Dr.

Vika Rizkia
Mechanical Engineering
Politeknik Negeri Jakarta
 There are few people today who are not familiar with some modern
applications of aluminium and its alloys and the enormous number of
applications is mainly due to the excellent corrosion resistance of this
metal.
The corrosion resistance of aluminium is achieved due to the affinity of
this metal for oxygen that generates on its surface a very thin oxide
film which covers the surface of a freshly-cut piece of metal is exposed
to the atmosphere.

in some cases it is necessary to have a higher degree of protection (corrosion or chemical

resistance) or to modify the surface appearance (changing, colour, texture, etc.) or creating
technical physical surface properties (increasing the abrasion resistance and hardness,
achieving coating with anti-friction properties, getting coatings with increased bonding strength,
etc.).
Nanotechnology, in combination with surface engineering focused on a fabrication of various
nanostructures and new materials, has recently attracted a vast amount of research attention, and
has become a subject of intense scientific interest.

Currently,much effort has been undertaken to develop an effective and technologically simple
method used for the synthesis of nanostructures over a macroscopic surface area

Today, the research spotlight is especially focused on self-organized nanostructured materialswith a

periodic arrangement of nanopores due to the high expectations regarding their applications

A highly desired densely packed hexagonal array nanoporous structure can be obtained by
anodization, which is a relatively easy process for nanostructured material fabrication

an electrochemical process for producing stable

oxide films on the surface of metals.

an electrochemical process in which the part is made the anode. A potential is applied to this
piece high enough to allow the development of oxygen on the aluminium surface.
that the anodic film consists of two layers, the porous
thick layer growing on an inert layer which is thin, dense
and dielectrically and normally called barrier layer

The thickness of the barrier layer depends on the

composition of the electrolyte and the operating
conditions

During anodizing the barrier layer is formed first and

its thickness varies directly with the forming voltage

The barrier layer is non-porous, and conducts current

only due to its thickness and faults, the outer layer, is
microsporous and built upon a columnar structure

the porous layer is due to a local dissolution

of the barrier layer, followed by the passage of
the current, which rises
 Proses elektrokimia untuk memproduksi lapisan oksida tipis pada permukaan
logam sehingga menjadi lebih dekoratif, tahan lama, dan tahan korosi
Proses ini disebut anodisasi karena Disamping itu anodisasi dapat
logam yang akan dilindungi atau meningkatkan ketahanan aus, serta
diberikan perlakuan dibuat menjadi memberikan pelekatan yang lebih
elektroda anoda dalam sebuah sirkuit baik terhadap cat dan lem
dibandingkan material awalnya

1. Lapisan yang jernih

Karakteristik dari lapisan 2. Keras dan tahan abrasi

oksida hasil proses 3. Tahan korosi

anodisasi yaitu : 4. Mudah dilakukan pewarnaan
5. Insulator termal dan listrik
 A DC, AC or a combination
of both can be used as
power supply for anodizing

An aluminium piece is
used as anode

the negatively charged ions

migrates to the anode where
one or more electrons are
discharged

For standard sulphuric acid anodizing a 24 V rectifier is suitable, however, for chromic
acid anodizing or anodizing in organic acid voltages up to 60-70 V are needed. For hard
anodizing and for production of barrier-layer films higher voltages are needed.
 Ketika tegangan diaplikasikan dalam sel elektrokimia,
reaksi terjadi pada interface substrat aluminium/oksida
hingga terbentuk kondisi yang seimbang :
2Al(s) + 3H2O  Al2O3 (s) + 6 H+ (aq) + 6e-

Pelepasan elektron menghasilkan arus anodisasi pada

permukaan elektroda anoda.
Sehingga dalam kondisi potensiostatik, pada permulaan
proses anodisasi terlihat bahwa arus yang terdeteksi
meningkat secara signifikan, hal ini mengindikasikan
terbentuknya lapisan oksida awal yang biasa disebut
lapisan oksida barrier (barrier layer)

Peningkatan arus secara signifikan ini dilanjutkan dengan penurunan arus drastis menuju nilai
yang relatif rendah ketika lapisan barrier ini mulai berkembang

Di waktu yang sama terjadi pelarutan lapisan oksida yang menghasilkan morfologi pori pada
AAO : Al2O3 (s) + 6 H+ (aq)  2Al+ + 6 H+ (aq)

Seiring dengan berjalannya waktu, struktur pori pada bagian dasar pori mulai tumbuh stabil
(pertumbuhan pori steady state) dan keteraturan susunan pori mulai meningkat yang ditandai
dengan terdeteksinya daerah rapat arus konstan
The thickness of the anodic film increases with
treatment time.

