Anodising (Topic: 14063)

Anodising is an electrolytic process. In the anodising process the aluminium extrusions are
electrically connected as the anode and the cathode may !e "lat !ars o" aluminium. The
most common electrolyte used "or architectural anodising is sulphuric acid. The
concentration is !et#een 160 and $00 g%l the temperature is usually !et#een 1& and
$$'( and the optimum current density is "rom 14 to 1& A%dm$.
)ther process parameters are mentioned in *Anodising process parameters*. To a+oid too
high temperature in the anodising !ath cooling and air agitation o" the electrolyte is
necessary.
Anodising tank with equipment mentioned above.
The anodic oxide gro#s at a rate o" approximately 1 ,m per $-3 minutes. To !uild up an
anodising layer o" $0 ,m #ill ta.e at least 40 minutes.
/ulse anodising is used to decrease the anodising time and to increase the 0uality o" the
anodic oxide layer.
Properties of the anodic oxide coating (Topic:
1400&)
The anodic oxide coating consists o" t#o layers the porous thic. outer layer gro#ing on an
inner layer #hich is thin and dense and called the !arrier layer. This layer is +ery thin
usually !et#een 01 and $01 o" the total "ilm and its thic.ness depends on the
composition o" the electrolyte and the operating conditions. The outer layer is porous due
to the attac. "rom the electrolyte. 2ee "igure !elo#. It is important to .no# that the anodic
oxide layer is an integrated part o" the metal and "la.ing or delaminating #ill not occur
#hich could happen #ith lac0uer coatings or plated coatings.
Structure of a typical cell of an anodic oxide coating showing basic units which determine
its size. The cell size is twice the cell wall thickness plus the pore diameter 3$&4
The attac. o" the electrolyte 5 and there"ore the porosity 5 is dependent o" the "ollo#ing
parameters:
1. Type and concentration o" the electrolyte
$. Temperature and agitation o" the electrolyte
3. Time in the anodising tan. (see also next point)
4. (urrent density
The porosity tells us something a!out the 0uality o" the anodic oxide layer. 6igh porosity
gi+es a poor 0uality and lo# porosity gi+es a good 0uality o" the layer. 6o#e+er it is the
pores in the anodic oxide layer that ma.e it possi!le to colour the sur"ace layer and in
addition anodising impro+es the "ollo#ing properties o" aluminium:
Response to colouring
7ue to the porous nature o" the !ul. o" the anodic "ilm it is possi!le to deposit colouring
media in the pores. The colour #ill hence !e incorporated in the layer and not lay upon
the oxide layer as #ith an organic coating. 8any colours are a+aila!le as a!sor!ed dyes
!ut only a limited num!er are suita!le "or exterior exposure. 9lectrolytic colouring is used
to impart !ron:e shades and !lac.. These are suita!le "or exterior use. At present it is not
possi!le to produce a pure #hite anodic "ilm.
Corrosion resistance
The oxide layer !uilt in the anodising process #ill impro+e the corrosion resistance o"
aluminium. A lo# porosity oxide "ilm #ill ha+e a good resistance against e.g. pitting
corrosion gal+anic corrosion and general corrosion. Accelerated corrosion tests li.e salt
spray test ha+e sho#ed that the chloride ions in the salt spray solution ha+e little e""ect on
the oxide layer. Increasing oxide thic.ness impro+es the corrosion resistance. /itting5 and
gal+anic corrosion are the most usual corrosion types on anodised aluminium and are
usually con"ined to applications #here thin poorly sealed anodic "ilms ha+e !een applied
or incorrect assem!ly practices ha+e !een used a"ter anodising.
Wear resistance
)ptimising the anodising parameters #ear resistance (a!rasion resistance) #ill !e
impro+ed. 9specially hard anodising #ill increase the a!rasion properties !ut also normal
architectural anodising #ill gi+e !etter #ear resistance.
Surface hardness
;ormal architectural anodising increases the sur"ace hardness "rom a +alue !et#een 60
and 130 </; to a +alue !et#een $00 and 3=0 </;.
Surface appearance
The appearance o" the anodised product can !e "urther enhanced !y sur"ace texturing
prior to anodising. 2uch treatment may !e mechanical (scratch !rushing linishing or
polishing) chemical or electrochemical polishing. (om!inations o" these methods are
o"ten employed.
lectrical resistance
The anodic oxide layer has high electrical resistance. Anodised aluminium is suita!le "or
electric components e.g. trans"ormers and capacitors.
