ALUMINIUM

How can I find aluminium? I find it in nature very easily, in bauxites minerals. It’s very a cheap material.
The aluminium alloys are very interesting in mechanical design world for three reason:
1. Very low specific weight (2,7kg/dm3 vs 7,9 kg/dm3 of the steel);
2. Electrical resistivity;
3. Very low melting temperature (600°C; it’s easy to cast; less is the energy less will be the cost).
The first and the third ones are very important for automotive applications.
It has a very low specific weight because it has a very small atomic number (smaller than aluminium there
are only lithium and magnesium).
It is ductile, malleable and has, as said before, a low melting point: for these three reasons he has a high
workability. Often, it is worked in cold process like cold rolling and cold extrusion, but also low energy
casting processes (the first largest fraction of aluminium in automotive application) are used to give to the
aluminium alloys the desired shape. Obviously, each process is optimized for a precise typology of products.
The heat treatments can give to alloys high mechanical properties.
Last, aluminium has a very good corrosion resistance obtained with passivation, that create a thin oxide layer
(10nm) on the material surface that protect the material below by the corrosive agents in the atmosphere. The
passivation is a natural process that occurs without treatment, but spontaneously as the material go in contact
with the air for the first time. If I want to increase the thickness of this layer, I use an anodizing process, an
electrochemically process, that also give a different hexagonal structure.
In automotive world, aluminium alloys are widely used for frame and body. The change from steel to
aluminium is made to reduce the weight of the car; other automotive components realized using aluminium
alloys are the engine heads and blocks and the wheels. The prospective is to realise the most possible
percentage of the chassis with aluminium. It’s important to underline that we, engineers, pay the aluminium
advantages with a cost growth. Not as the carbon-fibre using, but anyway there is a growth. We just knew that
high strength steel alloy have better mechanical properties than aluminium ones; in particular, if we put in the
same graphical space the stress-strain curve of HSS and
Aluminium we can see that steels are very more
performant than Aluminium alloys (steel YS is double
than aluminium best ones) but if we change the ordinate
axis name as we can see in the image, all curve change a
lot and aluminium 7075-T6 became the most performant
metal alloy, for the ratio stress/density parameter. We
can also see the big stress range where the aluminium
alloy can work and it is very big.

Designation of aluminium alloy

The first division is: wrought alloy (cold working) and
casting alloys (moulds and die). The standard used in the
world are a lot but the most important are the American ones (ANSI), the international organisation of
standardization (ISO) and the Comité Européen de Normalisation (CEN).

We start from the last, the European one. WROUGHT ALLOY. The designation is composed by the
following elements, in succession: the prefix EN (to indicate the “standard” used), the letter A (to indicate
the word Aluminium), the letter W (to indicate the words “wrought alloy”), a short dash - , and for last a
code of four digits, also known as “grade” (related to the chemical composition of the alloy).
Examples: EN AW-5052 or EN AW-5154
Now we analyse the grade: the first number of the grade refers to the main alloying elements; in the table
there is the link between number and elements.
Strain-hardening alloys Age-hardening alloys
1 3 4 5 2 6 7
Pure Manganese Silicon Magnesium Copper Magnesium- Zinc
aluminium (Mn) (Si) (Mg) (Cu) Silicon (Zn)
(Al) – no (Mg2-Si)
elements
intentionally
added
Sheets, plates, Plates, Welding plates Plates, Extruded Plates, bars,
tablet blisters food trays wires bars products extruded
products
Work- Work- Work- Work- TT TT TT
hardening hardening hardening hardening

Note: The grey background columns indicate the most important Aluminium alloys for mechanical
application. The red-head columns indicate the Aluminium types used for automotive applications. It’s also
important to underline that all Aluminium alloys can be reinforced with strain or work hardening, but only the
indicated alloys can be reinforced also with thermal treatment.
Other precisions about other Aluminium alloy families.
For 1xxx alloys: the last two number indicate the percentage of Aluminium exceeding 99%; it is an indicator
of purity; it’s important because of the electrical application of this Aluminium family: the more is the purity
the bigger are the properties; in particular the more is the purity the more is the Aluminium conductivity.
Example: 1050 indicates an Al percentage of 99,50.
For all other alloys, the last two number are a progressive number that indicated a specific alloy. It hasn’t a
physic meaning.
For the post-treatment, we must indicate it with a letter. The heat treatment designation system of EN 515 is
used for all forms of wrought aluminium and aluminium alloys. Property (mechanical and physical) limits
apply to individual alloy-temper-product combination.
• Basic temper designations consist of letters (F, O, H, W, T);
• One or more digits following the letter, where required, indicate sub-division of the basic tempers.
These designate specific sequences of basic treatments.
• Additional digits are added to the designation, if some variation of the same sequence of basic
thermo-mechanical operations should be applied to the same alloy, resulting in substantially
different characteristics.
I’ll explain what each letter means.
• F temper – as fabricated, no mechanical property limits specified;
• O temper – annealed, to obtain the lowest strength temper;
• H temper – strain-hardened, cold worked after annealing (or after hot forming) or in combination with
partial annealing or stabilizing;
• W temper – solution heat treated, unstable temper, only with indication of ageing time at RT: e.g. W
1/2 h;
• T temper – thermally treated to produce stable tempers more than F, O or H, solutions; heat treated
and aged at room or intermediate temperatures with or without supplementary strain-hardening.
The yellow background letters are the most important for us. Below, there are more explanations about H
temper.

Below, there are more explanations about T temper.

There is ANOTHER KIND OF DESIGNATION, the chemical one. The designation is composed by a
sequence of chemical symbol and numbers:
• For unalloyed aluminium: Al symbol followed by purity percentage (in weight); Al 99,7 or Al 99,98
or EAl 99,7 (the last example is used to indicate alloy for electrical application);
• For alloyed aluminium: Al symbol followed by all alloying elements (symbols, max 4, in order of
decreasing amount) and relative percentage (weight, mean value, rounded to the nearest 0,5 or, for
percentage lower than 1%, to the nearest 0,1);

Now, we present the European standard about CASTING ALLOYS.

