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CORROSION BEHAVIOUR OF ALUMINIUM

ALLOY METAL MATRIX COMPOSITE JOINTS


OBTAINED BY FSW
F. Zucchi, V. Grassi, C. Monticelli, A. Frignani
“A. Daccò” Corrosion Study Centre, Department of Chemistry, University of Ferrara, Ferrara, Italy.

Abstract Riassunto
It was studied the corrosion behaviour of two joints, obtained by Friction Stir Welding E’ stato studiato il comportamento a corrosione di due
(FSW), of aluminium alloy metal matrix composites (MMCs), reinforced with alumina giunti, ottenuti con tecnica Friction Stir Welding (FSW), di
particles. W6A20A and W7A10A composite joints were examined. Corrosion tests compositi a matrice metallica in lega di alluminio, rinforzati
were performed in EXCO or 3.5% NaCl solutions. The corrosion rates of MMCs and con particelle di allumina. Sono stati esaminati giunti di
joints were compared. Corrosion tests were performed on both the nugget and the compositi W6A20A (matrice AA6061, rinforzo Al2O3, 20%
thermally affected zones of the joints. Pitting potentials were measured on electrodes in volume) e W70A10A (matrice AA7005, rinforzo Al2O3,
prepared by isolating the different zones. Short-circuit currents were measured between 10% in volume). Le prove di corrosione sono state eseguite
the nugget, the thermally affected zone and the base.The results indicated the different in soluzione EXCO ed in NaCl 3,5%. Sono state confrontate
behaviour of the two joints: the corrosive attack on the W7A10 joint was concentrated le velocità di corrosione dei compositi e dei giunti. Si sono
on the nugget and in its adjacent zones both in EXCO and 3.5% sodium chloride solution; eseguite prove di corrosione sul nocciolo e sulla zona
in the case of W6A20A, the nugget remained protected while the adjacent zones and termicamente alterata della saldatura. Sono stati misurati i
the base material were corroded. Electrochemical measurements confirmed these results. potenziali di pitting su elettrodi preparati isolando le diverse
However, FSW, which produces welds without the formation of a fused zone, causes zone. Sono state misurate correnti di corto circuito fra il
structural modifications in zones near the nugget, due to the higher temperature produced nocciolo, la zona alterata termicamente e la base. I risultati
by the presence of the reinforcement.This negatively affects the corrosion resistance of hanno messo in evidenza il diverso comportamento dei
the composite, also in relation to the base alloy composition. due giunti: sul giunto W70A10 l’attacco corrosivo sia nella
soluzione EXCO che in cloruro di sodio 3,5% si concentra
sul nocciolo e sulle zone ad esso adiacenti; sul giunto
W6A20A il nocciolo rimane protetto mentre si corrodono
le zone ad esso adiacenti e la base. Le misure
elettrochimiche confermano questi risultati. La tecnica FSW,
che produce giunti senza la formazione di una zona fusa,
provoca comunque modifiche strutturali nelle zone
prossime al nocciolo, a causa della maggior temperatura
dovuta alla presenza del rinforzo, che influiscono
negativamente sulla resistenza a corrosione del composito,
anche in relazione alla composizione della lega base.

INTRODUCTION alterations in the distribution and features of the


reinforcement, with substantial modifications of
The most commonly used metallic matrix composites (MMC) are those weld joint resistance. Therefore, these methods
with an Al alloy base matrix.These are chosen for their light weight, ductility, are difficultly applicable.
low melting temperature and because their mechanical properties can be Recently, there have been obtained MMC welds
improved by thermal treatments. Alloys of the 7XXX (Al-Zn) series, along by FSW [1,2]. The technique consists in welding
with those of the 2XXX (Al-Cu) series, are the most commonly used in without material melting by exploiting the frictional
aeronautic field due to their high mechanical resistance and to weight ratio. heat. During FSW, a rotating tool, consisting of a
The reinforcement consists of ceramic materials, such as silicon carbide conical part and a shoulder, is forced between two
(SiC), alumina (Al2O3), titanium diboride (TiB2), graphite.The most common plates and moves along a contact line.The frictional
MMCs contain reinforcements in the form of particles, both for reasons of heat created by the contact of the shoulder against
cost and to improve isotropy. the workpieces produces a plastic zone on the
To expand the use of MMC, the problem of their weldability must be edges to be welded.
solved. The conventional welding methods with metal melting cause A rotating probe produces continuous hot work

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transporting the plasticized metal from the leading potential of the nugget and thermally affected zone was respectively 75 and
to the trailing edge of the shoulder, where 50 mV lower than that of the base alloy. SSR tests in 0.6 M NaCl solution
consolidation produces a continuous joint. showed that the joints were susceptible to stress corrosion.
Nearly flaw-free weld joints are thus obtained. Cracking appears on the interface between nugget and thermally affected
Indeed, mechanical strength and fatigue behaviour zone. Buchheit and Paglia [11] found that in FSW AA7075-T651 and AA7050-
tests have demonstrated the excellent quality of T7451 alloy joints, the welding zones were more susceptible to corrosion
the weldings. as compared to the base alloys. In the case of AA7075-T651 alloy, the
Changes in the corrosion behaviour of the nugget, thermally affected zones were more susceptible to corrosion and stress
in the thermally and/or mechanically affected zones corrosion, while for the AA7050-T7451 alloy the region between the nugget
adjacent to it with respect to the base alloy have and the thermo-mechanically altered zone showed maximum susceptibility
been found on different types of Al alloys welded to corrosion. In SSR tests, the FSW AA7075-T651 joint in general
by this technique. Corrosion tests yield different demonstrated a better resistance to cracking than 7050- T7451 joint, with
results. Thus, the altered microstructures around reversed performance in comparison to that of the base alloys.
the FSW AA5083 joints appear more resistant to Pao et al. [12] found that the fatigue crack growth rate in FSW AA7050
pitting and intergranular corrosion than the base joints in air was slightly higher than that of the base alloy. Both in air and in
material [3]. Frenkel and Xia [4] studied the pitting 3.5% NaCl, the fatigue crack advancement rate in the thermally affected
resistance of FSW AA5454 joints and found that zone was significantly lower and Kth was significantly higher than that of
pitting resistance of the joint was higher than that the base alloy. Gan and Meletis [13], examining the stress corrosion behaviour
of the base alloy. Hu and Maletis [5] evaluated of FSW AA2195 joints, did not find any reduction in ductility in SSR tests
corrosion and stress corrosion behaviour of FSW under constant immersion in NaCl solutions. A certain degree of
AA2195 and AA2219 joints. susceptibility to SCC appeared on specimens which, prior to the SSR tests,
The welded joints showed a corrosion behaviour were subjected to alternating immersion in NaCl solutions. In this case,
better than that of the base alloy. Davenport et al. cracking developed in the thermally affected zones.
[6-8] demonstrated that the nugget and the The object of this paper is to examine the corrosion behaviour of joints
thermally affected zones of the FSW AA2024 and obtained by FSW of Al alloy based MMCs reinforced with Al2O3 particles.
AA7010 joints were more susceptible to pitting As far as we know, no studies have been published on FSW aluminium alloy
than the base material. Lumdsen et al. [9,10] MMC corrosion. The presence of reinforcement should increase the
indicated that in FSW AA7050-T7651 and AA7075- temperature and cause higher thermal gradients, with greater influence on
T6 joints, the nugget and its adjacent zones were alloy microstructures in the zones around the nugget.
more sensitive to corrosion. Also the pitting

EXPERIMENTAL PART joint specimens,the nugget was in central position. The tests for the
evaluation of the weight losses due to corrosion were performed by dipping
The following composites were tested: AA6061 the specimens for 48 hours in an EXCO (Exfoliation Corrosion) solution
aluminium alloy reinforced with 20% (by volume) (4.0 M NaCl + 0.5 M KNO3 + 0.1 M HNO3 ) or for 21 days in 3.5% NaCl
Al2O3, and AA7005 aluminium alloy reinforced solution, in both cases at room temperature.
with 10% Al2O3. Both alloys were subjected to Before immersion in the corrosive environment, the specimens were
T6 thermal treatment: solubilisation, quenching and prepared to obtained perfectly flat surfaces. Grinding was performed using
aging.The chemical composition of the two alloys, sandpaper with mesh progressively decreasing to N. 600. These specimen
expressed as weight percentage, is shown in were then washed in distilled water, degreased in acetone, weighed with an
Table 1. accuracy of 0.01 mg, then immersed in the corrosive solution.At the end of
The corrosion tests were performed on specimens the test, the corrosion products formed during the immersion were
of the base material and on FSW joints, with an eliminated by 70% HNO3 pickling for a few minutes. The weight loss was
exposed surface of approximately 20 cm2. In FSW used to calculate the corrosion rate, expressed in mdd (mg/dm2 day).

