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Casting and Heat Treatment of AL-4%Cu Alloy

Abstract:
Copper has been the most common alloying element almost since the
beginning of the aluminum industry, and a variety of alloys in which copper
is

the

major

addition

were

developed.

In the cast alloys the basic structure consists of cored dendrites of aluminum
solid solution, with a variety of constituents at the grain boundaries or
interdendritic spaces, forming a brittle, more or less continuous network of
eutectics. Wrought products consist of a matrix of aluminum solid solution
with the other soluble and insoluble constituents dispersed within it.
Introduction:
Use of aluminium castings in automobiles has increased from non-structural
demanding, as it is the case of cylinder heads and engine blocks, to
structural parts, such as suspension struts due to the beneficial effects that
arise by combining light weight and mechanical properties. The requirements
for such structural parts are internal soundness, integrity, high strength and
toughness, and, as result of this, AlCu cast alloys are considered to be ideal
candidates. The parameter that exerts the highest influence on the levels of
strength and internal quality required is the solidification rate; as the
microstructure of the material is refined when solidification proceeds at a
higher rate. A further advantage of microstructural refining, when dealing
with aluminium alloys susceptible for heat treating, is the enhancement in
their mechanical properties; as particles formed during solidification will be
smaller and will require less time to dissolve during heat treating [1].
Experimental Procedure:
1. Sand mold was prepared of known specimen.
2. The weighed amount of Al & Cu were taken as per calculated
theoretically.
3. Al was melted in pit furnace.

4. After achieving Al in molten form, Cu was introduced in the form


of Cu wire.
5. Cu starts dissolving into the melt.
6. Solid degassing was done in order to remove all entrapped gases
to get sound casting.
7. Slag was removed mechanically.
8. After achieving a uniform melt of Al-4%Cu alloy , it was casted
into sand mold.
9. After solidification different samples were obtained and heattreated , there procedure is also discussed.
Fluxes and Degassers used in Al Casting:

Difficulties in Al Melting:
The main difficulties in Al melting are porosity, blow holes and gas
absorption.
Drossing: Molten oxide product of metal is called dross.
Gas Absorption: Solubility of gases in the molten metal is known as gas
absorption.
The following reactions take place during the melting of aluminum;
2Al + 3H2O ------------> Al2O3 + 3H2
8Al + 3CO2 -------------> 2Al2O3 + Al4C3
6Al + 3CO --------------> Al2O3 + Al4C3
6Al + 3SO2 ---------------> Al2O3 + Al2S3
Drossing will be more in case of pit furnace melting than induction melting.
As it is obvious from the above reactions that CO & CO2 is source for Dross
formation and it will be available in Pit furnace due to burning of Natural gas.
Dross is heavier than pure metal i.e Al density is 2.7 while Al2O3 density is
3.9. Dross formation always must be kept minimum. There is 80-90% Al in

dross thats why dross comes on top surface otherwise sink. These kind of
inclusions are detrimental to mechanical properties.
H2 gas is soluble in considerable amount in the molten Al. As the
temperature of molten metal increases the amount of H2 solubility also
increases. On solidification H2 solubility decreases and result in the
formation of pin holes and blow holes.
Hydrogen Removal:
Dissolved hydrogen levels can be reduced by a number of methods, the most
important of which is fluxing with dry, chemically pure nitrogen, argon,
chlorine, and freon. Compounds such as hexachloroethane are in common
use; these compounds dissociate at molten metal temperatures to provide
the generation of fluxing gas.

Flux:
A chemical substance used to refine metals by combining with impurities to
form a molten mixture that can be readily removed.

Degasser:
A chemical substance used to remove gas from liquid metal.

Fluxing of Aluminum Alloys:


Fluxes for melting aluminum are solid substances (commonly mixtures of
chloride and fluoride salts) used in aluminum foundries in order to reduce the
melt oxidation, minimize penetration of the atmospheric Hydrogen, absorb
non-metallic inclusions suspended in the melt, keep the furnace/ladle wall
clean from the built up oxides, decrease the content of aluminum entrapped
in the dross, remove hydrogen dissolved in the melt, provide aluminum grain
refining during Solidification, modify silicon inclusions in silicon containing
alloys, oxidize excessive magnesium.

Common practice of flux introduction is manual application.


Most of the fluxes are applied on the melt surface and stirred into the melt.
Some of the fluxes (degassing, grain refining) are plunged to the bottom by a
clean preheated perforated bell.

Fluxes may also be introduced into the melt by injection in form of a powder
in an inert gas (Argon or Nitrogen) stream.
The simplest flux injection technique is a lance immersed into the melt.
The most effective flux introduction method is injection by rotary degasser.