The designation is composed by the following elements, in succession: the prefix EN to indicate the “standard”
used; the letter A to indicate “aluminium” word; the letter B, C or M to indicate the shape if it was Billet, Cast
or Master; a short dash - ; a code of five digits related to the chemical composition of the alloy. Examples:
EN AC-21000 or EN AC-41000. The first number of the code indicates the same number (and so the same
element) of the wrought alloys standard coding system. The second number in the code indicates the other
elements present in the alloy. After the number code, there is letters, that indicate the casting process. The
used letters are: D (Die casting), K (chill or permanent mould casting), L (investment casting) and S (sand
casting). Example: EN AC-42000K.
Also for casting alloy, I can use a chemical designation; Al followed by a space; Symbol of the major alloying
element usually followed by the weight percentage; other alloying elements (max. 4 elements) in decreasing
order; if the mass fractions are the same, in alphabetical order.
The AMERICAN STANDARD CODE SYSTEM is very similar for wrought alloys but is very different for
casting alloys. We have no more 5 digits but only 4 digits with a point to separate the last from the first three.
Heat treatment for WROUGHT Aluminium alloy
As we said before, to increase the Aluminium alloys mechanical properties we can choose between two ways:
work-hardening (for all alloys family) or heat/thermal treatment (only for 2000, 6000 and 7000 families). This
way is particularly interesting for automotive applications because can increase a lot the mechanical
properties, a lot more than work-hardening. Now we let to study them.
Only three Aluminium families can receive a heat treatment and we must search the reason in the phase
diagram of each alloy; if the alloyed elements have a too much low solubility at hight temperature or have a
low solubility variation during the cooling, we can’t realize an heat treatment because in the first case it’s
forbidden the possibility to realize a solution at high temperature while, in the second one, we have a constraint
for the formation of the alloy that is the almost exact alloyed elements percentage to respect to obtain the
desired solid solution at room temperature (we can see this problem during quenching). So, only the alloys
belonging to those three families have feature, visible in the phase diagrams, that permits heat treatment.
An HT is usually divided in three moments and process: the solution heat treatment (bringing the solution
over the solvus temperature) than there is the quenching (a very rapid cooling phase) and, last, the ageing (a
re-heating at a temperature much below the solvus one).
In the alongside image, we can see the microstructural changing during a
heat treatment; we can see how the α phase, starting as solid solution, after the
quenching, became a super-saturate solution; after the ageing process,
the alloyed elements go outside the solution and became precipitates visible as
θ phase.
The ageing starts always from a super-saturated solution (that is
thermodynamically unstable) and then the nucleation develops itself, in a first
moment, in the Guinier Preston zones (where there is a small strain in the
structure and this last prevents the possibility of movement of the
dislocations) and then in three consecutive steps: the coherent, semi- coherent
and, final, incoherent precipitation, related to the matrix. It depends how the
alloyed elements nucleating crystals match the matrix lattice. During ageing
these four steps are consecutive, so at the end of ageing we will have an
incoherent precipitate, visible also in the alongside image.
All depends by the relative strain ε (mismatch): if it remains smaller than 1% we will have a coherent interface
while if it is between 1% and 25% we will have semi-coherent interface; last, if it is bigger than 25% (usually
it is 50%) we will have an incoherent interface.

|𝑎𝛼 − 𝑎𝛽 |
𝜀=
𝑎𝛼
Where “a” is the distance between two unstressed planes and α and β indicate each phase.
A coherent interface arises when two crystals match perfectly at interface plane so that the two lattices are
continuous across the interface. This can be achieved if, disregarding chemical species, the interfacial plane
has the same atomic configuration (orientation, interplane distance) in both phases and this requires the two
crystals to be oriented to each other in a special way. An example: in Cu-Si alloy, a coherent interface ca be
formed between the hexagonal close-packed Si-rich k-phase and the Cu-rich a-matrix. The lattice parameters
of these two phases are such that the two planes are identical. So, the two crystals can join along the interface
planes and the resultant interface is completely coherent.
Sometimes happens that the strain associated with a coherent interface raise the total energy of the system,
and for sufficiently large atomic misfit, or interfacial area, it becomes energetically more favourable replacing
the coherent interface with a semi-coherent interface in which the strained link is taken up by a misfit
dislocation. So, we can see with evidence the two different lattice structures.
When the interface plane has a very different atomic configuration in the two adjacent phases, there is no
possibility of good matching across the interface. The pattern of atoms may either be very different in the two
phases or, if it is similar, the interatomic distances may differ by more than 25%. In both cases the interface
is defined as incoherent and we will see an interphase boundary.
In the 2000, 6000 and 7000 families the phase could be different each other but all present a “step-
evolution” process.
In the image below, we can see for a given alloy the TTT curves that allow to evaluate which phase will be
predominant after a selected ageing treatment, in particular which phase state (coherent, semi-coherent or
incoherent) we will obtain after a given treatment time.
Following the red line, I can see that after five hours
treatment at 130°C, I’ll obtain the first step structure, the
coherent one. I also can see that to obtain the incoherent
precipitation, I must wait more than one year and I must
increase the temperature, because remaining at 130°C the
limit step will be the semi-coherent, after almost 1 year
treatment!!!! Those are huge time.
So, we can say that after the ageing process the material is
in the second step, called “Second phase nucleated on GP
zones, coherent with matrix”.

But why is this structure so important for Aluminium

alloy mechanical properties?
It’s all related to the difficulty for the dislocation to move
inside the lattice.
When I have coherent
precipitate, the
dislocation moves
through the strained
region while if I have
an incoherent
precipitate the
dislocation can’t go
inside the region but
it can only move
outside them. I obtain a reinforcement in both case but the rise of
energy is bigger in case of coherent precipitates (or semi-coherent
ones) instead incoherent ones. For example, for the 6061 alloy we
obtain the peak of strength at a partially coherent second phase, as we can see in the plot alongside. The choice
of the correct ageing time is fundamental, but it depends by the temperature. If I’m searching the highest peak
I must choice an ageing time very long at relatively small temperature; if I want reduce the time, to make the
process faster, I have to increase the temperature; in this last way I’ll obtain a strength peak a bit smaller than
in the first case but also I can complete the process in a reasonable time.

The natural ageing isn’t so performant, it happens in a very long time, more than 15 years!!!

