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PERGAMON
Corrosion Science 30 "0888# 418434

Corrosion behaviour of AA5950 and AA6994 reinforced with Al1O2 particles in aerated 2[4) chloride solutions] potentiodynamic measurements and microstructure evaluation
J[ M[ G[ De Salazar \ A[ Uren a\ S[ Manzanedo\ M[ I[ Barrena
Department of Materials Sciences\ Faculty of Chemistry\ Universidad Complutense de Madrid\ Av[ Ciudad Universitaria s:n\ 17939 Madrid\ Spain Received 12 June 0886^ accepted 4 September 0887

Abstract The in~uence of the heat treatments on the corrosion behaviour of three aluminium matrix composites "AA5950:Al1O2:09p19p and AA6994:Al1O2:09p# has been analysed in an aerated 2[4) sodium chloride solution[ Corrosion potentials were determinated in a 2[4) sodium chloride solution "NaCl# using the ASTM standard G58!70 0[ The galvanic series and the pitting potentials were calculated in this medium for all composites[ The following heat treatments were applied on the base composites] "a# as!received state "T3#\ "b# T5 treatment\ "c# an annealing\ consisting of a solution stage at 459>C for 2 h for the AA5950 MMC and "d# an annealing at 371>C for 1 h for the AA6994:Al1O2:09p\ followed by a cooling in the atmosphere furnace[ The localised corrosion susceptibility of each material and for each heat treatment were analysed by measure! ment of the cyclic potentiodynamic polarization[ Optical microscopy and SEM metallographic studies were carried out on the samples\ before and after corrosion tests\ to determine the in~uence of the microstructural changes during heat treatments on the corrosion behaviour[ 0888 Elsevier Science Ltd[ All rights reserved[
Keywords] Aluminium matrix composites^ Corrosion behaviour^ Polarization^ Microstructure

0[ Introduction Metal matrix composites "MMCs# as aluminium alloy "i[e[\ AA5950# reinforced with alumina particles are actually used in marine environments and are demanded\

Corresponding author[ E!mail] gsalazareucmax[sim[ucm[es 9909!827X:88:, ! see front matter 0888 Elsevier Science Ltd[ All rights reserved[ PII] S 9 9 0 9 ! 8 2 7 X " 8 7 # 9 9 0 2 4 ! 7

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in preference to the same unreinforced aluminium alloys\ for their superior mechanical properties "i[e[\ high sti}ness\ strength or wear resistance#\ and thermal or electrical properties[ These materials can also be tailored to satisfy speci_c requirements[ However\ in spite of their considerable properties\ MMCs based on particle reinforce! ment o}er minor property improvements when compared to those with _bre reinforce! ment\ but their lower cost make them more attractive than the continuously reinforced ones for applications such as automotive engines or airframe components 1\ 2[ Aluminium metal composites "AMCs#\ reinforced with alumina particles have\ as their main obstacle\ the anisotropic distribution of the particles in engineering applications generated during the fabrication processes "powder metallurgy\ com! pocasting\ squeezecasting\ in_ltration\ hot rolled extrusion etc[#[ Another con! sideration of AMCs is the in~uence of the reinforcement particles on the corrosion behaviour 3[ The possible reactions between some of the matrix components "i[e[\ Mg# with the Al1O2 particles during the fabrication process can have an important in~uence on the corrosion behaviour of aluminium:alumina composites 3\ 4 because of the depletion in Mg which occurs in the matrix around the particle produced by the interface reaction between the alloy and the alumina\ according to] 3Al1 O2 2Mg\2MgAl1 O3 and Al1 O2 2Mg\2MgO1Al[ There can also be other reactions in the matrix alloy\ such as 1MgSi\Mg1 Si\ "2# "1# "0#

which can provoke an additional Mg depletion\ in this case in the aluminium:Mg1Si intermetallic interface\ contributing in the same way to the corrosion behaviour of the AMCs[ Studies carried out on 5950:Al1O2 MMCs 5\ 6 have also reported the generation of a preferential corrosion through the ceramic:matrix interfaces[ On the other hand\ several corrosion studies 7 on MMCs showed that the reinforcements are the cause of the loss of corrosion properties due to chemical or mechanical facts\ such as] alloying segregation\ interfacial reactions\ oxidised layers\ residual stresses or high dislocation density around the reinforcements[