!ire protection
Anodic oxide layers gi+e a minor increase in the "ire protection o" aluminium constructions.
The melting point o" the oxide sur"ace increases "rom approximately 6=0'( to
approximately $000'(.
Anodising process parameters (Topic: 14064)
In the anodising !ath the "ollo#ing parameters are important in controlling the process:
Current densit"
The current density in"luences the 0uality o" the anodic oxide coating. As sho#n in "igure
!elo# the 0uality o" the oxide layer is optimum #hen the current density is !et#een 14
and 1& A%dm$ "or a con+entional electrolyte. I" the current density is too lo# long
anodising time #ill !e necessary leading to excessi+e electrolyte attac. on the oxide layer
#hich in turn gi+es poor 0uality o" the anodic oxide.
The quality of the anodic oxide coating as a function of current density.
6igh current density increases the possi!ility o" local heating o" the aluminium sur"ace
#hich #ill reduce the oxide hardness #ear resistance and corrosion resistance.
#oltage
The current density is usually .ept constant during the anodising step and the +oltage #ill
+ary due to changes in temperature and the increasing oxide thic.ness and hence
electrical resistance. In normal sulphuric acid anodising the +oltage is !et#een 14 to 1&
<olt.
7i""erent alloys ha+e di""erent resisti+ity in the anodising !ath. To achie+e a current density
o" e.g. 1= A%dm$ the +oltage has to !e higher "or a 3003 alloy than a 6063 alloy. To a+oid
this pro!lem pro"iles o" di""erent alloys should ne+er !e anodised at the same >ig or in the
same tan. at the same time.
lectrol"te concentration
The concentration o" the sulphuric acid is usually !et#een 160 and $00 g%l. That is a
optimum +alue regarding electric conducti+ity o" the !ath and the electrolyte attac. o" the
oxide coating. 2mall amounts o" oxalic acid is o"ten added to allo# higher processing
temperature.
Aluminium concentration
A "reshly5made anodising !ath #ill not #or. +ery #ell due to lac. o" aluminium in the !ath.
The !ath is in good condition #hen the aluminium content is !et#een & and 1$ g%l. ?hen
the content reaches approximately 1= g%l regeneration o" the !ath 5 or a part o" it 5 has to
!e done !ecause !uild5up o" aluminium in the electrolyte gi+es reduced conducti+ity and
raises the operating +oltage re0uired. Too much aluminium in the !ath may also gi+e a
grey colour shade o" the oxide layer. To achie+e a good oxide 0uality the concentration o"
sulphuric acid and aluminium ha+e to !e .ept #ithin narro# limits or constant as much as
possi!le.
Agitation$temperature
The temperature o" the pro"ile sur"ace is important to achie+e a good 0uality o" the oxide
layer. The "igure !elo# sho#s the decrease in oxide hardness #ith increasing
temperature. It is important to ha+e good agitation o" the electrolyte to pre+ent local
heating. 9+en i" the temperature o" the !ath is $0'( the sur"ace temperature could !e
much higher. This is illustrated in "igure !elo#.
Oxide hardness as a function of electrolyte temperature.
Surface temperature on anodised work as a function of air agitation 3$@4
Ay addition o" oxalic acid in the anodising !ath higher temperatures (approx. $&'() are
possi!le during the anodising process #ithout decreasing 0uality o" the anodic "ilm.
Colouring of the anodic oxide la"er (Topic:
14066)
7ue to the porosity o" the oxide coating it is possi!le to impregnate a colour to the anodic
"ilm. There are three main colouring processes #hich are in use: (2ee also "igure !elo#).
Main colouring processes of the anodic oxide coating.
%"eing of the anodic oxide la"er (Topic: 1406&)
7ye colouring or adsorption dyeing is a t#o5step process and is carried out !y means o"
dipping (dip colouring) the pro"ile in a colouring solution a"ter anodising and rinsing. The
temperature in the !ath is dependent o" the colour%dye and usually !et#een == and 6='(.