The typologies of HT are 10, indicated in the designation of wrought aluminium alloys as T1, T2, …T10. The
most important for us are the T3 (solution heat treated, cold worked and naturally aged to a substantially stable
condition, very common for 2000 alloys) and T6 (solution heat treatment and artificially aged, very useful for
6000 alloys). In general, heat treatment improves the mechanical properties but after that the alloy chemical
properties are weaker and the alloy suffers more the corrosive attach by the chemical agent.
Now we’re going to see what’s happen near to grain boundaries after ageing. From the image, we can see that
at the boundary line there is a strong nucleation of precipitates, it’s very easy for them to precipitates here.
This precipitation is very easy to see at microscope and it make possible recognize the grain boundaries. But
we also can see that between the grain boundary and the big region rich of precipitate, there is another one,
called PFZ, like Precipitate Free Zone, where there are no precipitates; it’s very clear and evident!! Why there
is this so evident differences between the two phases region and pure Aluminium region? It’s caused by the
fact that near the grain boundaries all the vacation of the lattice and all the solute presents are concentrate
exactly in the grain boundary to create them (the vacation create the space and the division that is partially fill
by the solute precipitates (creating the visible black line at grain boundary). It’s impossible to create
precipitates in PFZ due to the very small quantities of solute and vacations, moved to the grain boundary.
These zones are very important because the dimensions of these regions strongly influence the alloy corrosion
resistance.

Why the PFZ reduces the alloy corrosion resistance? We must to keep in mind that the pure metal have better
corrosion resistance than a two phase one; for example 1000 family Aluminium is chemically stronger than a
6000 or 7000 ones; this is due to the PFZ presence at the grain boundary that start a Galvanic effect between
the two precipitates region and the thin pure Aluminium region; the Galvanic effect produce the oxidation of
the pure Aluminium region and the reduction of the two phase region; so, the pure Aluminium region,
subjected to an oxidation process, is the weakest region in the material. It’s fundamental that this region is
narrow, small and thin as possible; smaller the dimension of this region smaller will be the corrosion process.

My main objective now is reducing the PFZ, to reduce the weak spot of the material. I have two ways: the
first one is increasing the number of vacations in the whole alloy; the technical strategies are cold working
treatments. In this way, the number of vacations increase also in the ex-PFZ so it became smaller and thinner.
The second strategy is lowering the ageing temperature, in way to reduce the vacancy concentration and so
on the PFZ extension can be reduce; this is explainable with the enhancing of Guinier Preston zones.
 Now, I’m going to show how do the properties change
for each Aluminium alloy families.
In this first graph we can see that the HT and the noble
metals (like Cu, Si, Zn) presence in 2000, 6000 and
7000 increase a lot the tensile strength, the hardness
and the impact sensitivity while the ductility drastically
decreases, as it was easy to imagine.

In second diaphragm, we can see how Young’s module

and the density aren’t so depending by the heat treatment
and chemical composition; the only exception is for the
6000 alloy family where the introducing of Lithium in
the alloy reduce the density, making the alloy lighter,
and at the same time increasing the Young’s module.

In this third one, the anodising property is almost the

same for all the alloy excepting for the heat treated; for
they, this property isn’t so good and it’s the worst for
2000 and 7000 family with Cu. The weldability is
influenced by the Cu presence, too.

The fatigue strength increases as also the hardness

increases; they are strongly linked. About corrosion
resistance, if we think to the consideration and reasoning
made before, it’s clear that the best property is for pure
Aluminium while the 2000 and 7000 families (with Cu)
have the worst resistance because of the Galvanic effect
that, in this alloys, is very strong.
Which are the differences in our interested alloy
families?
The 6000 family has the highest property of elongation and it’s not so bad for the UTS; the 7000 family is the
strongest, with the highest values of UTS while the elongation isn’t so good. The 2000 family is in the middle
with good values in both properties. The 6000 family is the most used in automotive applications because is
the best compromise also considering the corrosion resistance, the cost, the weldability and the density; the
other two families are selected only for very particular application where it’s better have the excellent property
in one field (because it’s necessary) losing property in all the other fields.

Now, we’re going to see each alloy family features.

2000 family
As said before, this alloy family is subjected to heat treatment. The mechanical properties are similar to a low-
carbon steel (thanks to the ageing process after the heat treatment) and it is subjected to an intergranular
corrosion (due to the Galvanic effect along the grain boundaries, enhanced by the presence of Cu); the most
famous alloys are the 2024 T3 and the 2099; this last is very important in automotive world for his lightness,
thanks to the Lithium presence. The 2024 is the Aluminium alloy of the, so called, Alclad, a particular
sandwiches composite structure. The 2024-T4 alloy is the main material and there is on his surfaces a thin
pure Aluminium layer; the objective is to protect the main material with a high corrosion resistance another
one.

7000 family
As said before, this alloy family is subjected to heat treatment. Generally, the mechanical properties are higher
than 2000 family and this is due to the dispersoids presence. The dispersoids are finely divided particles of
one substance mixed in another. These dispersoids are mixed and dispersed in the matrix lattice but they form
also intermetallic with Aluminium and intermetallics are compounds made up of two or more elements,
producing a new phase with its own composition, crystal structure and properties. They are usually hard and
brittle. Their secret is that they precipitate at grain boundaries, enhancing the grain stability and preventing
the grain coarsening. Their problems are the low fatigue resistance and low corrosion resistance (stress
corrosion cracking, it starts from grain boundaries and go on with crack along them). The most famous and
used alloy is the 7075 (called as Ergal), now substituted for 7055. It was selected for the possibility to have
better corrosion and fatigue resistance than the other 7000 alloys; in the image below, we can see that there
are several heat treatment that can reduce the strength to increase the corrosion resistance.

The corrosion resistance of alloy 7075 has been thoroughly studied (atmospheric corrosion, SCC, exfoliation)

for all available tempers. Corrosion resistance increases raising the aging time (T7). Usually T76 is
recommended for resistance to exfoliation while T73 for SSC strength. From the TEM micrograph we can see
very well the secondary phase precipitated and very well mixed in the Aluminium structure; this is the cause
of the good mechanical properties. We can also see the grain boundary, the precipitation along them, the PFZ
around the precipitation.

The 7055 today substitutes the 7075: the 7055 is stronger than the 7075, so we can use a smaller cross section
and in this way the whole structure is lighter (thanks to the increased concentration of Zi in the alloy and a
small increase of Cu) and has a much better corrosion resistance, also to the exfoliation process.

The Aluminium alloys most used in automotive world are the Al-Li and the Al-Sc; they have very high
mechanical properties, corrosion resistance and the cost.

The automotive most used Aluminium alloys belong to the 6000 family. They are characterised by low density,
good workability, strength, and corrosion resistance and they correspond well to demands for the materials
for bodies of cars and other road vehicles. These properties also fit to ever stricter environmental regulations
regarding pollution and simple and cheap recycling.
As just said, the Aluminium most important advantages in car world is the reduction of weight, and thus
reduces environmental problems related to the consumption of fuel. Ten percent lighter vehicle saves 5% of
fuel. Weight reduction of only 1 kg reduces CO2 emission for 20 kg for 170 000 passed kilometres.