However, the rate of thickness growing depends

of several factors such as: type of electrolyte,
current density, treatment time, etc

During anodizing there are a continuous,

thickness growth of the anodic film and a
dissolution by chemical attack. The actual
thickness is the theoretical thickness minus the
thickness of oxide dissolved
 Generally aluminium anodizes better
than its alloys

Size, shape and distribution

of intermetallic compound also affect the
behaviour and anodizing response

The composition of the alloy is quite

important in some applications such as
bright anodizing where the level of
insoluble particles must be a low as
possible

Generally among the aluminium alloys, the series 5xxx and 6xxx produce the best
decorative and protective coatings, some 7xxx series alloys also produce clear coatings with
good performance. Usually the 2xxx series produce coating colours of inferior quality
 The effect of an increase of electrolyte
temperature is a proportional increase in
the rate of dissolution of the anodic film
resulting in thinner, more porous and softer
films

Low temperatures are used to produce hard

coatings normally in combination with high
current densities and vigorous agitation

In decorative and protective anodizing

temperatures in the range of 15-25 °C are
normally used

If temperature is increased further the maximum thickness is reduced to lower values

due to the higher dissolving power of the electrolyte
 The range of current density used in
standard anodizing varies from 1-2
A/dm2, for certain application up to 3
A/dm2

Current densities below this range

produce soft, porous and thin films

As the current density is increased, the

film forms more quickly with relatively
less dissolution by the electrolyte,
consequently the film is harder and less
porous

At very high current densities, there is a tendency for "burning"; this is the development of
excessively high current flow at local areas with overheating at such areas
The effect of increased concentration on the
coating characteristics is similar to
temperature increase, although the effect of
temperature is more important than that of
concentration

The increase in concentration limitates the

maximum film thickness due to the higher
dissolving power of the concentrate solutions
Hundreds of commercial dyestuffs are available for colouring anodic films produced by
most anodizing conditions yielding a wide range of attractive colours. The colour intensity
depends on the amount of dye taken up by the film.

The absorption mechanism is produced in the upper part of the anodic film (in the 3-4
external mm)
 The electrolytic colouring or "Two Step anodizing"

The process consists of immersing the anodize work in an

and solution containing metallic salts and to apply and AC
or DC voltage

The colour depends on the nature of the electrolyte; most metals give a bronze to black colour
(Sn, Ni, Co, etc) some as copper gives reds etc

The colour is independent to a certain extent of the thickness of the anodic coating and is
only dependent of the amount of metal deposited (200 mg/m2 Sn produces a light bronze
and 2000 mg/2 Sn producer a deep black).
 In the late seventies electrolytic colouring took a step
forward with the development of interference colouring

This procedure allows to produce a wide range of colours

using an electrolyte due to a mechanism of optical
interference. Normally a pore enlargement treatment is
necessary between anodizing and electrolytic colouring in
order to increase the intensity of the colour

The main advantage of interference colour it is de wide variety of colours that it is possible to
produce
The colour is produced during anodizing in the first case due to the constituents of the alloy in
the second case due to the inclusions during anodizing produced by using special electrolytes

The colour and uniformity of the finishes are depending on composition and metallurgical
history

Probably the first integral colour anodizing is the oxalic process which under controlled
conditions can give coatings coloured from pale yellow to deep bronze. The colour on
these type of finishes is dependent on film thickness and the thicker the film the darker the
colour

The range of colour using integral colouring are: different topes of gold and bronze to deep
black.
Sealing is the last step in the anodizing process and is essential for retention during service
of the initial appearance of the anodized material

Water sealing seems to produce little change in the bulk oxide film (increases water content
up 4 to 10 percent) but causes major pore blockage

Sealing is commonly done by immersion in good quality water heated to 95-100 C at a

pH of 6.0 ± 0.5 for a period of 2-3 min/mm.

The salts are absorbed into the coating where they are hydrolysed and precipitated as
hydroxides.
 an electrodeposition process for producing a
dense, uniform, and adherent coating, usually of
Electroplating metal or alloys, upon a surface by the act
of electric current

Usually :
For decorative and/or protective purposes, or enhancing specific properties of the surface

Widely used for many industries, such as automobile, ship, air space, machinery,
electronics, jewelry, defense, and toy industries

The core part of the electroplating process is the electrolytic cell

Electroplating
The workpiece to be plated is the cathode (negative terminal)
The anode can be one of the two types: sacrificial anode (dissolvable anode) and
permanent anode (inert anode)
can only complete the electrical circuit, but cannot provide a
made of the metal that is to be
source of fresh metal to replace what has been removed from
the solution by deposition at the cathode (Pt and C)
deposited

Electrolyte is the electrical conductor in which current is carried by ions rather than by
free electrons (as in a metal)
• Upon application of electric current, the positive ions in the electrolyte will move toward the
cathode and the negatively charged ions toward the anode.
• This migration of ions through the electrolyte constitutes the electric current in that part of the
circuit.
• The migration of electrons into the anode through the wiring and an electric generator and then back
to the cathode constitutes the current in the external circuit.
 Electrochemistry
Fundamental
Voltaic/galvanic cells are driven by a spontaneous
chemical reaction that produces an electric current
through an outside circuit.
These cells are important because they are the basis
for the batteries that fuel modern society