Table 1. - Chemical composition (%) of the materials used


MMC Si Fe Cu Mn Mg Zn Ti Cr Zr Al
W6A20A 0.65 0.15 0.18 0.10 0.97 0.009 0.02 0.19 - to 100
W7A10A 0.25 0.24 0.08 0.43 1.33 4.59 0.03 0.13 0.13 to 100

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The tests in EXCO solution were performed on untreated base material between the nugget, the thermally affected zone
and on welded specimens. (TAZ) and the base material.
Coupons for weight loss tests and electrodes for pitting potential Finally, the base materials were subjected to four
determinations were obtained from the three characteristic zones of the different thermal treatments (375°C, 400°C, 450°C
joints (nugget, thermally affected zone and base material), evidenced by and 500°C, respectively) for two minutes.
2.5% HF attack. Then, on the specimens thus obtained, corrosion
The electrodes were connected to a copper wire to ensures electrical tests in EXCO solution were carried out, as well
contact and then incorporated in an epoxy resin. as pitting potentials determinations in 3.5% NaCl
The anodic polarisation curves were recorded with a scanning rate of 0.1mV/ solution.
s, starting from the corrosion potential attained after one hour immersion All the tests were provided with photographic
in the solution. documentation, macrostructural and
For both alloys, short-circuit tests were also performed in EXCO solution microstructural analysis by optical microscope.

Corrosion tests in EXCO solution Table 2. Weight losses in EXCO solution at room
temperature, of base and welded materials
Table 2 collects the corrosion rate values,
expressed in mdd, obtained from the weight losses
Aggressive Test time Material Vcorr
of W7A10A and W6A20A base material specimens,
not containing or containing the welding. environment (hours) (mdd)
The tests lasted 48 hours. W7A10A composite base 921
corrodes faster than W6A20A composite, i.e. 921 W7A10A
welding 1448
mdd in the former case and 588 mdd in the latter EXCO 48
case. base 588
By analysing the coupons containing the welding, W6A20A
welding 440
it was found that W7A10A weld joint showed a
considerably higher corrosion rate than the
corresponding base material, i.e. 1448 mdd for the
former and 921 mdd for the latter, respectively
(Table 2).
The difference appears even more evident if, as
documented in Figure 1, it is considered that the
corrosive attack is located on the nugget and in
the thermally affected zone only. Corrosion rates
higher than 2000 mdd were measured on
specimens taken from the nugget or thermally
affected zones (Table 3).
The behaviour of W6A20A joint is completely
different.
In this case the corrosive attack develops on the
base material and on the adjacent heat affected W7A10A W6A20A
zones.
From EXCO solution tests, it is evident a variation Fig. 1: Appearance of the FSW joints after soaking 48 hours in EXCO solution and
of corrosion resistance of the welded materials pickling
with respect to the base materials not subjected tests on the thermally treated composite specimens.
to FSW.The temperature increase during welding Lumsden et al [9] mapped the temperatures in the joint zone of 7075 alloy
indeed causes microstructural variations which subjected to FSW.
influence the corrosion behaviour of the two They found that in these joints, the zones most susceptible to corrosion
materials. The corrosion resistance modification were the thermally and the thermomechanically affected zones, which
of the two composites caused by a temperature reached temperatures from 375°C to 400°C.
increase was confirmed by performing corrosion Table 4 shows the corrosion rates determined on the base materials of the

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two composites subjected for two minutes to Table 3. Weight losses in EXCO solution, at room
thermal treatment at different temperatures. temperature, of nugget and TAZ in W7A10A joint
The corrosion tests performed on W7A10A Aggressive Test time Material Zone Vcorr
thermally treated specimens indicate an environment (hours) (mdd)
intergranular type corrosion, caused by the
formation of copper-rich precipitates at grain Nugget 2413
boundaries. EXCO 48 W7A10A
TAZ 2092
The consequent copper depletion in the adjacent
matrix causes the lower resistance of the W7A10A
material.
The corrosion rate of the W7A10A composite Table 4. Weight losses in EXCO solution at room
increases as the thermal treatment temperature temperature for two base materials subjected to
increases. Furthermore, the corrosion rate value different thermal treatments
of the material treated at 450°C (2199 mdd) is Aggressive Test time Base Vcorr (mdd)
close that of the thermally affected zone of the environment (hours) Material 375°C 400°C 450°C 500°C
corresponding welded joint. W7A10A 1631 1657 2199 -
AA6061 MMC shows a very similar behaviour to EXCO 48
that above-described for AA7005 MMC, although, W6A20A 621 823 968 1207
in this case, a corrosion rate comparable to that
of joint TAZ is reached only after a thermal
treatment at 500°C. 450°C for AA7005 MMC and 500°C for AA6061 MMC, both higher than
It is evident that the thermal treatment those recorded by Lumsden [9].
temperatures which caused higher corrosion rate, This phenomenon is attributed to the presence of Al2O3 reinforcement, with
comparable to that of joint TAZs, are respectively a volumetric fraction of 10% in AA7005 MMC and of 20% in AA6061 MMC.

Tests in 3.5% NaCl solution

It must be observed that in this solution, pitting is


normally the corrosion attack and the low
corrosion rates determined from weight losses
give a very inaccurate indication of the entity of
the attack.
In fact, the corrosion rates range from 0.32 mdd
(FSW W6A20A) to 1.10 mdd (W7A10A base
material).
After 21 days of exposure, the welded W7A10A
W7A10A W6A20A
specimen showed that the corrosive attack was
Fig. 2: Appearance of FSW joints after soaking 21 days in 3.5% NaCl
concentrated on the nugget and in the immediately
solution and pickling
surrounding zones (Figure 2).
After pickling, a deep attack of the nugget was
observed, while the adjacent zone was unaffected.
The base material specimen shows only a strip of horizontal side and on the transversal sections of the specimen.
corrosion products arising from the hole drilled In 3.5% NaCl corrosive environment, considerably less aggressive than the
to hang up the specimen. EXCO solution, only in the case of W7A10A joints, corrosion was localised
After the same exposure time in the same solution, in the nugget zone.The pitting of the W6A20A joint did not appear, indeed,
pitting was clearly evident on the surface of particularly stimulated by the structural modifications occurring during
W6A20A specimen. welding; the corrosion points, not particularly deep, developed on the base
In this case, pits were distributed both on the material, while the nugget remained unaltered.