Al-Li alloy
The presence of the Lithium is crucial because it can strongly reduce the alloy weight. An Al-Li alloy have,
as average, from 8 to 10% lower density than other Al alloys. They also have an increased Young’s module
and a higher stress/density ratio. The Lithium is very performant from this point of view (for only 1% more
Li in the alloy, we’ll have 3% less density and 6% more Young’s module). The problems are the low ductility
and toughness and the cost that’s very high: almost 2-3 times more than 7055. But an alloy with only Lithium,
as alloyed elements, is useless because, during the heat treatment, Al-Li precipitates make mechanical
properties like fatigue and toughness worse. So, in this alloy there are always other alloyed elements like Cu,
Mg, Zr. Other problems are the segregation of the Lithium during casting because of its very low density, it
isn’t easy to handle it because it oxidizes very fast. Last, it is subjected to fractures at the grain boundaries,
due to the low toughness.
Many treatments are used to improve the mechanical properties, in particular the precipitation hardening; to
eliminate PFZ and precipitates at grain boundary, a slight plastic deformation (2-6%) is applied after
quenching to create dislocation that enhance the formation of precipitates during the aging treatment. A
particular treatment is the T8 (solution heat treatment, cold worked and artificially aged).

The 2099 is one of the most interesting for automotive application because can reach the same mechanical
properties of 7050 and 7075 alloys with also a higher Young’s module and very lower density. The fatigue
stress is almost the same. It’s usually used in helicopter, airplane and supercars.

Al-Sc alloy
The Scandium is a very expensive elements; fortunately, it’s necessary a very small quantity of Scandium to
improve a lot the alloy mechanical properties. The reason is linked to the formation of dispersoids (a very
small and coherent with matrix secondary phase) that produces lattice strain; impeding the motion of grain
boundaries, it can strongly increase strength (1) and keep small the grain size (2) and it also increases a lot
the recrystallization temperature. Going deeper, the Al3Sc dispersoids are a phase which is coherent with the
Aluminium matrix. An extremely high coherency mismatch is observed for the Al3Sc phase, resulting in
significant lattice strain to block dislocation motion and to impede grain growth. This mismatch is 1.2%

compared with 0.8% for Al3Zr, one of the next most powerful dispersoids. It’s the highest mismatch as
possible for a fully coherent double-phase.
From the image above, we can note how the Scandium addition improve all Aluminium alloys seen before
strength. It’s very powerful. Other two advantages are: 1) the improved resistance to hot cracking, that
produce a good weldability and the elimination of possible cracks between the welded material and the base,
and 2) a higher temperature for ageing than the common alloys one.
As said before, the Scandium is very expensive: Al-2%Sc alloys can be bought at a price in the order of 50
USD/kg!!!!! Also, in Scandium alloy case, it isn’t the only alloyed element present in the alloy: there are also
Mg, Zn, Li, Cu.

CASTING Aluminium alloys

Why do we cast Aluminium?
Because it’s a simple, inexpensive and versatile way of forming Aluminium into a wide array of product. For
this reason, the cast products make up more than half of the whole Aluminium used in the cars (for engine
components, block, pistons, transmission housing…). The Aluminium has low melting temperature, low
solubility of gases (except H2, the low solubility is good because the gas present create porosity), good fluidity
and surface finishes (in some cases, following machining process aren’t necessary).
The bad feature is the high solidification shrinkage.
To control these properties, we can act to impurity level, grain size, solidification rate (with this we can
change microstructure and grain size) and melting and pouring practices.

We have a lot of manufacturing processes to cast the Aluminium; we can divide them in two big groups:
1) Sand casting;
 2) Die casting (d.c.);
1)gravity casting;
2)high pressure d.c.;
3)low pressure d.c.;
4)vacuum d.c.;
5)squeeze d.c.;

The choice between all this strategies is made considering as main parameter the castability; it depends by
alloyed metals (Si, Cu, Mg, Zn) that influence properties like fluidity and susceptibility to hot-cracking, that
are all linked to castability. The Al-Si (300.0 and 400.0) is the most important group and the best for casting:
it constitutes the 85-90% of the total Aluminium casting. They make a eutectoid composition, for 11,7%w
Si, where the alloy melts at lower temperature then all other percentage.
At this crucial point, the solidification process starts for both components and creates the microstructure in
the image: a mix of Al and Si lamellae, very thin and sharp (it requires modifications, the product is very

brittle). If I use a hypo-eutectic Al-Si, the Al starts the solidification for first and form large grains and in
“empty” spaces between them there are the Si lamellae; if I use a hyper-eutectic Al-Si, the process is reversed
and at the end I obtain not only lamellae but also Si grains (mixed in the eutectic microstructure). Generally,
the casting Aluminium alloy have eutectic composition or hypo one; the hyper one is rare (too much brittle
and difficult to machine working).
The pure Al-Si alloy have also good weldability and a low solidification shrinkage than the casting alloys
without Si.
To avoid the lamellae microstructure, I put, in the alloy, elements like Sr and Na, that change the lamellar
microstructure; in particular, if Sr added is more than 0,02%w, the microstructure is completely changed into
fibrous one, that is less brittle. This change also produces the improvement of tensile strength, elongation,
hardness and fracture toughness. We can also add a lot of fluxes, solid components, to modify melt and
microstructure properties. Some examples are the cover fluxes, the cleaning fluxes and the Silicon modifiers
(based on Na).
We are going to watch it in detail:
1) the cover ones are applied on the surface of molten Aluminium where it melts, forming a continuous
layer protecting the liquid metal from oxidation and absorption of atmospheric hydrogen.
2) the cleaning ones remove oxides suspended in the melt.
3) The Si modifiers, based on Na, act on the nucleation and growth of the eutectic Si grains/lamellae
during solidification. The Na segregates at periphery of Si plates, blocking them, and prevents its
growing. They produce a more fibrous structure. But we must pay attention to P effect: it produces a
huge growing of Si particles, giving poor mechanical properties to the final product.
It is a, so called, over-modification. It occurs when Na is more than 0,018-0,02%; in this situation, it is
rejected in front of the solidifying interface and forms Al-Si-Na which serves as nucleation sites for coarse Si
particles, bad thing! Sr excess, also, causes over modification.

The impurities present in the melt are:

1) P, it makes modifications more difficult;
2) Mg, it makes modifications easier.

The freezing rate is positive for the modification process.

