depending on physical-chemical conditions the layer (Al2O3 = aluminium
oxide), to a greater or lesser extent, is hard. The picture also shows the formation of the
barrier layer on the base material.
Depending on the alloy composition, the anodised coating will be formed more or less in
accordance with the following formula:
3 A/dm2 x 1 minute = 1 µm layer thickness
Hypothetically, the layer grows to 50 % inwards and to 50 % outwards. As specialist
literature describes, due to inevitable re-dissolution the layer grows to 2/3 inwards and to
1/3 outwards. Therefore, under optimum operating conditions, it is also possible to
achieve layers that meet DIN or ISO fits.

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The pore diameter is proportional to the current density and amounts to some
200-400 angstroms which corresponds to 200-400 x 10-10 m.
The distance between pores is proportional to the direct current (DC) and can be
summarised as follows:
DC = 30 V: corresponds to a small distance with small amounts of Al2O3,
i.e. copper containing alloy
DC = 80 V: corresponds to a large distance with large amounts of Al2O3,
i.e. highly silicon containing alloy
The limits of physical layer formation become quite obvious with regard to:
layer thickness
hardness
abrasion resistance
The thickness of the barrier layer is also directly proportional to the DC giving vital
information on corrosion resistance properties. The following applies:
high DC implies a thick barrier layer and vice versa
each layer possesses a specific voltage for breakdown to the base material:
the so called burner
a burner also has something to do with cooling and is therefore dependent
on the electrolyte temperature
for example: AlMgSi12 breakdown at about 80 V
and with AlPbZnCu breakdown already at about 28 V

Fig. 2: Geometrically formed pores, perpendicular to the base material;

both the crystal structure of the Al2O3 as well as the barrier layer can be clearly
recognized. (see A.W. Brace and P.G. Sheasby)

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Fig. 3: Correlation between current and voltage during hard anodising process

In order to generate beautiful pores perpendicular to the base material, it is necessary to

apply constant currents with alloy specific voltage limiting. Exposition must be suspended
as soon as the declining current reaches about 50 % of the nominal current density. This
is how the balance between layer formation and re-dissolution is created. Required
parameters are the temperature of the electrolyte and the flow rate for derivation of
reaction temperature.

Current densities that can be realized with various processes:

direct current = 2-3 A/dm2

direct current + pulse = 4-6 A/dm2

Due to the fact that growth of the barrier layer is proportional to the voltage even a small
increase, i.e. application of pulse, can induce a significant change in current,

e.g.: a base current density of 3 A/dm2 corresponds to 40 V

a pulse current density of 6 A/dm2 corresponds to 45 V

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Fig. 4: Russian patent in comparison to a pulse current system; the graph clearly
highlights the similarities

it is possible to series-connect a battery to an alternating current source

a rectifier, on the other hand, cannot be series-connected to a transformer
due to the magnetizing current
As an alternative the use of a pulse rectifier, since it achieves the same effect,
proved beneficial.

2. Function of Pulse and its Benefits to Direct Current

pulse current continuously regenerates and constantly forms a barrier layer;

re-dissolution is largely avoided even at declining currents
constantly growing barrier layers allow for higher current densities
exposition times can be reduced by 30-50 % resulting in less re-dissolution,
increased hardness and abrasion resistance properties
a superimposed pulse voltage automatically results in a larger distance
between pores and consequently a larger amount of Al2O3
Compared to direct current, the layers on aluminium achieved with pulse under the same
chemical-physical conditions are

clearly of a superior quality!

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Fig. 5: Correlation between specific conductivity and concentration of sulphuric acid

The curve indicates that conductivity reaches its peak at about 30 % and rapidly declines
beyond this point. One also needs to take into consideration that re-dissolution
significantly increases with large concentrations of H2SO4.
In order to achieve maximum voltage at a constant current density with copper
containing alloys, i.e. the most stable and thickest barrier layer, the electrolyte used is to
possess the following parameters:
concentration:
H2SO4 250 g/l
SurTec 312 50-60 g/l
aluminium 3 g/l
temperature: - 5°C up to + 5°C (depending on alloy)
voltage limiting: 25-32 volt

Generally the following applies:

The higher the concentration of sulfuric acid, the larger the formation of pores and vice
versa.
The limits of aluminium oxide formation become recognizable. Hardness and abrasion
resistance are physically restricted by the alloy. Depending on rate of flow the use of
oxalic acid as inhibitor can be omitted.