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Pitting potential Similar or slightly more negative pitting potential
values were found on the electrodes made of the
Pitting potential values (Epit) of the two materials were obtained from the base material thermally treated from 375°C to
anodic polarisation curves performed in 3.5% NaCl. 450°C.
The electrodes used were taken from the zones of most concern: nugget, These measurements confirm the observations in
TAZ, TAZvn (thermally affected zone near the nugget), TAZvb (thermally 3.5% NaCl corrosion tests performed on the
affected zone near the base), base, and thermally treated base material. welded material in which corrosion was
In the case of W7A10A base material, Epit was -820 mV/ECS, while the concentrated in the central zone of the joint,
thermally affected zone and the nugget presented an Epit from -872 mV/ the one subjected to a highest heating
ECS (nugget) to -880 mV/ECS (TAZ) (Figure 3). temperature.

Fig. 3: Pitting potentials of the characteristic zones of the W7A10A joint and the base material after thermal treatment at different temperatures.

The Epit values of electrodes taken from the characteristics zones of to the thermally affected zone (-688 mV/ECS), to
W6A20A joint and of the thermally treated material are considerably more the base material (-730 mV/ECS).
positive than the corresponding values measured on the first composite The thermally treated specimens present an Epit
(Figure 4). value which tends to increase as the treatment
This aspect confirms a higher resistance to pitting corrosion of this alloy in temperature increases. The specimen treated at
this environment. 500°C for two minutes shows a value of Epit close
The pitting potentials decrease gradually from the nugget (-672 mV/ECS) to that of the thermally affected zone.

Fig. 4: Pitting potentials of the characteristic zones of the W6A20A joint and the base material after thermal treatment at different temperatures

Galvanic coupling measurements Figure 5 shows the corrosion currents related to


W7A10A composite.
From the galvanic coupling measurements in EXCO solution, the nugget- The behaviour of the nugget is anodic with respect
TAZ and nugget-base material short-circuit currents were obtained. The to the base material.
specimens were modelled to have exposed surfaces of equal area. In the nugget-base material galvanic coupling, after

25 - Metallurgical Science and Technology


a few minutes, the short-circuit current stabilises area when in contact with TAZvn.
at 2.5x10-3 A/cm2 and remains constant for the The corrosion potential (Ecorr) measurements in the same solution confirm
entire duration of the test. the above-mentioned results.
The currents between the nugget and the Ecorr of the base material starts from -880 mV/ ECS, after ten minutes it
thermally affected zone are considerably lower.The reaches -820 mV/ECS, then it remains constant until the end of the test.
nugget behaves as an anodic area with respect to For the nugget, the potential starts from -910 mV/ECS and stabilises at
the TAZvb and for most of the time as cathodic -890 mV/ECS after ten minutes. The Ecorr values of the thermally affected

Fig. 5: Short-circuit currents and corrosion potentials of the characteristic zones of the W7A10A joint in EXCO solution

zones, initially equal to that of the nugget, increase nugget, with respect to both the base material and the thermally affected zone,
more slowly. Furthermore, at the end of the test, an inversion is observed, in which the nugget behaves as a cathode.
Ecorr of the TAZvn was slightly more positive The corrosion potentials confirm this trend.The nugget potential after the
than that of the nugget. first moments stabilises at approximately -750 mV/ECS, while the base
Figure 6 shows the trends of short-circuit currents material and the thermally affected zone potentials nearly coincide and are
and potentials of the single zones for W6A20A equal to approximately -780 mV/ECS.The short-circuit currents are reduced
composite.After the first minutes in which the short- and, at the end of the 24 hour test, they reach a value not greater than
circuit currents show an anodic behaviour of the 2.5x10-4 A/cm2.

Fig. 6: Short-circuit currents and corrosion potentials of the characteristic zones of the W6A20A joint in EXCO solution

DISCUSSION Similar results were obtained in 3.5% NaCl tests. The thermally affected
zones and the nugget are those which show lower corrosion resistance.
The tests show the considerably different The electrochemical measurements (pitting potential, short-circuit currents,
corrosion behaviour in FSW joints obtained from corrosion potential) confirm the corrosion test results.
the two MMCs. Since no studies have been found on the corrosion behaviour of FSW joints
In W7A10A joints, corrosion in the EXCO solution of aluminium alloy MMC, the results could not be compared. In agreement
is concentrated in the nugget and in the adjacent with [9-11], concerning the corrosion behaviour of FSW 7XXX series alloys,
zone. The attack is enhanced by the contact with we can affirm that in this type of alloy, FSW causes decaying in the corrosion
the base material, which is more noble and works resistance of the joint. This decrease can be attributed to the increase of
as a cathode. precipitates in the zone adjacent to the nugget, with consequent variation
26 - Metallurgical Science and Technology
BASE NUGGET
MATERIAL

TAZ BASE
MATERIAL
(TT 450°C)

Fig. 7: Optical microscope micrographs of the base material, the nugget, the TAZ of the W7A10A joint and the base material after thermal
treatment at 450°C

of the composition in the grain boundaries, thus making them more W7A10A specimens, i.e., the base material, the
susceptible to intergranular corrosion and pitting. nugget, the TAZ and the 450 °C thermally treated
The tests performed on the thermally treated W7A10A base material base material.
validate this conclusion. It can be observed a considerable increase in the
Indeed, the W7A10A specimens, treated for two minutes at 450°C, show a size of the grains in the TAZ, due to heating, with
corrosion rate in EXCO similar to that of the thermally affected zones of the formation of a nearly continuous series of
joints, approximately double that of the W7A10A base material.Also the pitting precipitates at the grain boundary. A similar
potentials of the thermally treated material are similar to those of the welded structure was reproduced by the thermal
zones and lower by around 60 mV than those of the base alloy. treatment at 450°C for two minutes.
The micrographs in Figure 7 show the most interesting structure of the On the W6A20A joints, with an alloy notoriously

BASE NUGGET
MATERIAL

TAZ BASE
MATERIAL
(TT 500°C)

Fig. 8: Optical microscope micrographs of the base material, the TAZ of the W6A20A joint and the base material after thermal treatment at 500°C

27 - Metallurgical Science and Technology


more corrosion resistant than 7XXX alloys, the No modifications in the grain size were observed, but there was an increase
FSW process does not decrease so drastically the of precipitates in the grain boundary zone of the thermally treated material.
corrosion resistance, although the mechanical The nugget has grains of smaller size.The EXCO solution attack, as shown
features of the joint are subjected to the same in the micrographs in Figure 9, is essentially intergranular. It can be
variations (hardness, fatigue strength, etc.) as the hypothesized that the lower corrosion rate of the nugget.
W7A10A joint.The micrographs in Figure 8 show Is linked to a complete recrystallisation, with formation of very small crystals.
the microstructure variations found in the TAZ The extended grain boundary area prevents the formation of a continuous
and in the specimen thermally treated at 500°C network of precipitates in the grain boundary zone, so that the material
as compared to the base alloy. results much less susceptible to intergranular corrosion.

BASE
TAZ MATERIAL
(TT 500°C)

Fig. 9: Optical microscope micrographs of the TAZ and of the base material of the W6A20A joint after thermal treatment
at 500°C and exposure to EXCO solution

CONCLUSIONS The intergranular attack and the pits are concentrated in the nugget and in
its adjacent zones in the W7A10A joint.
FSW is used to weld materials not weldable by In the W6A20A joint, the nugget, entirely re-crystallised with very fine grains,
other techniques. Both joints present a fatigue corrodes at a lower rate than the base material and the both thermally and
strength comparable to that of the base materials thermo-mechanically altered zones.
providing the welding technique is applied with In both cases, it is evident the need to thermally treat the welded material
correct parameters. to improve the corrosion behaviour.
Resistance to intergranular corrosion and to pitting
of the two MMCs welded by FSW is entirely ACKNOWLEDGEMENTS
different: lower in the W7A10A welds, better in
the W6A20A welds. We thank Linda Pellegrini for contributing to the experimental part.