The Si role: as higher is the amount of Si as higher is the amount of modifier that are needed to obtain complete
modifications.
The most important Aluminium alloys are four:
1) Al-Si-Cu; more Si for pressure die casting, less Si and more Cu for sand and permanent mould casting;
the Cu increases strength and machinability, reduces castability, ductility and corrosion resistance; it’s
largely used for engine cylinder blocks and heads (replacing cast irons);
2) Al-Cu; precipitation hardening and dispersion one by intermetallic compounds increase strength and
hardness; the strength is higher than other casting Al alloys and it’s comparable to wrought alloy; it’s
largely used in high temperature applications (but not used a lot in automotive ones).
3) Al-Mg; Mg content between 4%w and 10%w, it has oxidation problem, they are less preferable than
Al-Si; the most of them are sand casted;
4) Al-Zn-Mg; very good alloy; high corrosion resistance, good weldability, attractive anodised surface;
some applications are the chemical and sewage and the kitchen utensils; the binary Al-Zn, today, is
used only for sacrificial anode for steel structure protection. It’s sand casted because the permanent
mould tends to cause hot-cracking. It’s not suitable for high temperature applications due to the rapid
softening.

Anodizing
The principle anodizing aim is the increasing of thickness of oxide layer on the surface of Aluminium
component. The layer acts like a barrier protecting the material from the contact with oxidating agents; it can
be divided in two parts: the barrier layer (compact, thick few nanometres) and porous layer (with a lot of
vertical pores, 10-100 nanometre diameters). There isn’t interface between them; the passage from one to the
other is continuous.
((The passivation is the natural process that bring to the formation of a very thin layer (2-5 mm) at the room
temperature on the pure Aluminium surface; it happens in a very fast way when pure Al get in contact with
oxygen in the air; it’s fast and thin because it ends when there is no more Al with the possibility to get in
contact with oxygen; with anodizing we want increase the thickness realised spontaneously)).
If I stop downloading process after 1-15μm, I’ll call it “Decorative anodizing process”, while if I stop it
between 30-100 μm, I’ll call it “Hard anodizing”.

But why do I need to increase the thickness? I have two reason:

1) In the Decorative anodizing case, I realised it to improve a bit the corrosion resistance (the new one
is stronger than the natural one) and to obtain aesthetic properties (coloration and pigmentation). I
can colour the material without painting but filling up the pores; in this way I’ll obtain an external
surface with improved scratch resistance in relation to the painted layer (that’s very easy to scratch).
2) In Hard anodizing, I'll obtain high hardness, high wear resistance, the process improves the
resistance of the layer, it becomes stronger. In this one, I can fill up the pores with some substance
with a function, for example a solid lubricant to reduce the friction.
In both cases, the process is not so expensive, it's possible to use it to correct the dimensional errors
(tolerance); it has a very good adhesion to the surface, because it grows up directly from the surface.

Negative elements (drawback) that anodizing process produces: worsening fatigue resistance (due to residual
stresses on materials); the process is very difficult to handle for high strength Aluminium alloys; low resistance
to thermal shocks (the thermal expansion coefficient of pure Aluminium is much higher than the oxide one);
furthermore, the oxide is going to be solubilize if it goes in contact with a high pH solution, for this reason an
anodized material has a low resistance to alkali (pH>10).

Now, we are going to understand why I need to improve corrosion and wear resistance.
Corrosion: in the high strength Aluminium alloys, there are a lot of PFZ subjected to strong Galvanic effect;
increasing the thickness, I protect this zone, covering them; it’s isn’t easy to obtain this protection and it hasn’t
sure advantages: but it’s better than nothing.
Wear: light strength Aluminium alloys have very low hardness, with anodizing I’ll make the surface stronger,
increasing hardness.
Now, we are going to analyse the anodizing process: it’s an ELECTRO-CHEMICAL process.
1) The name “Anodizing” means that, during the process our component take the “anode role”;
2) “Electro” means that we can control it with a Galvanostatic or Potentio-static controller;
“Chemical” means that it happens chemical reaction and that an electrolyte (water solution) is needed;
I can have two possible scenarios: a solution with neutral pH or with acid pH;
1) Neutral pH is interesting for electronical applications, not for mechanical ones;
2) Acid pH, I obtain both barrier layer and porous layer; the final thickness is high (max 100
μm); it’s used for mechanical applications.
In an acid pH solution, what do I mix with the water? How the solution could be composed?
1) Sulphuric Acid;
a. It’s the most common;
b. The product has a high wear resistance;
c. It's very easy to post treat them;
d. For automotive industry.
2) Chromic Acid;
a. the oxide product is soft and ductile;
b. The product has high corrosion resistance;
c. It's useful in frequent thermal changing application;
d. it's dangerous for natural element;
e. it's used in aircraft application, for automotive only in the past.
3) Phosphoric Acid;
a. the nanopores at the end are bigger;
b. usually it's a strategy used as pre-treatment for painting and lacquering
The formation of the oxide layer happens follow this overall reaction: 2Al + 3H2O = Al2O3 + 3H2
At the interface between oxide layer and Aluminium material, two mechanism happen:
2Al = 2Al3+ + 6e-
2Al3+ + 3O2- = Al2O3 + 6e-
It’s important to remember that the process become more and more difficult as the thick improve his
dimensions, due to the bigger path that the aluminium atoms must make to arrive to the oxide surface.
Difficult means more energy used and more time necessary.
We’re going to watch the pores layer structure; the overall structure is a hexagonal lattice due to compactness
reason: the pores start to generate in random places but, then, there is a re-organisation of each position in
way to obtain the most compact structure. This one is the hexagonal disposition. The pores are created by a
dissolution process between the acid and the oxide; it starts where there are micro-fractures because here there
is a concentration of electric field and, so, in that point it will be concentrated the dissolution process; in the
other region the anodizing process still going on and still “adding” oxide material, around the starting pores.
From the image, we can see a section of oxidated Aluminium; some part of the oxide derives from converted
Al, replacing its thickness, and then, above it, the “extra” oxide material expands the thickness. It's common
to use the equation Vox/Vmet to evaluate how much deep the oxide is gone inside the Aluminium original
material, but we have to distinguish the theoretical one from the real one: in the first case, we don't consider
the presence of the pore while, in the second one, we do it; if we have a ratio equal to 1,6 means that the pores
are not so big while if we have a ration equal to 2,0 means that pores are bigger. It's important to keep in mind
that the thickness grows only for a half of the value of the equation (50 μm of oxide means 25μm of expanded
thickness because the other 25μm are gone inside the original material).
The main problems that an anodized surface can have are four: the secondary phase inclusions, the conical
asperities, the crazing phenomenon, the very sharp geometry.
Starting from the first, it occurs when we want to oxidize an Aluminium material with a secondary phase (f.e.
Si plates) like the casting alloys and aged alloys; the anodizing process produce an oxide layer with different
thickness and the Si lamellae inclusions are present in the layer thickness. These inclusions make the layer
MORE BRITTLE. In general, the second phase presence produces problems because it has: different
oxidation susceptibility (some elements are easier or harder to be oxidize than Aluminium so the process
starts before/after it; in the first case, the second phase oxide has different properties respect to Aluminium
one; in the second possibility, the second phase nucleation remains purely inside the oxide layer); different
electrical conductivity (electric field concentration of precipitates); different property of their oxide respect
to Aluminium oxide (in particular, different molar volume and generation of residual stress and crack).
The different electrical field concentration of precipitates brings to the conical asperity problem; the dual
phase particles increase the local electric field while in the nearest regions the electric field is reduced; but in
more distant region the electric field remains constant; so, the oxidation process happens with less intensity in
these nearer regions than in secondary phase and
farer regions; this brings to the formation of conical
asperities, or, if the process go much deep inside
the Aluminium, also it brings to the separation of
the second phase particles that will completely
immersed in the oxide creating an inclusion, a
damage for the oxide, that reduce the mechanical
properties. The mechanism is showed in the image
alongside.
The crazing phenomenon is due to thermal shock;
the strong and compact oxide layer (produced with hard anodizing) can break with small internal cracks. The
process to close the pores (hot sealing), after anodizing, is made after filling up the pores with colourant or
lubricants. It's very simple: I put the material inside hot water (very near to 100°C). But the anodizing was
performed at very low temperature. So, here we have the thermal stress that brings to crack.
In case of very sharp geometric parts, like screw, the oxide formation couldn’t cover the top of the sharp
geometry, leaving a small region uncovered.