Classification of fluxes for melting aluminum:

Cover fluxes
Drossing fluxes
Cleaning fluxes
Treatment fluxes

Cover Fluxes:
Melting point of a cover flux is lower than that of aluminum. Cover flux is
applied on the surface of molten aluminum where it melts forming a
continuous layer protecting the liquid metal from oxidation and absorption of
atmospheric hydrogen. Cover fluxes are composed of a mixture of NaCl and
KCl and may also contain some additions of CaCl2, CaF2 or KF. Fluorides
(CaF2, KF) provide further decrease of the flux melting point and improve its
cleaning ability. The disadvantage of fluoride containing fluxes is harmful
fumes released by the flux at work temperature. Sodium free cover fluxes
are used for melting hyper-eutectic aluminum-silicon alloys (alloys containing
above 12.6% of Si). Hyper-eutectic alloys are modified by phosphorus,
additions of which cause refining of the primary crystals of silicon. Sodium
reduce the refining effect of phosphorus in such alloys.

Drossing Fluxes:
Drossing fluxes promote separation of molten aluminum entrapped in the
dross (sometimes up to 80%). Besides chlorides and fluorides drossing fluxes
contain oxidizing component (KNO3) reacting exothermically with aluminum
when heated. Heat generated by drossing flux improves wettability and
fluidity of the entrapped aluminum, drops of which coalescence and flow
down to the melt. The dross treated by the drossing flux is powdery and dry.
It is easily removed from the furnace. Drossing fluxes helps to reduce losses
of aluminum, which makes it very economically effective particularly in
remelting aluminum scrap (chips, turnings etc.).

Cleaning Fluxes:
Cleaning fluxes remove oxides suspended in the melt. Similarly to the
Drossing fluxes a cleaning flux is composed of mixture of chlorides, fluorides
and an oxidizing agent. Cleaning fluxes generate less heat therefore their
aluminum separation effect is lower. However they possess better ability to
absorb oxides inclusions from the melt.

Treatment Fluxes:
These fluxes enhance the properties of the metal by treatment of metal. eg.
Grain refiner.
Grain refining fluxes composed of salts containing titanium and boron
(K2TiF6 and KBF4). The fluxes cause formation of numerous nuclei of
TiAl3 TiB2 when

aluminum

melt

cools

down.

Aluminum

grains

start

solidification on the nuclei surface. The average solid grain size is


determined by the concentration of the nuclei in the melt before
solidification. Fine grain structure is characterized by better fluidity during
solidification, low Microsegregation of impurities, low shrinkage porosity.
Alternative method of aluminum grain refining is introduction of master
alloys containing titanium and boron (eg. Al-5%Ti-1%B).

Degassing:
Removal of dissolved gases from the liquid metal is known as degasing.
Degassing of molten Aluminum alloys is a foundry operation aimed to
remove Hydrogen dissolved in the melt.

Hydrogen in aluminum
Degassing by fluxes
Rotary degasser

In the case of diatomic gases such as H 2, O2, or N2, the amount dissolved at
any particular temperature may be expressed by the equation:

Where V is the volume of diatomic gas dissolved, K is a constant, and P is the


pressure of the gas above and around the metal. The equation shows that, if
hydrogen is completely removed from the atmosphere around a melt, any
hydrogen gas dissolved will tend to escape.

Melting & pouring under vacuum:


Melting and pouring under a vacuum is one method but a very expensive
one for obtaining dissolved gas free casting.
Flushing of inert gas:
Flushing with an inert gas is the most common method of removing gas. In
this method, the inert gas is bubbled directly through the metal; the pressure
of the dissolved gas (usually hydrogen) within each inert gas bubble is zero,
and any dissolved gas migrates readily to the bubble where it collects and is
flushed from the metal baths.
Hydrogen in Aluminum:

Liquid aluminum actively dissolves hydrogen, which forms as a result of


chemical reaction with water vapor:
2Al + 3H2O = Al2O3 + 6H
Solubility of gaseous hydrogen in liquid aluminum at its melting point
(1220.7F/660.4C) is 0.61 in3/lb (2.2 cm3 per 100 g).Solubility of gaseous
hydrogen falls sharply when aluminum solidifies: solid aluminum at melting
point contains only 0.014 in3/lb (0.05 cm3 per 100 g).
Therefore aluminium alloys release excessive amount of hydrogen during
Solidification. This results in porosity defects distributed throughout the solid
metal. Size of the hydrogen pores and their quantity is determined by the
initial content of hydrogen, the alloy composition and the solidification
conditions.