2ome dyestu""s could !e used in cold !aths ($0B() !ut the #eathering resistance o" such
a coloured oxide coating is +ery poor. The colouring pigments (metal complex dyes) are
either inorganic or organic. These pigments penetrate only into the outer part o" the pores
in the anodic oxide coating and there"ore oxide coatings coloured !y dyeing ha+e not the
same permanence as oxide coatings coloured !y electrolytic colouring #here the pigment
is at the !ottom o" the pores in the anodic "ilm.
8any colours are a+aila!le "or instance !lue red yello# green and !lac.. 7ye colouring
has !een impro+ed during recent years !ut still the dye coloured oxide layer do not o!tain
the same light "astness as other colouring methods. 7ye colouring should !e restricted to
colouring o" anodised pro"iles "or indoor use. They should only !e used "or external
application #here una+oida!le.
8ost o" the dye #ill !e adsor!ed in the "irst part o" the dyeing time. There"ore control o"
colour upta.e is much more di""icult i" short dyeing times are employed. An important
implication #ith dye colouring is that it #ill al#ays !e more di""icult to secure good colour
matching #ith short dyeing times since small +ariations in temperature p6 and agitation
can ha+e a disproportionate e""ect on the rate o" dye upta.e. Curther since the "ormation
o" chemical !onds proceeds slo#ly light"astness #ill !e reduced #ith short dyeing times.
lectrol"tic colouring &C colouring' (Topic:
1406@)
9lectrolytic colouring is also a t#o step colour anodising process. It is carried out !y
means o" dipping the pro"iles in a colouring tan. a"ter anodising and rinsing. The di""erence
"rom dye colouring is in the use o" electric current. The colouring agent is also di""erent. It
is possi!le to use direct current (7() or alternating current (A() !ut most electrolytic
colouring processes use A(. 7( current can cause a de"ect called spalling #here the
anodic "ilm "la.es o"" the su!strate. This type o" current the colouring processes are also
more sensiti+e to impurities.
In the colouring tan. the electrodes (e.g. stainless steel) are placed at the tan. #all. The
colouring electrolyte solution is usually composed o" sulphates o" nic.el tin co!alt or
copper in addition to an acid. Dnder the action o" electrical energy metal particles are
deposited at the !ottom o" the pores in the anodic oxide coating. The pores are then
sealed. The p6 in the solution is !et#een 1 and == (dependent on the metal ion species
used) the current density !et#een 01 and 0= A%dm$ and the +oltage used is !et#een =
and $0. The temperature is !et#een 1= and 3='(. Air agitation o" the !ath is not
recommended !ecause o" oxidation o" the metal salts and also that air poc.ets #ould
create areas o" di""erent (lighter) colouring.
The "inishes produced are light !ro#n !ro#n pin. maroon (red5!ro#n) and !lac.. This
9(5colouring processes anodic oxide layers #hich ha+e a good #ear and outdoor
resistance.
Sealing &hot water sealing' (Topic: 140E$)
2ealing is one o" the most important steps in the anodising process. The sealing process
in"luences #ear and corrosion resistance chemical resistance and colour sta!ility. Dsual
the sealing operation is carried out in hot #ater (near the !oiling point). A temperature o"
!et#een @6 and 100'( is optimum. In the sealing process aluminium oxide is con+erted to
aluminium hydrate (!oehmite). The con+ersion is accompanied !y an increase in +olume
#hich !ridges o+er and closes up the porous structure. An easy explanation "or this
reaction is that the aluminium oxide a!sor!s the hot #ater and the +olume increases. I"
the temperature is too lo# the "ormation o" a so"ter and less resistance coating can ta.e
place.
It is important that the #ater in the sealing tan. is +ery clean. 7eionised #ater has to !e
used since impurities in the sealing !ath could ha+e serious e""ect on the sealing 0uality o"
the anodic oxide layer. The p6 should !e !et#een == and 6= to o!tain the !est
properties o" the oxide layer. To a+oid rapid changes o" p6 caused !y carry o+er o"
sulphuric acid into the sealing !ath ammonium acetate is added as a !u""ering agent. The
sealing time is $-3 minutes per ,m.