CORROSION BASICS
Here we see in detail each mechanism of corrosion. The chapter is divided in two parts: corrosion mechanism
and protection system. The all type of corrosion mechanism we’re going to see are: wet corrosion, Galvanic
effect, Pitting, Crevice corrosion, SCC for steels and Aluminium. The two type of protection system are:
coatings or corrosion inhibitors.

Corrosion mechanism

Wet corrosion
Water, atmospheric condition, small quantity of moisture is sufficient to give the start to the corrosive process.
The simplest example of which kind of process occurs in a corrosion mechanism is the electrochemical
generator; to realize it I need:
1) the Anode, it lives the oxidation reaction; it’s put inside a water solution;
2) the Cathode, it lives the reduction reaction; it’s put inside a water solution;
3) the Electric contact, the cable;
4) the Ion exchange, the salt bridge;
In the liquid solution, there are ions of their relative solid elements; the electrons move from the anode to the
cathode through the wire; the element ions move from the solid material (producing its consumption) to the
solution for the anode, while the reverse process happens for the cathode (a consumption of positive ions
located in the liquid solution). The excess of positive at one side and the leakage at the other one is balanced
by a salt bridge that permits the passage of ions without the mixing of the solution (it’s like an ion conductor).
A system built as in the image can go on until the solid anode is finished. The voltmeter along the wire
measures the potential energy between the two parts; each reaction has a standard potential measurable in
normalized condition (a single metal in contact only with water). The reference is the reduction of Hydrogen:
a positive potential means that the reaction happens in the reduction direction, while if it is negative, it
means that the reduction isn’t spontaneous but needs energy to happens; so, the spontaneous one is the
reverse. So, if I put in contact two elements with semi-reaction with different sign, they start a reaction
(spontaneous for both) where one element will be spontaneously the cathode and the other one the anode (it’s
Cu-Zn case). From that table, we also can see that the most used metallic material for mechanical and
automotive applications (Fe, Zn, Al) have a positive potential reaction for the oxidation reaction; it means that
in a simple wet environment, they can be corroded by the spontaneous oxidation reaction with the hydrogen.
The Cu, for example, has oxidation reaction potential lower than the hydrogen one (the reduction reaction
potential is higher than 0) and so the Cu can't be corroded by hydrogen in wet environment. Cu can be, instead,
corroded by oxygen that has a higher standard reaction potential (the oxidation gives to Cu the typical green
colour, like in the dome). The Cu is very useful applied in all close system here there is a very small amount
(or null) of oxygen. Gold (Au) has a very high corrosion resistance against both oxygen and hydrogen reaction.
Resuming:
For a wet corrosion, I need an electrochemical system, made by four things:
1) anode oxidation, it removes material from the solid metals, it produces positive metallic ions and free
electrons;
2) cathode reduction, it consumes positive ions from the water solution and free electrons; it produces
solid metal on metal surface;
3) electric contact, to give to the electrons the possibility of motion from anode to cathode;
4) Ion exchange, there is the necessity of a salt bridge, to give to the positive ions the possibility to move
where there is a their low concentration, in a negative environment; Is there isn’t the salt bridge but
only a water bridge, the positive ions don’t have the possibility to move. Sal bridge is like a conductor
for ions. Its correct name is electrolyte: moisture condense with dissolved salt (or even gases).

Galvanic effect
When two different conductive materials in electrical contact are exposed to an electrolyte, a current flow
between them: this current is called galvanic current. A 50mV potential difference between the two metals
is enough to trigger galvanic corrosion. To evaluate this potential, to know early if between two metals
galvanic effect can occur, I can start from the standard
potential table but it isn’t enough because those values
was obtained in a standard condition, very different
from the real condition (just only the spontaneous
passivation phenomenon change the standard potential
values; also the environment, where the metal is, affects REFERENCE ELECTRODE
the real metal potential, with changing also of 1V in
some case, like Aluminium). The new calculated
potential is called Galvanic potential and it’s evaluated SEA WATER
using the alongside device: the alloy is put inside a
solution that simulates the real working condition and INDUSTRIAL
I’m free to choose the best solution composition that is ATMOSPHERE
as nearest as possible to real working conditions (in the
image, there are two examples). There is also a reference electrode, based on Silver (Ag) and its chloride; we
know the standard potential of this electrode (referred to H one) so, measuring the potential difference with
the electrode, we can know the potential of our alloy, in operative conditions; also, referred to H one. As just
said, this potential takes the name of Galvanic potential (we must specify the composition of the environment
when use this value). If I want evaluate if the Galvanic corrosion starts between two metals, I simply put them
inside the liquid solution that I want and I must measure the potential with a Voltmeter: if the potential
difference is at least 50mV, Galvanic corrosion occurs.