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28 - Metallurgical Science and Technology
FOURIER THERMAL ANALYSIS APPLIED
TO SODIUM EUTECTIC MODIFICATION
OF AN ALSI7 ALLOY
F. Piasentini**, F. Bonollo*, A. Tiziani*
* DTG - Department of Management and Engineering - University of Padova
** ENDIF - Engineering Department - University of Ferrara

Abstract Riassunto
The so-called “Fourier Thermal Analysis” (or FTA) is an evolution of the “integral thermal La “Fourier Thermal Analysis” (FTA) è una tecnica avanzata
analysis”, which is actually used as a process control in Aluminium and cast iron foundries. di analisi termica, sviluppata negli anni ’80-’90 per
It has been developed since late 80’s in order to investigate nucleation and growing determinare il calore latente rilasciato in fase di
kinetics of the various phases in multi-component alloys. FTA is based on the evaluation solidificazione, allo scopo di indagare le cinetiche di
of the thermal gradient in one-dimensional thermal field that arises in a cylindrical nucleazione ed accrescimento delle varie fasi coinvolte. I
solidifying specimen. risultati delle indagini condotte con questa metodologia
During the last twenty years, both the traditional thermal analysis and FTA have been hanno contributo allo sviluppo dei codici di calcolo per la
applied to the experimental determination of the solid fraction during solidification, in modellazione dei fenomeni di solidificazione di leghe da
order to assess results from numerical simulation. Nevertheless, FTA has not been fonderia, come le ghise e le leghe di alluminio. Non è
applied to foundry process control or optimisation. attualmente impiegata nell’ambito della fonderia come
Eutectic modification is extensively used in low-pressure permanent mould processes, strumento di controllo di processo o come metodo per la
in order to improve tensile properties and toughness of Al-Si alloys.The effectiveness of caratterizzazione dei fenomeni di solidificazione.
the treatment is subjected to the presence a minimum amount of modifying elements, D’altra parte neanche l’analisi termica “tradizionale” viene
such as Sr, Na or other elements. Traditional thermal analysis is useful in determining utilizzata in modo diffuso nella fonderia di Al-Si, al contrario
modification level of the alloy, then to control the modification treatment. della fonderia di ghisa.
Aim of this work is to verify the potentiality of gradient-based thermal analysis method, Scopo di questo lavoro è di verificare le potenzialità della
such as FTA, in eutectic modification investigation. FTA nello studio della modifica eutettica di una lega Al-Si,
An A356-type hypoeutectic Al-Si alloy has been modified with metallic sodium at four e più in generale nella dinamica della solidificazione delle
different modification levels. Two-thermocouple thermal analysis curves have been leghe Al-Si. La modifica eutettica viene impiegata allo scopo
recorded, in order to perform FTA analysis. Fraction solid versus time (fs(t)) and di incrementare le caratteristiche di resilienza e resistenza
temperature (fs(T)) have been determined at different modification levels. a fatica delle leghe Al-Si, l’efficacia del trattamento è
Microstructural characterization has been made using automatic image analysis.Average vincolata alla presenza di una percentuale minima di
values of dimension and roundness of eutectic Si have been compared to thermal analysis elemento modificante. L’analisi termica può essere
results. impiegata per verificare il livello di modifica della lega, e
A significant correlation between the so-called “eutectic depression” and silicon quindi l’efficacia del trattamento.
morphology has been observed. More relevant is the behaviour of the fraction solid é stata presa in considerazione una lega della classe A356,
curves, from which it is possible to note a significant delay in the start of eutectic modificata con il Na, e sono state confrontate le curve
reaction. This delay has been observed not only in time but also in temperature and fs(t) e fs(T) ottenute con diversi livelli di modifica, allo scopo
fraction solid domain. di correlare le caratteristiche delle curve di frazione di
fase solida rispetto al tempo ed alla temperatura con le
caratteristiche microstrutturali della lega.
Sono stati riscontrati effetti della modifica sull’evoluzione
nel tempo delle varie fasi, compresa la fase primaria, ricca
di alluminio.

11 - Metallurgical Science and Technology


INTRODUCTION where, apart from the already defined symbols, DH is the solidification
volumetric latent heat and VS represents the volume of already solidified
In a foundry process, the possibility of monitoring metal [1,4-5].
in detail the evolution of solidification is At the end of solidification, temperature decreases again, with a different
fundamental, in order to have the correct slope, due to the change in r and cp values from the liquid to the solid state.
understanding of the final microstructure and These general considerations must be integrated including the role of
metallurgical quality of the casting. Thus, the so- nucleation (heterogeneous nucleation is considered) and growth
called “cooling curves” (even if a more correct mechanisms, whose effect depend specifically on the processing conditions.
definition is that of “solidification and cooling In particular, undercooling must be considered, being the real driving force
curves”) are assuming an increased relevance and of the whole solidification phenomenon [1]. Nucleation and growth rate
diffusion, both from literature and industrial can be described with specific reference to undercooling degree. Applying
application viewpoints. the continuous nucleation model, it can be written
A liquid metal or alloy, placed into a mould,
N = µ . ∆Tn
1
(3)
decreases its temperature, due to the heat transfer
phenomena (conduction, convection, radiation). and
The amount of these phenomena is dependent ∂N ∂T
= − n . µ1 . ∆T(n-1) . (4)
on various factors, including the geometry of the ∂t ∂t
mould, the insulation conditions, the possible where N is the number of nuclei formed in the volume unit, DT is the
motion of the liquid, the presence of cooling undercooling, n and m1 are the so-called nucleation parameters.
devices, and so on [1-7]. For the growth rate (Vaccr), it can be written
Generally speaking, a temperature vs. time diagram Vaccr = µaccr . ∆T
2
(5)
allows the description of the thermal evolution of
the metal or of the alloy. In the liquid state, the where µaccr = growth constant [1,6].
analytical description of the phenomenon is given A “real” solidification curve is thus characterised by the presence of
by the equation undercooling, associated with the progressive development of the latent
dT heat, leading to the recalescence phenomenon, which is well described by
A . q = V . ρ . cp . (1)
dt the first derivative of the cooling curve (i.e. the cooling rate).
where V and A are, respectively, the volume and The parameters of the above equations, correlating undercooling with
the surface of the casting, ρ and cp are, respectively, nucleation and growth rate, are strictly dependent on composition and
the density and the specific heat of the material technological aspects. In other terms, the evolution of solidification is strongly
under investigation, q is the density of the thermal related with the specific properties of the cast alloy and on the foundry
flow going from the metal to the mould.The term processing conditions adopted.
q can be evaluated, for instance, by the Fourier The acquisition and the analysis of the cooling and solidification curve of a
equation, once known the starting and contour cast alloy have demonstrated their industrial relevance for alloys presenting
conditions of the system. The variables T and t eutectic solidification, such as the Fe-C-Si (cast irons) and Al-Si systems [8-
are, respectively, the metal temperature and the 14], both in terms of process control and of microstructure understanding
time; thus dT/dt (i.e. the derivative of temperature [11,13].
with respect to time) is the cooling rate of the A recent development of this approach has been introduced for analysing
metal [1,4-5]. the kinetics of nucleation and growth of eutectic systems. It is the “Fourier
Under the hypotheses of small variations in ρ and Thermal Analysis” approach, requiring the acquisition and the subsequent
cp with temperature and of q = constant, the elaboration of at least two T(t) curves, as well as cylindrical or spherical
cooling rate is also constant, with the cooling curve crucibles [15-16].
assuming a linearly decreasing aspect. In this paper, such an approach is developed and applied on Al-Si foundry
The liquid to solid transition is associated to the alloys, to monitor their solidification conditions and to describe the effects
release of the latent heat. Consequently, equation of the modification stage.
(1) must be properly modified and becomes:
dT dVS
A . q = V . ρ . cp . − ∆H . (2)
dt dt