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For magnesium and silicon containing alloys the use of an electrolyte with the following
parameters proved beneficial:
concentrations:
H2SO4 150-160 g/l
SurTec 312 20-30 g/l
aluminium 3-5 g/l
temperature: - 5°C to + 10°C (depending on alloy)
voltage limiting: 50-80 volt
Pore formation is relatively low allowing for a large amount of Al2O3. The barrier layer is
very stable and thick. Hardness and abrasion resistance ranges from good to excellent.
Physical requirements for bath installation:

visible cathode surface corresponds to 100 % to maximum part surface

cross section of cathode max. 0.5 A/mm2 to avoid heating of electrolyte and
reduction in performance
cross section between rectifier and bath max. 1 A/mm2 with aluminium (Al)
and max. 2 A/mm2 with copper (Cu)
racks on the rim always made of aluminium with a cross section of max.
1.2 A/mm2
contra directional electrolyte feed for similar electrical field and uniform
current density over the entire bath volume
bath circulation at least 15 x per hour, preferably 30-40 x per hour to
minimize re-dissolution and to discharge reaction temperature from the
pores as quickly and vigorously as possible to the electrolyte:
!!!This is the only way to produce hardness and abrasion resistance!!!
air ducts on the bottom must be H-shaped, installed for vertical flow
air output: 0.3 m3/m2 bath surface / minute
or: 18.0 m3/m2 bath surface / hour

3. Hard Anodising in Practice

low sulfuric acid concentration

low temperature
low aluminium content
high current density
high flow rate
short exposition time
excellent contacting
result in thick, hard, uniform and abrasion resistant layers and vice versa!

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4. Sealing (Compacting) of Hard Anodised Aluminium

due to the substantial distance between the pores, a sealing time of about
0.5 minutes/µm in 96-98°C deionised water is sufficient
NOTE: the longer the hard anodised aluminium stays in hot water the softer
the layer!
the following applications are available: hot sealing - cold sealing and a
combination of both (automotive parts)
for lowest friction properties a post-treatment with PVDF proved beneficial
for highest corrosion resistance properties anodising must always be
followed by a chemical passivation

working parameters:
SurTec 650: 10-20 %vol
pH-value: 3.7-3.95
temperature: 30-33°C
time: 0.1-0.3 minutes/µm

5. Pulse Rectifier

Fig. 6: Pulse rectifier, type DTOWG500-80/12000 of Co. BEFELD-SYSTEME GmbH,

with external oil-water cooling and a capacity of 80 V, 12,000 A

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Fig. 7: Pulse rectifier, type DTWG 380-60/15000 of Co. BEFELD-SYSTEME GmbH,
with water cooling and a capacity of 60 V, 15,000 A

Fig. 8: Pulse control unit of a rectifier type DTLG 400-80/3000 of Co. BEFELD-SYSTEME GmbH,
with analogous measurement devices and set value potentiometer for pre-setting of:

voltage limiting
ramp time
base time
base current
pulse duration
pulse current

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For the pulse control unit we will provide the corresponding adjustment value table. After
defining the values for the various alloys hard anodising can either be carried out
manually in accordance with the table or via automatically controlled computer formula
with analogous input signals.

Calculation example
For exposition time needed for nominal layer thickness of 50 µm per 2,000 dm2 aluminium
surface:
2
Al-surface: 2,000 dm
base current: 6,000 A
pulse current: 3,000 A
base time: 1s
pulse duration: 0.5 s
1 A min A
base current volume : 3 (2.4 with Al - alloy 7075 + 2025 )
dm² µm dm² µm
nominal layer thickness: 50 µm

pulse current x pulse duration

DC-mean value = base current + [A ]
(base time + pulse duration )
3000 A x 1 s
= 6,000 A +
(0.5 s + 1 s )
= 8,000 A

DC − mean value  A 
mean current density =  dm² 
Al − surface  

8,000 A
=
2,000 dm²

A
= 4
dm²

base current volume

exposition time = nominal layer thickness x [min]
mean current density

3 (2.4) A min dm²

= 50 µm x
4 A dm² µm

= 37.5 (30) min

1 2
This current volume is required to generate 1 µm anodised layer on 1 dm aluminium

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