Below, there is a table that put in

relation a lot of metals and alloys; it’s
sufficient to follow each line finding the
intersection between them. Here there
is a letter and reading the legend we can
understand if the two metals are
compatible in working condition or if
Galvanic corrosion occurs.
When Galvanic corrosion occurs, as we
can imagine, two reaction happen: the oxidation and the reduction. The
first one involved the anode (the metal with lower potential will oxide and
corrode), the second one doesn’t involve the cathode metal: it’s only the thing that make possible the
corrosion process and the place where a reduction reaction can occur but it doesn’t occurs on the cathode.
Who lives the reduction process? The hydrogen or the oxygen present in the wet environment.
An important role is played by the Electrolyte; if it is a good ions conductor (like in sea water) there is a
huge but homogeneous remotion of metal material from the anode while in electrolyte with low conductivity
(like the tap water) the corrosion process is very localized, so the total amount of material that is removed by
the process is much lower than in the sea water; but the real problem is that the mechanism can go very deep
inside the material (like a perforation). It’s more dangerous and a problem because from an external view the
material aspect is good but inside the corrosion mechanism is in an advanced state. This mechanism, in
automotive world, involve the fasteners (cerniere, chiusure, viti).
The luck is that Galvanic corrosion is easy to prevent with a sacrificial coating or with a conversion coating,
like black oxide and phosphate-base treatment (for details, see in the protection system chapter).
Special cases are the SS and the Titanium that have high potential; but in their case, this doesn’t mean high
corrosion rate because if they take the anode role a very fast passivation occurs, protecting themselves by the
corrosion. Another special case is very big surface dimension differences. If the anode is very smaller than
the cathode, the corrosion is very localised and very dangerous. In reverse case, the corrosion will be very
diffused (if the electrolyte is a good conductor) and easy to see and recognize. The last special case is that
some materials invert their polarity by varying the T°, like Zn and Fe; at room temperature the Zn protect the
Fe (being the anode) but over than 70°C the Zn will be the cathode and the Fe is the anode so the corrosion
involves the Fe.

Pitting
The starting point is the just known definition. But there are other two possible activations: 1) a localized
damage of the oxide film or 2) a localized damage (mechanical or chemical) of a noble metal protective coating
(when the coating material is more noble than the substrate, Cr/Au/Ni-Fe). The break becomes the anode (a
very small one) while all the remaining material is the cathode. So, the corrosion mechanism is very localized
and go deep inside the material; this is the also called second phase of the corrosion: after the activation there
is the propagation. The bigger protagonist of this mechanism is, once again, the Cl ions, because, as just
seen, the Al ions bond with them, instead of oxygen ones (so, no passivation). Without Cl ions the pitting
process doesn’t propagate. The pitting is very dangerous because it is very difficult to see. One allied against
pitting process is the Mo: it forms sulphur inclusions in the surface, stronger than the Mn ones, that are the
principle starter of the pitting process.

Crevice
A corrosion mechanism that, as just said before in the SS chapter, happens in a region protected by the
corrosive medium (that is the oxygen) by a body (called shield). So, the metal region where there is high
oxygen concentration is the cathode, while the region
where there is low oxygen concentration is the anode.
Another kind of “shield” is the water drop; the metal
point at the centre of the drop is the anode region while
the metal points at the drop circular boundary is the
cathode (this is explainable in terms of distance that
oxygen have to cover to arrive in contact with the
metals). At the boundary there is high oxygen
concentration while at centre there isn’t.
The most dangerous problem, it’s visible in sea water,
where the NaCl concentration is high. The lack of oxygen and the presence of Cl are very dangerous because
avoid the start of passivation process for SS, Aluminium and Zn; the crevice corrosion is most dangerous for
that metals. As we know, the passivation process produces spontaneously the oxide layer but, in this case, it
can’t happen because the Cl ions take the oxygen place in the bond with the Fe or the Al. So, the layer doesn’t
form and the material remains chemically weak.
Furthermore, also the Cu and Zn can make problems.
Typical crevice corrosion example: SS screw (see the difference with a
brass screw, where the corrosion take place outside the crevice), where
the big corrosion is localized in the place where oxygen can’t move. Other
kind of fasteners made by SS, Aluminium or Zn are affected by
crevice (in addition to galvanic effect). Often it can happen under paint;
crevices are formed between the paint and the metal and here the water
move producing the corrosion.

SCC
A particular crack system that follow the grain boundary lines to go inside the material. It can start by an
oxide damage, a pit, a crevice, an inclusion or a notch. The common denominator is the localized corrosion
of the oxide layer that is a stress concentration. The applied tensile stress concentrates here e propagates
the crack inside the material; if we stop the tensile stress the SCC ends. The new fresh metal is exposed to the
aggressive environment and the corrosion of all cracked region occurs and goes on, also if we stop the stress.
The SCC rarely occurs in pure metals; sometimes it depends on the presence of precipitates or intermetallic
compounds on the grain boundaries. The SCC are common for passive metal, because they are protected
only in the surface while inside material in chemically very weak.
As just said in the SS chapter, the SCC occurs in Austenitic SS, while doesn’t occur in Ferritic and Duplex
ones. Aluminium alloys are, also, susceptible to SCC: Aluminium alloys, infact, contain appreciable amounts
of soluble alloying elements, primarily copper, magnesium, silicon, and zinc, are susceptible to stress-
corrosion cracking (SCC); the most damaged are the 7079-T6, 7075-T6 and 2024-T3. The Aluminium alloys
problem is the very weak PFZ, chemically easy to attach (creating the starting point for the crack propagation).
Protection system
Coatings
They are classified depending on 1) the nature of the coating (metallic, organic, inorganic) and 2) the
technology used to realize the coating (mechanical, physical, chemical).
Before to apply any type of protective coating, the metal surface must be thoroughly cleaned in
order to remove organic (oils and fats) and inorganic (salts, rust, oxides, etc.) contaminants; moreover, usually
each type of coating requires an appropriate surface finishing to be applied. I have two way: degreasing
(organic solvents, alkaline degreasing (NaOH or NaHCO3), degreasing with surfactants) and finishing
(mechanical, thermal and chemical). To have a good adhesion, I want a high roughness. But that roughness
will be present on the coating surface, with a good adhesion. It isn’t a good result: I prefer a final coating
surface with very low roughness (and a very high roughness at the coating/steel interface. The final coating
roughness depends by the used technique.