2ealing !loom or sealing smut "ormation is a side e""ect o" the sealing reaction and it
represents the "ormation o" !oehmite crystals at the "ilm sur"ace. It appears as a thin
po#dery layer #hich on clear #or. is usually in+isi!le until the sur"ace is dried and ru!!ed
#ith the "inger #hen a #hite mar. appears li.e a chal. mar.. )n coloured #or.
particularly the dar.er colours it appears as a hea+y +el+ety smut layer #hich is irregular
in appearance. 2ealing !loom ne+er appears unless sealing has !een #ell per"ormed and
constitutes there"ore a guarantee o" good sealing.
To pre+ent sealing !loom the most common practice is the addition o" organic additi+es to
the sealing !ath. 8ost o" these additi+es must !e used #ith care as particularly #hen high
le+els o" additi+e are present they can inhi!it the sealing reaction #ithin the pores as #ell
as at the "ilm sur"ace. ?hen additi+es are used "re0uent chec.s o" seal 0uality pre"era!ly
using an acid dissolution test are essential.
Special sealing processes (Topic: 140=6)
2ealing o" the anodic oxide coating in hot #ater at a temperature slightly !elo# 100B( is
the most used type !ut other *sealing* processes are also much in use special "or indoor
applications. In 9urope cold sealing is used. Cor outdoor application cold sealing is o"ten
used in com!ination #ith hot #ater sealing. 9lectrophoretic sealing is the main sealing
method "or many products in Fapan.
Cold sealing (Topic: 141$=)
(old sealing is a process to o!tain sealing o" the anodic oxide coating at a much lo#er
temperature than con+entional hot #ater sealing. The increasing cost o" energy has made
many companies see. #ays o" reducing the cost o" the sealing operation. (old seal
systems are o"ten !ased on solutions #hich contain "luoride or silica compounds in the
presence o" nic.el salts and o"ten in a #ater5alcohol mixture. The #ater5alcohol sol+ent
apparently lo#ers the solu!ility o" the salts and "acilitates precipitation #ithin the pores o"
the anodic "ilm.
(on+entional hydrothermal sealing is not in+ol+ed in these processes and pore plugging
!y nic.el salts "luorides or silicates is more the mechanism o" cold sealing. Cor this reason
there ha+e !een some o!>ections to the term *cold sealing* and *impregnation* has !een
suggested instead.
A typical cold sealing solution may consist o" a nic.el compound a "luorine compound
and o" $-!utanol. In some "ormulations part o" the nic.el is replaced !y co!alt #hich
mas.s the green coloration #hich can de+elop i" the nic.el concentration is high. The
optimum sealing time appears to !e 1 minute%micron at a temperature !et#een $4 and
3$B( is recommended. 2hort sealing times are ine""ecti+e and can gi+e rise to a #hite
po#der de+eloping later on the sur"ace. The p6 is !et#een == and 6=. ?or. sealed in
this #ay has !een sho#n to ha+e good corrosion resistance and good seal 0uality and is
!y many considered e0ui+alent in per"ormance to that produced !y con+entional sealing.
The cold sealing system is !ecoming #idely used in many countries and has recently
!een appro+ed !y uras &(ualanod' for outdoor use. Aut there is still concern
particularly in external architectural applications a!out long term properties. To o+ercome
this sealing can !e carried out "irst in the cold seal and then gi+ing a short treatment in a
con+entional seal.
As the sealing mechanism does not depend on normal !oehmite "ormation there is also
contro+ersy o+er #hether the normal corrosion and seal 0uality tests can !e applied to
#or. sealed in this #ay. (ertainly the mechanism is +ery di""erent as #or. tested soon
a"ter sealing #ill usually gi+e +ery high #eight loss +alues and it is only a"ter $4 hours or
more that they "all #ithin normally accepted limits. This creates pro!lems in terms o" on5
line production e+aluation o" seal 0uality. To o+ercome this sealing can !e carried out as
mention a!o+e.
Which allo"s are suitable for anodising)
(Topic: 1400=)
/ure aluminium has a !etter anodic response than its alloys and an apprecia!le
di""erence is to !e detected !et#een the appearance o" coatings produced on the +arious
grades o" aluminium. The di""erence !et#een commercial50uality material (@@1) and
super5purity aluminium (@@@@1) is particularly noticea!le. The ta!le !elo# gi+es a general
guidance on alloy !eha+iour #ith respect to those suita!le "or protecti+e anodising
decorati+e and colour anodising !right anodising and hard anodising.
Guide to selection of finishes for wrought alloys 3$E4.