12 - Metallurgical Science and Technology


FOURIER THERMAL ANALYSIS heat exchanged is determined only by the heat
exchange at the interface between metal and the
Theoretical aspects external environment.
In “Fourier Thermal Analysis”, instead, the heat
The slope of the curve T(t) of a generic alloy, solidifying in a thermal analysis
exchanged is supposed to be related to
cup, is due to two contributions: the rate of volumetric heat exchanged to
temperature gradient inside the alloy. The slope
the environment (HEXC, [Jm-3s-1]) and the rate of volumetric latent heat
of solidification curve is then related also to the
released during solidification phenomena (HGEN, [Jm-3s-1]). The slope of
thermal diffusivity a [m2s-1] of the alloy (a quantity
solidification curve is given by equation (6), where Cv is the volumetric
related also to the heat conductivity of the material
heat capacity [Jm-3K-1] of the system.
HEXC(t,T) + HGEN(t,T,fs) [15-16]) and the Laplace operator 2T [Km-2], as
dT
= [Ks-1] (6) reported by equation 7.
dt CV(t,TfS) HGEN
∂T
HGEN depends on the phase transformations that occurs during solidification, = α 2T + Cv (7)
∂t
so it is influenced by the melt treatment (grain refining, eutectic modification)
In the case of a cylindrical cup, temperature
and also by the rate of heat extraction from the melt (the late influencing
gradient can be estimated by means of a two-point
the depth of undercooling in solidification transformations).
temperature measurement [15-16], each located
HLOSS is related to the conditions of heat exchange between the specimen
to a certain radius Ri from the centre:
and the external environment. In the so-called “Newtonian Thermal Analysis”
2
4(T2 - T2 )
[8,14-15], the alloy is supposed to be uniform in temperature, so that the T = 2 2 2 1 [°C/m2] (8)
R 2- R 1
So that the rate of volumetric heat generated can
be obtained as:
∂T
HGEN = Cv -α 2T [J/s] (9)
∂t
In this equation the term α 2Tgives the so-called
“base line” for the heat measurements, i.e. the
theoretical cooling curve of a material not having
phase changes.
If absence of phase changes (in liquid and solid
state), thermal diffusivity a can be expressed as
the ratio between the slope of T(t) curve in the
centre of the specimen and the Laplace operator.
(∂T/∂t)
α= 2 (10)
T
From this equation, having a bigger diffusivity gives
a bigger capacity of the material of releasing heat
when subjected to the same thermal gradient.
Fig. 1: thermal diffusivity as obtained from (4) (in black) and estimated inside the
solidification interval (in red) Once kwon thermal diffusivity in solid and liquid
state, diffusivity during solidification can be derived
using a simple linear correlation [15]. An example
of this approach is given by figure 1.
From the product of diffusivity and thermal
gradient, a base line (or “zero line”) Z F can
calculated and used to determine the heat released
during solidification, according to (9).
In figure 2 the zero curve ZF is plotted against the
slope of solidification curve, or dT/dt.

Fig. 2: first derivative of T(t) curve for the central thermocouple (black) and baseline
for latent heat determination (ZF, green).

13 - Metallurgical Science and Technology


Practical application of FTA 3. thermal diffusivity in liquid and solid state
4. thermal diffusivity during solidification
The experimental set up for FTA requires only
5. base line ZF
two additional features: a symmetrical cup
6. heat released during solidification
(cylindrical or spherical) and a second
7. fraction solid with respect to time and temperature
thermocouple.
One of the critical aspects is the thermal diffusivity calculation. Some authors
Once measured the two time-temperature curves
suggest evaluating diffusivity in function of fraction solid, using and iterative
(Tint(t) e Text(t)), their elaboration consists in this
procedure, in which diffusivity is initially supposed to be linear function
calculation steps:
with time [15-17].
1. first derivative in the inner point
2. thermal gradient

SODIUM EUTECTIC - it does not form compounds or intermetallic phases


MODIFICATION OF AN AL-SI It has been recently pointed out the up-to-dateness of sodium modification,
ALLOY having care that the overall process is controlled by means of suitable process
control, such as thermal analysis [23]
Eutectic modification is one of the more effective In practice, sodium fading effect makes necessary a process control on the
techniques for microstructure and mechanical modification level of the melt, in order to develop a constant quality in the
properties optimisation in Al-Si foundry alloys. casting.
It consists in the addition of specific elements, or A traditional thermal analysis system can be useful in order to investigate
“modifying” elements (such as Na, Sr, Ca), in order on the effect of sodium and other modifying elements on the solidification
to modify the structure of eutectic Si, from lamellar mechanisms and on the final properties of the modified alloys. Traditional
to fibrous and spherical.This leads to a substantial thermal analysis uses features of the T(t) curves such as eutectic depression
improvement in mechanical properties such as and recalescence, and can be used in conjunction with chemical analysis in
toughness and tensile strength. Other elements order to characterize the melt and its modification level [12-14,17]
have been reported to have modifying properties Fourier Thermal Analysis (FTA) has been developed in order to evaluate
(i.e. Ba,Y,Yb) [18-26]. heat released during solidification in different cooling conditions, so to
Speaking about Na modification, one of the critical determine the dependence fraction of solid with time and temperature.
aspects in the use of this element is the short fading The potentiality of the application of this technique to the study of eutectic
time, after which the modifying effect disappears. modification has not yet been verified in literature, and it’s the main task of
Being a “temporary modification”, it has also some this work.
advantages, because: The knowledge of the dependence of fraction solid with different
- it does not affect significantly properties like solidification condition (heat exchange, melt treatment) is also one of the
fluidity and viscosity crucial points in numerical modelling of microstructure evolution.As a matter
- modified alloys can be recycled without of fact, FTA has been used by different authors to characterize the various
additional treatments foundry alloys behaviour [2,6-7].

EXPERIMENTAL SET UP for thermocouple has been used, consisting in stainless steel tube (AISI
316), inner diameter 1.7 mm, thickness 0.1 mm. The distance between the
The present study has been carried out using an inner thermocouple (T1) and the outer is 20 mm. Sampling frequency: 10
alloy belonging to the EN AB 42100 class (an A356 Hz.
equivalent). Chemical composition of the The various step of the application of FTA are listed in the following points:
investigated alloy is given in table 1. 1. alloy melting and overheating (750°) in muffle furnace, addition of
A steel thermal analysis sampling cup, preheated metallic Na, thermal analysis crucible preheating (750°C);
before sampling, has been used. Thermocouples 2. sampling of specimen M01, 5 minutes after modification
are K-type, outer diameter 1.5 mm, shielded with 3. sampling of specimen M02, 25 minutes after modification
stainless steel (AISI 316).An additional protection 4. sampling of specimen M03, 45 minutes after modification

Table 1. Chemical composition of the investigated alloy


Alloy type\elements Si Mg Cu Mn Fe Zn Ti Al
AlSi7MgTi 7,06 0,448 0,036 0,007 0,13 0,002 0,125 Bal

14 - Metallurgical Science and Technology


5. sampling of specimen M04, 65 minutes after modification - average area, roundness and aspect ratio of
Traditional thermal analysis and FTA have then been performed on the eutectic silicon
recorded T(t) curves. Results of the analysis have been compared to the Details on the microstructure evaluation as well
main microstructural features of specimens: as on thermal analysis are reported in the next
- secondary dendrite arm spacing (SDAS) of a-phase paragraphs.

RESULTS AND DISCUSSION

Traditional and Fourier thermal analysis have been


applied to the specimen taken at various fading
time. Results from these analyses have been
compared to specimen microstructures.
Solidification curves T(t) of the various specimens
are reported in figure 3. Red curves refer to inner
thermocouples, black curves to the outer ones.
Arrows show the effect of Na fading on eutectic
depression. The minimum temperature reached
during eutectic transformation gradually rises with
fading time.This tendency is coherent with results
reported by other authors [22, 23].
Fig. 3: T(t) curves at different modification level, corresponding to Curves have then been elaborated according to
specimens M01-M04. the procedure presented in previous paragraphs,
in order to obtain the dependence of fraction of
solid with time and temperature fs(t) e fs(T), and
to evaluate the effect of Na modification on the
shape of these curves.