1[ Experimental procedure 1[0[ Materials] composition and microstructure The aluminium matrix composites evaluated in this investigation were two AA5950 alloys reinforced with 09 and 19 vol[) of Al1O2 particles and an AA6994 alloy reinforced with 09 vol[) of Al1O2p[ These composites were manufactured by

J[M[G[ De Salazar et al[:Corrosion Science 30 "0888# 418434 Table 0 Chemical composition composite matrices "elements wt)[# Material AA5950 "09)# p AA5950 "19)# p AA6994 "09)# p Si Fe Cu Mn Mg Cr Zn Ti Al

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9[44 9[95 9[16 9[994 0[11 9[01 9[992 9[997 bal[ 9[44 9[95 9[16 9[993 0[04 9[01 9[90 9[90 bal[ 9[59 9[962 9[28 9[87 9[04 2[7 bal[

DURALCAN USA and supplied in the form of 5 mm thick sheets in the extruded condition[ Table 0 shows the chemical compositions of the aluminium matrices[ Several heat treatments were applied\ both on the composites and the parent alloys as indicated below 8] 1[0[0[ AA5950 09pAA5950 19p 0[ As received "T3# 1[ Solution at 459>C for 2 h\ quenched in water at 19>C and aged for 7 h at 064>C "T5#[ 2[ Solution at 459>C for 2 h\ quenched in water at 19>C and aged for 09 h at 249>C "Over!Aged# "OHA#[ 3[ Solution at 459>C for 2 h\ and slow furnace cooling "annealed# "An#[ 4[ Solution at 459>C for 2 h\ quenched in water "solubilisation# "Q#[ 1[0[1[ AA6994 09p 0[ As received "T5#[ 1[ Solution for 1 h at 371>C\ and slow furnace cooling "annealed# "An#[ Figure 0 "AA5950:Al1O2:09p as representative sample# shows the typical micro! structure of one of these materials with Al1O2 particles aligned along the extruded direction "marked L#\ particle!free zones and clustering areas are commonly observed[ The stereological parameters have been determined using image analysis and quan! titative metallography] "length perimeter\ roundness\ and area ) of the alumina particles#[ The results shows values very similar along the L\ TL and TC directions[ Table 1 shows these average values[ Figure 1 shows the microstructure "by TEM# of the interface between alu! mina:aluminium in these composite materials[ Idiomorphic crystals of spinel "MgAl1O3# are present[ The presence of this spinel in these composites originates during their fabrication process "Duralcan U[S[A[#[ The proportion of this Mg!spinel will depend on the process temperatures and of the presence of other alloying elements such as Zn or Si\ which is di}erent for the 5950 and 6994 AMMCs Table 0[

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Fig[ 0[ Microstructure of the MMC:AA5950:Al1O2:09p "SEM#[

Table 1 Stereological parameters of the MMCs obtained by image analysis[ Material Length "mm# 0622 1622 0722 Perimeter "mm# 4122 7522 4622 Roundness Area "L# ")# 0123 1323 0123 Area "TL# ")# 0223 1023 0123 Area "TC# ")# 0223 1223 0123

AA5950 "09)# p AA5950 "19)# p AA6994 "09)# p

9[5029[94 9[4529[94 9[4629[94

1[1[ Electrochemical measurements The electrochemical behaviour of the composites was carried out using an AgCl:Ag reference electrode in a 2[4) NaCl aerated solution "pH 5[73#[ The cyclic polarisation curves were obtained using the same electrolyte and a reference electrode[ A Pt counter!electrode was used[ Tests were carried out using a scanning rate of 0 mV:s[ Pitting potential "Epit#\ corrosion potential "Ecorr# and intensity of corrosion "icorr# were calculated from the polarization curves[ Pitting on samples was carried out using the pitting corrosion potential "49 mV above Epit# for 04 min[ The polarisation behav! iour was examined for the range 899 mV to 499 mV and then returning to 899 mV[ Test samples were allowed to equilibrate their corrosion potential "Ecorr# before measuring it[