Sources of hydrogen in molten aluminum:

atmosphere humidity;

wet metallic charge;

wet furnace lining (crucible, transfer ladles);

wet foundry instruments;

wet fluxes and other consumables;

furnace fuel combustion products containing hydrogen.

Heat Treatment Of Al-4%Cu Alloy:


Precipitation hardening, or age hardening, provides one of the most widely used mechanisms for
the strengthening of metal alloys. The fundamental understanding and basis for this technique
was established in early work at the U. S. Bureau of Standards on Duralumin.
The importance of theoretical suggestion for the development of new alloys is clear from the
historical record. At the end of the 19th century, cast iron was the only important commercial
alloy not already known to western technology at the time of the Romans. When age hardening
of aluminum was discovered accidentally by Wilm, during the years 1903 -1911, it quickly
became an important commercial alloy under the trade name Duralumin.

The strength and hardness of some metal alloys may be enhanced by the formation of extremely
small uniformly dispersed second-phase particles within the original phase matrix in a process
known as precipitation or age hardening. The precipitate particles act as obstacles to dislocation
movement and thereby strengthen the heat-treated alloys. Many aluminum based alloys, coppertin, certain steels, nickel based super-alloys and titanium alloys can be strengthened by age
hardening processes.
In order for an alloy system to be able to be precipitation-strengthened, there must be a terminal
solid solution that has a decreasing solid solubility as the temperature decreases. The Al-Cu
(Duralumin is an aluminum alloy of 2XXX group) phase diagram shown in Figure 1 shows this
type of decrease along the solvus between the and + regions. Consider a 96wt%Al 4wt
%Cu alloy which is chosen since there is a large degrease in the solid solubility of solid solution
in decreasing the temperature from 550C to 75C.

Figure 1: The aluminum rich end of the Al-Cu phase diagram showing the three steps in the agehardening heat treatment and the microstructures that are produced.
In an attempt to understand the dramatic strengthening of this alloy, Paul D. Merica and his
coworkers studied both the effect of various heat treatments on the hardness of the alloy and the
influence of chemical composition on the hardness. Among the most significant of their findings

was the observation that the solubility of CuAl2 in aluminum increased with increasing
temperature.
Although the specific phases responsible for the hardening turned out to be too small to be
observed directly, optical examination of the microstructures provided an identification of
several of the other phases that were present. The authors proceeded to develop an insightful
explanation for the hardening behavior of Duralumin which rapidly became the model on which
innumerable modern high-strength alloys have been developed.
They summarized the four principal features of the original Duralumin theory:

age-hardening is possible because of the solubility-temperature relation of the hardening


constituent in aluminum,

the hardening constituent is CuAl2,

hardening is caused by precipitation of the constituent in some form other than that of
atomic dispersion, and probably in fine molecular, colloidal or crystalline form, and

the hardening effect of CuAl2 in aluminum was deemed to be related to its particle size.

The precipitation-hardening process involves three basic steps:


1) Solution Treatment, or Solutionizing, is the first step in the precipitation-hardening process
where the alloy is heated above the solvus temperature and soaked there until a homogeneous
solid solution () is produced. The precipitates are dissolved in this step and any segregation
present in the original alloy is reduced.
2) Quenching is the second step where the solid is rapidly cooled forming a supersaturated
solid solution of SS which contains excess copper and is not an equilibrium structure. The atoms
do not have time to diffuse to potential nucleation sites and thus precipitates do not form.
3) Aging is the third step where the supersaturated , SS, is heated below the solvus temperature
to produce a finely dispersed precipitate. Atoms diffuse only short distances at this aging
temperature. Because the supersaturated is not stable, the extra copper atoms diffuse to
numerous nucleation sites and precipitates grow. The formation of a finely dispersed precipitate
in the alloy is the objective of the precipitation-hardening process. The fine precipitates in the
alloy impede dislocation movement by forcing the dislocations to either cut through the

precipitated particles or go around them. By restricting dislocation movement during


deformation, the alloy is strengthened.
Age Hardening Precipitation. The strongest aluminum alloys (2xxx, 6xxx and 7xxx) are
produced by age hardening. A fine dispersion of precipitates can be formed by appropriate heat
treatment.
A general model for decomposition is given, followed by details of the precipitation sequences in
4 specific alloy systems: Al-Cu, Al-Cu-Mg, Al-Mg-Si and Al-Zn-Mg. The Al-Cu system is used
as the main example of decomposition, i.e.
a0 (SSSS) GP zones '' '

or, more fully:

a0 (SSSS) 1 + GP zones 2 + '' 3 + ' 4 +


Age Hardening Strengthening. The 3 main mechanisms are:

Coherency strain hardening;

Chemical hardening;

Dispersion hardening

Coherency strain hardening results from the interaction between dislocations and the strain fields
surrounding GP zones and/or coherent precipitates. Chemical hardening results from the increase
in applied stress required for a dislocation to cut through a coherent (or semi-coherent)
precipitate. This in turn depends on a number of factors, including:

the extra interfacial area - and hence energy - between precipitate and matrix;

the possible creation of an anti-phase boundary (APB) within an ordered precipitate and

the change in separation distance between dissociated dislocations due to different


stacking fault energies of matrix and precipitate.