Microstructural investigation
Microstructure of specimen named M01ÖM04 has
been characterized by means of Automatic Image
Analysis, in order to quantify alloy modification
level in terms of average roundness and dimensions
of eutectic Si. Other phases have been also
identified, as reported in figure 4.
For each specimen, a total of 9 different areas have
been investigated, as reported in figure 5. In each
Fig. 4: microstructure of specimen M03 (200x). of these areas, 9 fields taken at a 500 magnification
have been photographed and analysed. This
procedure has been performed by means of an
automatic image analysis system (LEICA QWIN),
including the field individuation, data recording and
analysis.

Fig. 5: position of the nine areas for metallographic investigation in the thermal
analysis specimen.

15 - Metallurgical Science and Technology


In figure 6-9, examples of microstructures taken perimeter and area). Both aspect ratio and roundness are useful in describing
on different specimens are presented. At higher the morphology of eutectic silicon: when they are close to unit, the eutectic
fading times, eutectic Si grows in dimension and is close to spherical shape. On the contrary, if their values are far from the
its shapes moves from fibrous to lamellar. unit, the shape of eutectic is lamellar.
Geometric parameters of the eutectic silicon that Average values for the various specimens are listed in table 2.
have been investigated are: area, aspect ratio Fading of Na modification, that occurs during time, leads to the reduction
(length/width), roundness (a parameter defined in modification level. This causes the drop in roundness of eutectic silicon,
inside the image analysis software, linked to and the contemporaneous increase in its size.

Fig. 6: specimen M01-5’. Fig. 7: specimen M02-25’.

Fig. 8: specimen M03-45’. Fig. 9: specimen M04-65’.

Table 2. Geometric parameters of eutectic silicon vs. sodium fading time


M01-5 min M02-25 min M03-45 min M04-65 min
Area [mm2] 10.8 13.1 35.9 77.6
Roundness 3.3 3.6 5.8 8.4
Aspect ratio 2.5 2.4 3.2 4.3

Microstructural characterization has been between secondary dendrite arms of Al-rich a phase.The SDAS (Secondary
completed with the measurements of the spacing Dendrite Arm Spacing) has been evaluated in 81 different fields. Results from

16 - Metallurgical Science and Technology


Table 3. SDAS variation with fading time. these measurements are listed in table 3.
Specimen time [min] SDAS [mm] s [mm] The variation of roundness and aspect ratio with
fading time is presented in figure 10. The average
M01 5 64.0 5.0 values of both these features have a strong increase
M02 25 68.0 5.5 between 25 and 45 minutes, showing a decrease
in modification level. After 45 minutes from the
M03 45 68.1 7.2 introduction of Na in the melt, the modification
M04 65 68.1 4.1 level reaches a critical point, from which the
properties of the material are supposed to show
a significant decrease.

Rate of heat released versus time


With FTA it is possible to evaluate the rate of
heat released during time (or HGEN), so that fraction
of solid can be calculated as the fraction of heat
released until that time on the total of heat
released.
A visualization of the various stages of the
solidification processes is then visible, as reported
in figure 11, referred to 5 minutes after
modification occurred. Three different areas are
visible, the first one related to the primary a phase,
the second one belonging to Al-Si eutectic and
Fig. 10: variation of eutectic silicon roundness and aspect ratio
for different fading time.
the third one to the secondary phases and
intermetallic compounds with other alloying
elements (like Mg2Si and Fe-Mn-Mg rich phases).
The area related to the last solidifying phases
seems to be more evident at the highest fading
times, as reported in figure 12-13.The contribution
on heat generated gradually tends to get mixed
up with the contribution of eutectic silicon.

Fig. 11: latent heat released vs. time, 5 min. after modification, specimen M01.

Fig. 12: latent heat released vs. time, 25 min. after Fig. 13: latent heat released vs. time, 65 min. after
modification, specimen M02. modification, specimen M04.
17 - Metallurgical Science and Technology
Rate of heat released versus dependence. In this way it’s possible to compare results obtained in different
solid fraction cooling conditions.
From figures 14-15 it is evident the shift in the initial point for eutectic
Latent heat released can be compared to fraction
reactions, which is moving towards lower fraction of solid.
of solid, in order to free the results from time

Fig. 14: latent heat released vs. solid fraction, 5 min. after modification, Fig. 15: latent heat released vs. solid fraction, 65 min. after modification,
specimen M01. specimen M04.

Fraction of solid versus


temperature
Fraction of solid fs, as measured by means of FTA,
can be plotted against the temperature measured
in the centre of the thermal analysis cup.The effect
of modification on transformation kinetics is then
visible in the curve fs(T).
Figure 16 collects the various fs(T) curves for
specimens M01-M04. Starting point for eutectic
reaction is identified with the minimum point of
fs(T) curves.
Not only modification shifts this point to lower
temperatures (as shown also from traditional
thermal analysis), but also seems to shift the
fraction of solid of this point to higher values. Fig. 16: solid fraction vs. temperature, at various fading time.
In other terms, eutectic reaction starts at lower
temperatures, when a higher quantity of Aluminium
rich a-phase has been already formed.

18 - Metallurgical Science and Technology


Table 4. variation of eutectic start with fading Data regarding the shift of the eutectic start point
time. are listed in table 4.
The presence of sodium in the melt seems to
Specimen Fading time fs at start of T at start of
influence also the primary solidification, not only
[min] eutectic reaction eutectic reaction
the eutectic formation.
[°C]
M01 5’ 0.66 558.0
M02 25’ 0.55 558.5
M03 45’ 0.52 560.1
M04 65’ 0.51 565.0

CONCLUSIONS

The so-called Fourier Thermal Analysis (FTA) has been used to monitor
the effect of modification on the evolution of solid fraction during
solidification of an A356 Al-Si alloy.
The latent heat released during solidification has been measured, and from
that the solid fraction has been obtained during the various stages of
solidification.The evolution of solid fraction in temperature (the fs(T) curves)
has been found to be the most effective in evaluating the effect of melt
treatment on the solidification phenomena.
Solid fraction curves fs(T) have been obtained at different modification levels,
showing significant effects of the sodium modification level on the starting
point of formation of eutectic phases.
These results confirm the feasibility of using FTA as an experimental method
for evaluating fs(T) curves in different melt treatment conditions, in particular
regarding eutectic modification. These curves can be used also as input
parameters for numerical modelling of microstructure formation in foundry
alloys.

ACKNOWLEDGMENTS

Authors want to thank professor Ingvar Svensson and dr. Attila Diószegi
(Jonköping University, SE) for the theoretical support; Roberto Losco,
Giacomo Mazzacavallo, Enrico Della Rovere and Alice Dal Martello for their
irreplaceable contribution in the test realization and in the microstructural
characterization of the specimens.