Metallic coating
1) Cathodic: it’s the simplest protective coating that use a metal more noble than the substrate (Cu, Ni,
Cr, Pb, Sn, Ag); it has a counter-indication: if there are some defects in the coating (always there are)
the steel “at open air” is subjected to corrosion and the material asportation go deep inside the
thickness, it’s very dangerous and frequent because it’s so difficult to obtain a good protection to the
steel. It must be used only if we are sure to obtain a coating without defects and if we are sure it’s
sufficient only a thin protective layer (1-2μm), properly thanks to its protective feature. The only
reason to increase the layer thickness is to be sure of the lack of defects.
2) Anodic: protective coating that use a metal less noble than the substrate (Zn on carbon steel); defects
are accepted because the steel is more noble than protective layer so the corrosion process doesn’t
involve the steel but the layer; the layer is the anode, the steel is the cathode. A high protective layer
thickness is better because have longer durability.

Zinc coating
Zinc can act as sacrificial anode once underlayer steel is exposed. Zinc also makes passivation so over its
surface a zinc oxide forms and it make an additional layer on its surface; according to Pourbaix diagram, the
Zn passivation happens only if it is in environment with 7.5<pH<12. If the environment is simply moisture
condensed its pH is lower than 7.5, but if we are in an urban or industrial environment, two gases are dissolved
in the moisture, CO2 and SO3, so the moisture is acid, with a probable pH higher than 7.5; if it is bigger than
12 also the Zn can be corroded. The corrosion products, however, tends to react with dissolved CO2 in water
and form basic hydrated carbonate on the surface, protecting the Zn and the steel, like a reinforcing. In seaside
environment, Zn is also better than steel and it is a working condition chemically lighter than acid industrial
atmospheres.
How can I apply Zn coating?
 1) Hot dipping, immersing object in molten Zn bath (455°C, very low melting point, easy to obtain with
low energy); the typical thickness is 50-150 μm (high values); the layer has a metallurgically adhesion
to the steel below, thanks to intermetallics that are formed by the reaction between steel and Zn (in the
image we can see the different properties and composition for each intermetallic layer. This adhesion
is good because it isn’t only roughness depending and it is very hard: as we can see from the values in

the image, the intermetallics hardness is higher than pure Zn one and base steel one, so they are a great
reinforcement.
Drawback: I can’t control precisely thickness everywhere; it could be a problem in some case, like
the screw.
2) Electroplating; it works with an electro-chemical system where there is a 1) cathode, 2) an anode and
3) a battery. The two ends of this system are immersed in a Zn aqueous solution. The anode is made
by Zn and the battery makes the corrosion of the Zn plate, each atom is divided in Zn+ ions and e-
electrons, the electron arrive to the metal (steels) at the other end through the wire while the Zn + ions
move inside the solution and create, with the free electrons, a Zn on the metal surface. In this way, the
thickness is very easy to be controlled, depending by the reaction time duration: so, if I stop the reaction
after a precise time, I obtain a precise and exactly value of Zn layer thickness. It’s particularly used for
small component. Drawback: hydrogen embrittlement, caused by H+ ions diffusion inside the surface
making it brittle. I can remove them with a thermal treatment at 400°C for maximum 4 hours at open
air to permits to H+ to move outside the surface.
3) Sendzimir; it is a hot dipping but it involves steel coils and sheets, so it is a continuous process; the
coil is pre-heated, than immersed in molten Zn bath, than the extra-Zn is removed (to obtain only the
desired thickness) and at the end it is cooled. The thickness is normally about 15 μm; this kind of
coating maintain a good adhesion (I don’t have de-touching after strong bending stress).
Hot dipping: used for high protection, for big structure;

Electro-plating: used for small components, like fasteners.

Avantgarde: a duplex coating, the Zn-Al coating, realized from an aqueous dispersion of Zn and Aluminium
lamellae; it’s particularly indicated for hot working conditions; it’s applicable to ferrous material by spraying
or by immersion and centrifugation (the last one is designed exactly for the fasteners). The advantages are that
1) don’t require the dehydrogenation post-treatment and 2) higher corrosion resistance (compared with the
same thickness of Zn obtained from hot dipping or electroplating).

Galvanizing in automotive
Typical thickness is 7.5 μm, normally used to achieve performance like 5 years freedom form cosmetic
corrosion and 10 years freedom from perforation. The thickness can change a lot depending by the coating
strategy used: from 3.0 to 7.5 (or up to 20) μm.
 Conversion coating: Coatings localized over Fe, Zn layer but below the painting; it’s obtained with
chemical reactions that generate compounds that have high chemical stability (oxidation-resistant) on
the surface of the metal. In general conversion coating:
- are extremely thin (few atomic/molecular layers ÷ few microns);
- have high adhesion to the substrate (they are generated by conversion of the metal);
It can be realized with oxide, phosphate and chromate. The phosphate one is a process of chemical
conversion on a metal surface to produce thin adherent phosphate compound coatings. The phosphate
crystals formed on the surfaces of materials can be iron, zinc, or manganese phosphates. Among
these phosphates, manganese phosphate is more suitable for wear applications. The chromate coating
is like previous but today it isn’t available for automotive application because it’s a very dangerous,
carcinogenic.

Phosphatizing: Phosphating is obtained by immersing steel or galvanized steel components in acids

solutions of metal phosphates that form a layer of phosphate on the metal surface: this layer, which
itself is capable of carrying out only a mild anticorrosion action, is an excellent and economical pre-
treatment for the optimal adhesion of subsequent painting cycles or for the temporary protection of
semi-finished products. It could be Mn-based (for fasteners thanks to its good anti-friction property)
or Zn-based (only as pre-treatment for painting). It happens at 60-80°C to enhance diffusion
Chromating: it can do “self-healing” so stopping the metal corrosion by self-repairing the coating
damage that expose steel at open air.

Corrosion inhibitors
There are two types: organic inhibitors and vapour phase inhibitors. In both cases, I use inhibitors (like
sperm cells, with the head and the hydrophobic tail), adsorbed by the metal surface, forming a chemical or
physical bond, and they protect them from the aggressive external environment.
In the organic case, they are organic compound in the liquid solution used for the bath.
In the vapour phase, the metal components are put inside a room where there is a substance in solid state
with inhibitors inside; it starts to evaporate and the vapor contains inhibitors; after they have saturated the
air, inhibitors start to create a chemical bond with the metal and so on the thin protective layer. They are
used to prevent atmospheric corrosion in small, enclosed spaces such as packages for transport for storage.