Dispersion hardening occurs in alloys containing incoherent precipitates or particles - i.e.


typically those that have been overaged. This hardening results from the increased shear stress
required for dislocations to by-pass these obstacles.
As mentioned above, the precipitation reactions in Al-Cu are quite complex. The equilibrium
phase CuAl2 is difficult to nucleate so its formation is preceded by a series of metastable
precipitates. Guinier and Preston first discovered many of the age hardening phenomena. The
first two precipitates to form in the sequence are, therefore, known as GP zones. GP1 consists of

10 nm diameter copper-rich plates on {100}Al planes. These develop into GP2 zones which are
also coherent plates 10 nm thick and 150 nm diameter. These lead to maximum
hardening. Theta' /'/ precipitates then replace the GP zones as semi-coherent particles, a stage
known as over-aging because the hardness begins to decrease. The equilibrium phase CuAl2 has
a tetragonal crystal structure and contributes little to hardness.
In the field of 6000 series precipitation hardening aluminum alloys, for instance, process models
have been able to describe the effect of quench-induced precipitation on structural defects on the
hardening potential during isothermal low-temperature aging.
The fracture toughness of 7000 series alloys has been related to some elements of the
microstructure resulting from the thermo-mechanical treatment in phenomenological models.
The general strategy of process modeling is to use individual equations which have been
developed for well defined experiments and try to integrate them in an integrated manner for the
more complex practical situations where coupled effects operate.
However, a good description is still lacking when several of these phenomena are simultaneously
operative. The understanding of competitive precipitation of several phases (metastable and
stable) on several nucleation sites (e.g. homogeneous and on structural defects) is very limited,
as well as the understanding of the shearing/by-passing transition leading to the maximum
strength for precipitation hardening materials. The strain hardening behavior of materials
containing precipitates (and thus necessarily a solid solution) is poorly understood, and
predicting the fracture toughness in cases where several fracture modes are simultaneously
operating is not possible in the present state of the art.
Experimental Procedure for Precipitation Hardening:

Samples were solution treated at 580 oC for 2 hours and then air
cooled.
Artificial aging was done at 180oC for 1 hour.

Microstructures were obtained, by etching sample in NITAL solution,


using Metallurgical Microscope. These are also attached.

Micro-structure after solution treatment and Artificial age


Hardening:

Figure 2: Microstructure of Al-4%cu Alloy solution treated at 580oC


for 2 hours, at 100X , etched in NITAL reagent

Figure 3: Microstructure of Al-4%cu Alloy solution treated at 580oC


for 2 hours, at 200X , etched in NITAL reagent

Figure 4: Microstructure of Al-4%cu Alloy solution treated at 580oC


for 2 hours, at 400X , etched in NITAL reagent

Figure 5: Microstructure of Al-4%cu Alloy Artificial Aged at 180oC for


1 hours, at 100X , etched in NITAL reagent

Figure 6: Microstructure of Al-4%cu Alloy Artificially aged at 180 oC


for 1 hours, at 200X , etched in NITAL reagent

Figure 7: Microstructure of Al-4%cu Alloy Artificially aged at 180 oC


for 1 hours, at 400X , etched in NITAL reagent
References
1.Characterization

of an AlCu cast alloy ,M.A. Talamantes-Silvaa, A.

Rodrguezb, J. Talamantes-Silvab, S. Valtierrab, Rafael Colsa, a Facultad de


Ingeniera Mecnica y Elctrica, Universidad Autnoma de Nuevo Len, A.P.
149-F, 66451 San Nicols de los Garza, N.L., Mxico bNemak, S.A. de C.V.,
Libramiento Arco Vial km 3.8, 66221 Garca, N.L., Mxico.
2. Registration Record of Aluminum Association Alloy Designations and Chemical Composition
Limits for Aluminum Alloys in the Form of Castings and Ingot, The Aluminum Association, July
1985
3. R.C. Gibbons, Ed., Woldman's Engineering Alloys, 6th ed., American Society for Metals, 1979
4. Handbook of International Alloy Compositions and Designations, Metals and Ceramics
Information Center, Battelle Memorial Institute, 1976

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