19 - Metallurgical Science and Technology


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20 - Metallurgical Science and Technology
SOLIDIFICATION BEHAVIOUR AND
MICROSTRUCTURE OF A360-SICP
CAST COMPOSITES
P. Bassani*, B. Previtali**, A. Tuissi*, M. Vedani**, G. Vimercati**, S. Arnaboldi**
* CNR IENI, Lecco, Italy
** Politecnico di Milano, Milan, Italy

Abstract Riassunto
In the present investigation, the solidification microstructure of Al based composites Nel presente studio si sono volute analizzare le
was studied. The materials investigated were a commercial A360 aluminium alloy and microstrutture di solidificazione di materiali compositi a
the corresponding composites reinforced with 10 and 20 vol. % SiC particles.The materials matrice in lega di alluminio. I materiali utilizzati sono stati
were cast under different conditions for a first set of laboratory tests, aimed at studying una lega commerciale A360 di alluminio e i corrispondenti
the solidification behaviour and the related microstructures. The reinforcement compositi rinforzati rispettivamente con il 10% e il 20% in
distribution in the cast composites revealed to be governed by the pushing action exerted volume di particelle di SiC. I materiali sono stati colati in
by the matrix solidification front during casting, giving rise to clustering effects of the differenti condizioni per una prima serie di analisi di
SiC at dendrite boundaries, especially in sand castings. Copper mould castings, laboratorio, con lo scopo di studiare il comportamento di
experiencing reasonably high cooling rates during solidification, showed a very fine solidificazione e le relative microstrutture. La distribuzione
microstructure within which the segregational effects of the reinforcement was of limited del rinforzo nei getti in composito si è rilevata essere
relevance. SiC particles also revealed to be a site for heterogeneous nucleation of coarse governata da fenomeni di “pushing” esercitati dal fronte di
Si crystals in the composites solidificazione durante la colata, generando, in particolar
modo nei getti in sabbia, fenomeni di segregazione del SiC
ai bordi delle dendriti. Colate in lingottiera in rame, che
come noto garantiscono elevate velocità di raffreddamento
in fase di solidificazione, hanno permesso di ottenere
microstrutture molto fini, con fenomeni di segregazione
del rinforzo di limitata rilevanza. Inoltre nei compositi le
particelle di SiC si sono rilevate essere in grado di
promuovere una nucleazione eterogenea di grossolani
cristalli di silicio primario.

3 - Metallurgical Science and Technology


INTRODUCTION MMCs in advanced industrial applications [3].
The solidification behaviour of particulate reinforced MMCs is strongly
Metal matrix composites (MMCs) are a promising influenced by the interaction of the solid reinforcement phase with the
group of materials, produced by combining a solidification front. Depending on physical properties of ceramic
metallic alloy matrix, usually an aluminium alloy, reinforcement and liquid matrix, and on solidification conditions (e.g.:
with a hard and stiff ceramic reinforcement. Their temperature gradient and solidification rate), particle pushing ahead of the
properties can be tailored by a proper selection of solidification front rather than reinforcement engulfment in the solidified
matrix properties and by changing the composition, metal matrix can occur. These possibilities in turn significantly affect the
shape, size and volume fraction of the reinforcing degree of reinforcement distribution of the cast composite since, when the
phase. Interesting application fields exist in the particles are rejected in the liquid phase, they will concentrate in the
automotive and aerospace sectors, electronic interdendritic regions of the structure, leading to harmful segregation effects
packaging as well as in sport equipments [1,2]. [1,4-8].
Discontinuously reinforced MMCs, such as From a technological perspective, there are other peculiar aspects that
particulate reinforced aluminium alloys, offer the deserve special attention when comparing the foundry procedures of Al
additional advantage of being amenable to a large based MMCs with respect to those of the unreinforced alloys. Melting is
part of the conventional metalworking techniques usually performed in conventional furnaces based on gas combustion,
usually adopted for the corresponding resistance or induction heating. However, particle settling must be prevented
unreinforced alloys. However, due to the effects by periodical stirring of the melt.Temperature should be strictly controlled
of the abrasive ceramic particles in the composite, at any time in order to avoid unwanted reaction between SiC and Al that
machining undoubtedly remains one of the less would occur on overheating [9-12]. Skimming as well as degassing to increase
attractive routes for obtaining complex parts. For melt cleanliness are not usually accomplished in MMC melts due to the
this reason, cast composite parts, whose final shape tendency of reinforcement accumulation at melt surface that would result.
is directly obtained by solidification, are considered Therefore, the starting ingots and all the equipments to be used in contact
of strategically importance for a rapid uptake of with the composite melt have to be carefully cleaned and devoid of humidity.

MATERIALS AND under controlled Argon atmosphere at a pressure of 650 mbar and the
EXPERIMENTAL PROCEDURES materials were cast in a square-section (70x70 mm) water-cooled copper
mould.A thermocouple was positioned at the centre of the mould in order
The materials studied in the present investigations to record the ingot temperature during solidification and cooling.To evaluate
are an A360 alloy and two composites obtained the effectiveness of electromagnetic stirring of the liquid Al alloy and the
by the addition of 10 and 20% (nominal content) suspension of the solid SiC particles, no mechanical stirring of the melt was
of SiC particles.The composition of the materials performed.
investigated is listed in Table 1.The materials were A second set of castings was then produced with an industrial gas furnace
provided in the form of commercial foundry ingots at a foundry plant. For this case, the melt was periodically stirred both
weighting about 12 kg. during melting and just before pouring to prevent particle settling. For a set
A first set of castings was produced by a laboratory of castings, modification of the alloy was performed by using Na-based
vacuum induction melting furnace (Balzers VSG10) additives, according to conventional foundry practice.The molten alloy and
equipped with a ZrO2 (65%)/SiO2 (35%) crucible. composites were then poured in dry sand moulds having two different
For electromagnetic coupling, the melting crucible shapes. Simple cylindrical shaped castings of 50 mm in diameter and 80 mm
was inserted in an external graphite crucible in height were produced as samples for the laboratory analyses. Also in
(Figure 1). Melting operations were conducted these circumstances, the temperature was measured by a thermocouple

Table 1. Chemical composition (mass %) of the A360 alloy and of the matrix
of the composites investigated
Alloy Si Fe Cu Mn Mg Cr Zn Ti Ni Sr Al
A360 9,23 0,49 0,079 0,30 0,34 0,017 0,063 0,03 0,001 - bal.
A360-10%SiC 10,8 0,90 0,004 0,76 0,63 0,002 0,005 0,09 0,005 0,010 bal.
A360-20%SiC 9,94 0,89 0,007 0,62 0,63 - 0,013 0,08 - - bal.

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Fig. 1: Experimental set-up for laboratory scale castings. Insight of the vacuum chamber (a) and schematic section
of the water-cooled copper mould (b).

placed at cylinder axis. In addition, a series of much larger castings, weighting of the A360 alloy. Optical and scanning electron
about 10 kg, were produced as depicted in Figure 2. Detail on the properties microscopy (SEM) as well as hardness and
of these latter castings will be presented in a future paper. microhardness measurements were adopted for
Samples cut from the sectioned castings were then investigated for the microstructural analyses presented in this
microstructural analyses to study the effects of the different solidification paper.
conditions and of the different amount of reinforcement on the structure

Fig. 2: MMC castings produced according to foundry practice. Pouring of the composite melt in the sand mould (a)
and MMC complex-shape casting (b).