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Fig[ 1[ MgAl1O2 crystal growing from the Al1O2 to the Al matrix "TEM#[

For all tests\ three rectangular electrodes of each material were tested in order to ensure a good reproducibility of the results[ They were cut from sheets with an area of 0 cm1[ Electrical connections were obtained by welding a copper wire using a condensater discharge and mounting it in polyester resin[ The surfaces were ground in emery paper\ up to 599 grade\ in order to obtain 9[0 mm Ra roughness in the aluminium alloy matrix\ and ultrasonically washed to degrease them[ The real areas of the aluminium matrix were calculated by subtracting at the parallelepiped the total area occupied by the alumina particles Table 1[ For metallographic studies by SEM\ the samples were washed in an ultrasonic bath to clean the corrosion products and to obtain good conductivity in the alumina particles\ it was necessary to coat them with a gold _lm by sputtering 09[

2[ Experimental results 2[0[ Corrosion behaviour The cyclic polarisation curves of both AA5950 and AA6994 composites in aerated 2[4) NaCl solution\ and the Rp curves were found to be similar for all tests "Figure

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Fig[ 2[ Representative potentiodynamic polarization curve "Ag:AgCl:2[4) NaCl#[

2#[ 2D bar graphics show the experimental values Fig[ 3"AD# and\ in Table 2\ the same parameters for the aluminium AA5950 and AA6919 alloys are shown[ From the potential:current density curves Fig[ 4"A\B and C#\ it can be deduced that the studied AMCs present a similar behaviour in NaCl solution "2[4)#\ although the corrosion mechanims could be di}erent[ Only a change in the Ecorr for the AA6994:Al1O2:09p composite has been observed\ due to its elevated Zn composition with respect to both the AA5950:Al1O2:09p and AA5950:Al1O2:19p composites[ Another fact is the variation that exists with respect to the ERp value\ which changes with the heat treatment carried out on the samples although this variation is not signi_cant[ There is only a di}erence of 49 mV among them " for the same aluminium matrix#[ In order to compare the corrosion behaviour of the MMCs with the unre! inforced aluminium base alloys "AA5950 and AA6919#\ the same tests were carried out on them[ Table 2 shows these results[ 2[1[ Morpholo`ical studies Pitting morphological studies were carried out using the ASTM G35!65 standard on specimens held for 04 min at 49 mV above Epit in 2[4) NaCl solution[ Pitting corrosion on the MMCs "both with AA5950 and AA6994 matrix# in the T5 condition begins around the intermetallic compounds such as Mg1Si or Al2Fe "Figure 5 and Fig[ 6\ respectively#[ Similar corrosion mechanisms are present around the alumina particles with formation of spinel in the interface "Figure 7#[ When the heat treatment is the T3 one\ the pitting corrosion is higher on the tested

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Fig[ 3[ "a# icorr values for the di}erent specimens in an aerated Ag:AgCl:2[4) NaCl solution[

Fig[ 3[ "b# EOp[C[ values for the di}erent specimens in an aerated Ag:AgCl:2[4) NaCl solution[

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Fig[ 3[ "c# Ecorr values for the di}erent specimens in an aerated Ag:AgCl:2[4) NaCl solution[

Fig[ 3[ "d# EPit values for the di}erent specimens in an aerated Ag:AgCl:2[4) NaCl solution[