But they aren't the only kind of electrochemical cell

The reverse reaction in each case is non-spontaneous and requires electrical energy to occur
Composed of two half-cells--one is a reduction half-cell, the other is
an oxidation half-cell

The definition of both cathode and anode remain the same, where
reduction takes place at the cathode and oxidation occurs at the
anode

A consistent flow of electrons from the anode to the cathode

Galvanic Cell
A Galvanic cell converts chemical energy into
electrical energy
Here, the redox reaction is spontaneous and is
responsible for the production of electrical energy
The two half-cells are set up in different
containers, being connected through the salt
bridge or porous partition.
Here the anode is negative and cathode is the
positive electrode. The reaction at the anode is
oxidation and that at the cathode is reduction.
The electrons are supplied by the species getting
oxidized. They move from anode to the cathode in
the external circuit.
Electrolytic cell
An electrolytic cell converts electrical energy into
chemical energy
The redox reaction is not spontaneous and
electrical energy has to be supplied to initiate the
reaction
Both the electrodes are placed in a same container
in the solution of molten electrolyte
Here, the anode is positive and cathode is the
negative electrode. The reaction at the anode is
oxidation and that at the cathode is reduction.
The external battery supplies the electrons. They
enter through the cathode and come out through
the anode
Electrochemistry
Fundamental

When a direct electric current passes through an

electrolyte, chemical reactions take place at the
contacts between the circuit and the solution

This process is called electrolysis

Electrolysis takes place in an electrolytic cell

Electrolysis is used to drive an oxidation-reduction reaction in a direction in which it does

not occur spontaneously by driving an electric current through the system while doing
work on the chemical system itself, and therefore is non-spontaneous
 To explain what happens in an electrolytic cell let us examine the decomposition of
molten sodium chloride into sodium metal and chlorine gas
If molten NaCl (l) is placed into the container and inert electrodes of C(s) are inserted , attached to
the + and - terminals of a battery, an electrolytic reaction will occur

Electrons from the negative terminal travel to the cathode and are used to reduce sodium ions into
sodium atoms. The sodium will plate onto the cathode as it forms. The sodium ion are migrating
towards the cathode.

The negative Chlorine ions migrate towards the anode and release electrons as they oxidize to form
chlorine atoms. The chlorine atoms will combine together to form chlorine gas which will bubble away

Note that the site of oxidation is still the anode and the site of reduction is still the cathode, but the
charge on these two electrodes are reversed. Anode is now + charged and the cathode has a - charged.
The substance that is the strongest reducing agent (the substance with the highest standard cell
potential value in the table) will undergo oxidation. The substance that is the strongest oxidizing agent
will be reduced. If a solution of sodium chloride (containing water) was used in the above system,
hydrogen would undergo reduction instead of sodium, because it is a stronger reducing agent that
sodium.
 to remove
contaminants, such as
dust and films, from the
substrate surface.

Extrinsic, composed of Intrinsic, such as a

organic debris and native oxide layer.
mineral dust from the
environment or
preceding processes

• Contaminants and films interfere with bonding, which can cause poor adhesion and even
prevent deposition
• Therefore, surface pretreatment is important to ensure plating quality
• Most (metal) surface treatment operations have three basic steps: surface cleaning,
surface treatment, and rinsing
1. Mechanical Preparation
Mechanical preparations include polishing, buffing, and some variations

2. Solvent Degreasing
Contaminants consist of oils and grease of various types, waxes, and miscellaneous
organic materials. These contaminants can be removed by appropriate organic solvents,
either by dipping the workpieces in the solvent or by vapor decreasing.

3. Alkaline Cleaning
Workpieces are immersed in tanks of hot alkaline cleaning solutions to remove dirt and
solid soil. A special type of alkaline cleaning is electrocleaning.

4. Acid Cleaning
Acid cleaning can move heavy scale, heat-treat scale, oxide, and the like. The most
commonly used acids include sulfuric and hydrochloric. Pickling can also be combined with
current to be more effective.
 The anode and cathode are both connected to an
external supply of direct current. The anode is
connected to the positive terminal of the supply, and
the cathode (article to be plated) is connected to the
negative terminal

When the external power supply is switched on, the

metal at the anode is oxidized from the zero valence
state to form cations with a positive charge.

These cations associate with the anions in the solution.

The cations are reduced at the cathode to deposit in the
metallic, zero valence state
Perbedaan dasar
dimensi logam hasil
anodizing dan
elektroplating
adalah :

Lapisan anodizing
terbentuk dari substrat
logam itu sendiri,
sedangkan lapisan
elektroplating
merupakan deposit
logam lain yang
menempel pada
substrat.
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