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RESULTS AND DISCUSSION

Cooling curves and cooling rates


In Figures 3 and 4 the cooling curves of the
materials investigated are reported for water-
cooled copper-mould castings and cylindrical sand
castings, respectively.
An estimation of the cooling rates experienced
by the composites on solidification was obtained
by calculating the first derivative of the
temperature-time curves.The cooling rate curves
are also reported in figures 3 and 4.
Interpretation of the cooling curves and their
derivatives can be obtained by knowledge of the
equilibrium solidification sequence and by other
published works [13,14]. It is well established that
the initially high cooling rate corresponds to liquid Fig. 3: Cooling curves and cooling rate curves of the copper permanent mould
castings.
cooling, solidification onset is marked by the
nucleation of primary a-Al phase from the liquid,
resulting in a large decrease of the solidification
rate with its main thermal effects corresponding
to the first downward peak in the cooling rate
curves.After a short period, the Al-Mg2Si-Si ternary
eutectic solidification occurs under quasi-
isothermal conditions, resulting in a plateau of the
cooling curve profiles.As a rough estimation, from
the recorded cooling curves, it is possible to state
that, at the first stages of solidification, the cooling
rate in the water cooled copper mould was of the
order of 200°C/min whereas the cooling rate in
the sand castings was of about 25°C/min.
Completion of cooling was reached after about
60 second in water cooled mould, while it took
about 10 minutes for sand mould.
Inspection of the cooling curves of the three
materials also suggests that the solidification Fig. 4: Cooling curves and cooling rate curves of the cylindrical sand castings.
behaviour of the matrix alloy is apparently not
affected by the presence of the SiC particles. As
expected, the length of the eutectic solidification
Microstructure
plateau is a direct function of the amount of alloy
poured into the moulds and therefore not strictly Preliminary analyses on the as received composite ingots were carried out
constant for the tests performed in this to identify the main phases in the unreinforced A360 alloy and in the
investigation. More accurate considerations would composite matrices. Irrespective of reinforcement content, the matrix alloy
suggest that the solidification time of the eutectic was formed by the α-Al solid solution and by four types of secondary
should also be proportional to the amount of phases. Electron probe microanalyses were carried out on unetched samples
matrix alloy (i.e. decreasing with increasing SiC to identify the nature of these constituents. Their chemical compositions
content) [14]. were analytically treated to account for the unwanted interaction of the X-
ray beam with the matrix surrounding the smallest phases [15]. Si platelets
and coarse primary Si crystals, Mg2Si, FeMg3Si6Al8, (FeMn)3Si2Al15 were
identified as the main intermetallics constituting the matrix alloy. These
phases could also be easily recognised in optical micrographs due to their
contrast in colour and typical shape, as shown in Figure 5a. The composite
structure additionally featured the presence of blocky-shaped, roughly
equiaxed SiC particles, whose average size was of 6 micrometers, as depicted
in Figure 5b.

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A) B)

Fig. 5: Representative micrographs of the as received A360 alloy (a) and of the A360-20%SiC composite (b). In figure 5a the labels
correspond to the following phases: (1) FeMg3Si6Al8; (2) (FeMn)3Si2Al15; (3) Si platelets; (4) Mg2Si.

A) B)

C) D)

Fig. 6: Micrographs of the unmodified sand cast A360 alloy (a), of the A360-10%SiC composite (b and c) and of the A360-20%SiC composite (d).

Analyses on the cylindrical sand castings showed that the reinforcement eutectic constituent at dendrite boundaries. High-
distribution was fairly homogeneous, at least on a macroscopic scale. From magnification views of the structure showed that
a microstructural viewpoint, it was noticed that the reinforcement particles the SiC particles featured well defined edges and
were preferably segregated in the interdendritic regions (Figure 6), i.e. SiC a shape substantially comparable to those detected
was pushed by the growing α-dendrites and gathered together with the in the as-received ingots, thus supporting the

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A) B)

Fig. 7: Comparison of the unmodified (a) and Na-modified (b) structure in the sand cast A360-10%SiC composite.

hypothesis of absence of significant matrix- observation that SiC particles can promote the formation of primary Si
reinforcement reactions occurring during melting crystals even in hypoeutectic alloys such as the A360 alloy matrix. The
and casting of the materials. In addition, it was nucleation role played by SiC is also confirmed by the fact that no primary
observed that coarse Si crystals were distributed Si crystals were detected by careful observations of the unreinforced A360
in the structure of the composites (arrowed dark alloy samples (see Figure 6a).
grey phases in Figure 6b). From inspection at higher The effect of Na-based modifier in order to change the shape of the Si
magnification, there was reasonable evidence that platelets is depicted in figure 7. It is inferable that the modified eutectic
these coarse crystals took their origins by features tiny Si particles whose shape is nearly spherical or at least equiaxed,
heterogeneous nucleation at SiC particles (light as opposed to the more elongated shape of the unmodified samples (see
phase containing several SiC particles in Figure 6c). also figure 5b). It is well established that this morphology gives improved
Similar conclusions concerning the nucleation of ductility properties when compared to the unmodified eutectic [14,18,19].
the Si phase at SiC particles were already given in Figure 8 depicts representative micrographs of the water-cooled copper-
literature for the eutectic Si platelets [2,13,16,17] mould cast composites. As already mentioned, these castings underwent a
and for the primary Si crystals [14]. Of particular rapid solidification leading to a much finer grain structure. For this condition,
relevance for the present investigation is the the size of the matrix grains became of the same order of magnitude of the

A) B)

Fig. 8: Optical micrographs of the water-cooled copper mould castings (a) A360-10%SiC composite, (b) A360-20%SiC composite.

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reinforcement particles. The tendency toward SiC clustering to dendrite reinforcement distribution in the liquid melt before
boundaries was thus less evident due to the limited segregation path allowed casting.
to the reinforcement. For this reason, the dispersion of reinforcement in Finally, it is worth emphasizing that the only casting
the copper mould cast composites was remarkably improved. However, defects detected consisted of small and isolated
lack of homogeneity was still noted in the A360-10%SiC composite in lower microvoids related to shrinkage phenomena, a few
magnification micrographs, where regions of reinforcement free matrix were tenths of micrometer in size, often located within
observed (Figure 8a). This effect was supposed to be related to uneven SiC particle clusters.

Hardness From analysis of the hardness data it can be stated


that the largest effect is played by the
Table II summarizes the average Vickers hardness values of the materials
reinforcement content, leading to a monotonic
investigated together with the standard deviation of data.
increase of hardness when increasing the SiC
Table II. Vickers hardness values of the materials content. As expected, solidification rate also plays
investigated a remarkable role, especially in the unreinforced
alloy, while the effects of Na-modification revealed
Alloy Copper mould Sand Sand casting to be less defined, being of the same order of the
casting casting (Na modified) experimental data scatter.
A360 78,6 ± 4,5 63,6 ± 2,6 -
A360-10%SiC 105,6 ± 4,1 97,0 ± 9,1 93,3 ± 8,0
A360-20%SiC 125,3 ± 10,8 107,3 ± 14,9 109,3 ± 11,8

CONCLUSIONS 4. In the solidified composites, the SiC particles


were generally located at dendrite boundaries
From the investigations on the A360-alloy based particulate-reinforced due to the pushing action exerted by the
composites, the following conclusions could be drawn. solidification front.When the dendrite-branch
1. The composites could be satisfactorily cast in different shapes and by size became of the same order of magnitude
different processes, experiencing a large range of cooling rates. of the particle size (copper moulds), this
2. Induction melting generally allowed to achieve good homogeneity of effects was less relevant. However, local SiC-
the molten alloy due to electromagnetic stirring.This effect also revealed depleted regions related to uneven
to be suitable to retain a satisfactory dispersion of the reinforcement reinforcement distribution in the liquid
particles, preventing SiC settling due to difference in density with the composite were still noticed in the 10%SiC-
matrix alloy. reinforced composites.
3. Sand casting were successfully produced by mechanical stirring of the 5. The presence of SiC particles also revealed
melt. Due to larger dendrite size, the SiC distribution was less to promote the formation of coarse primary
homogeneous from a microstructural viewpoint. Only small casting Si crystals in the composite structure.
defects related to microshrinkage phenomena were detected in the 6. Na-based modification of the eutectic was
sand cast samples. used during a set of sand casting of the
composites. The effectiveness of the Si-
platelets modification was demonstrated.

ACKNOWLEDGEMENT

The present research was performed with the financial support of


Fondazione CARIPLO. The authors would also like to acknowledge the
skilful contribution of Fonderia F.lli Liotti SrL (Verbania, Italy) for their support
in preparing the foundry sand castings and Mr. M. Pini for the laboratory
copper-mould castings.

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