8ost aluminium alloys can !e pro+ided #ith an anodic oxide coating #hich is moderate to
good pro+ided that the appearance is o" no great concern and that protection is the
o!>ecti+e. Also "or general decorati+e #or. the ma>ority o" these #ill !e satis"actory
pro+ided that they do not !ecome excessi+ely dar. or patchy. 6o#e+er #here !rightness
is the primary re0uirement there are "e# alloys to choose "rom as the ta!le indicates. )nly
metal o" high purity is classed as excellent. In the case o" hard anodising characteristics
the comments are !ased on the a!ility to produce a satis"actory =0 ,m anodic coating.
Among the #rought alloys the Al58g52i alloys (60005alloys) #ith or #ithout small additions
o" 8n produce the !est decorati+e and protecti+e coatings and Al5Gn58g alloys (E0005
alloys) are also good. Alloys containing apprecia!le amounts o" (u and other hea+y
metals usually produce coatings o" in"erior colour.
ffects of allo"ing elements on the
anodising appearance (Topic: 1400E)
*ron + is the principal impurity #hich detracts "rom the specular !rightness o" the high
purity !right anodising alloys e+en in 0uite small amounts (00&1). Iron additions to super5
purity aluminium (@@@@1) lead to dar. grey or !lac. strea.s. ?hen iron is at 031 a
typical le+el "or alloy 10=0 the coating !ecomes 0uite grey in comparison. It may !e a
uni"orm light grey colour or striated or mottled according to the distri!ution o" the iron5
containing particles. The max. iron content o" the alloys in this 7esign support manual is
0E1 (30033103 and 6061) !ut only one o" them is a *real* extrusion alloy (6061).
Silicon + leads to cloudiness #hen out o" solution (precipitation o" AlCe2i or 8g$2i
intermetallic particles) !ut a!out 0&1 can remain dispersed. It is !ene"icial #ith the iron
impurity. In 8g alloys silicon goes more readily into solution. At the =1 le+el alloys
anodising to dar. grey or !lac. are o!taina!le. Alloy 60&$ has the highest +alue #ith 131
o" the alloys listed in this 7esign support manual.
,itanium 5 detracts "rom !rightness in the same #ay as iron !ut is added to produce "ine
grain. Along #ith !oron it also promotes nucleation helping to get a "ine uni"orm structure.
-agnesium allo"s 5 can gi+e clear colourless coatings "or 8g up to 31 pro!a!ly
!ecause magnesium oxide has a re"racti+e index +ery near to that o" aluminium oxide.
;one o" the alloys mentioned in the manual has 8g5content a!o+e 1=1. Alloy E10& has a
max. +alue o" 1=1.
Copper + up to $1 can gi+e alloys #ith a clear protecti+e coating in the solution treated
condition. This amount o" copper is much higher than in the actual alloys in our manual
#here alloy 6061 has the highest content #ith max. 041. Alloy 6463 #ith max. 0$01 (u
is suita!le "or !right anodising.
-anganese allo"s 5 up to 11 8n may anodise to clear sil+er grey !ro#n or mottled
according to production history and particle si:e o" the constituent. ?ith the thic.er anodic
"ilms 8n contents o" 03-0=1 gi+e 0uite !ro#n anodic oxide coatings on all o" the alloys
#here the metal is present. Cour o" the alloys descri!ed in the manual ha+e high 8n
content (a!o+e 041) !ut only t#o o" them are *really* extrusion alloys. These are 60&$
(max. 101) and 600= (max. 0=1). They #ill turn !ro#n in the anodising process. Alloy
3003 and 3103 !oth #ith max. 1=1 8n #ill o!tain a colour a"ter anodising according to
the production history.
.inc allo"s 5 "orm good protecti+e coatings #ith :inc up to =1. These may !e colourless
#hen homogeneous or 0uite !ro#n or mar!led in appearance #hen second phase
precipitates are present. Alloy E10& has a :inc content o" max. =&1. Too much :inc in the
alloy or in the etching !ath (pre5treatment !e"ore anodising) #ill cause spangle e""ect
Chromium 5 at 031 leads to coatings #hich are yello# in colour. There are only $ alloys
in this manual #ith a chromium content up to 031. That is 600= (max. 031) and 6061
(max. 03=1).
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