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Table 2 Eoc\ Ecorr\ Epit and icorr values obtained from three tests of the aluminium base alloys tested in aerated Ag:AgCl:2[4) NaCl solution[ Material AA5950 as rec[ "T5# AA5950 "Q# AA5950 "OHA# AA5950 "An# AA6919 as rec[ "T5# AA6919 "An# Eoc "mV# 697 581 611 602 756 780 Ecorr "mV# 575 589 630 580 744 763 Epit "mV# 564 569 564 589 723 758 icorr "mA:cm1# 9[23 9[19 1[0 9[44 9[17 9[18

specimens[ The natural ageing leads to a fault of homogenisation around the alumina particles with spinel formation[ The level of pitting corrosion is higher in MMC5950:Al1O2:19p than in MMC5950:Al1O2:09p\ as a consequence of the higher percentage of alumina particles[ Figure 8 shows an SEM image of the holes formed along the grain boundaries of the matrix[ The annealed treatment "An# on the AA5950 MMCs favours a more generalized attack on the surfaces\ which takes place principally through the interface between the alumina particles with spinel formation and the aluminium matrix[ This corrosion process can be due to the presence of intermetallic compounds formed during the slow cooling in the furnace[ The Mg depletion means that the zones adjacent to the particles present a lower Mg content and\ for this reason\ the corrosion is more intensive[ It leads to the presence of holes and free alumina particles on the tested surfaces\ which has been observed by SEM in the MMC5950:Al1O2:19p[ If the sample is the MMC6994:Al1O2:09p "An#\ the corrosion is more generalised[ The interface alumina:matrix presents a low corrosion susceptibility in relation to the AA5950MMCs[ It is because there is a lower spinel formation around the alumina particles\ due to the presence of Zn in the matrix\ which compensates for the e}ect of Mg depletion00 "Figure 09#[ The over!aged heat treatment "OHA# carried out on the MMCs "5950:Al1O2:09p and 5950:Al1O2:19p# leads to intensive pitting corrosion both on the matrix and through the interface alumina:matrix[ In Fig[ 00\ the presence of holes and free alumina:spinel particles are again observed[ The typical morphology of the pits in a transverse section is shown in Fig[ 01[ The depth of these pits\ having a variation from 19 to 02922 mm\ depends on the heat treatment carried out on the MMCs[

3[ Discussion Both from microscopic and analytical observations\ the following corrosion mech! anism for these aluminium based composites reinforced with alumina can be proposed "Figure 02#]

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Fig[ 4[ "a# Potential versus current density curves of the AA5950:Al1O2:09p MMC[

Fig[ 4[ "b# Potential versus current density curves of the AA5950:Al1O2:19p MMC[

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Fig[ 4[ "c# Potential versus current density curves of the AAC6994:Al1O2:09p MMC[

Fig[ 5[ Mg1Si present in the matrix of the both AA5950 metal matrix composites[

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Fig[ 6[ Al2Fe present in the matrix of the AA6994 metal matrix composite[

Fig[ 7[ Incipient pitting corrosion in the matrix through the interface Al1O2:matrix in the AA5950: Al1O2:19)p "T5# MMC[

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Fig[ 8[ SEM image of the holes formed along the grain boundaries in the matrix of the AA5950:Al1O2:19)p "T3# MMC[

Fig[ 09[ Localised corrosion of the aluminium matrix around alumina particles in the AA6994:Al1O2:09)p "An# MMC[

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Fig[ 00[ Holes and free facetted alumina due to an intensive matrix corrosion in the AA5950:Al1O2:19)p "OHA# MMC[

Fig[ 01[ Typical morphology of the pits in a transversal section in both AA5950 MMCs[

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Fig[ 02[ Diagram of the theoretical corrosion model of aluminium matrix composites[

Mg depletion zones have an anodic behaviour in relation to the adjacent zones that present higher Mg contents "cathodic zones#[ The corrosion of the composites takes place preferentially near to the intermetallic phases\ such as Mg1Si "noble precipitate\ Fig[ 5#\ because of the minor Mg content in the adjacent matrix 5\ and around the alumina particles that present higher amounts of magnesium spinel Fig[ 7[ Around Al2Fe precipitates\ which are also considered as a noble phase by other authors 01\ a very local matrix dissolution can appear Fig[ 6[ If in the matrix there are higher amounts of alumina particles with spinel formation in cluster form\ these zones will show preferential corrosion behaviour in relation with others which have lower proportion of alumina crystals[ From these considerations\ the corrosion behaviour in relation to the heat treatment is the next] Samples with T5 and T3 heat treatments show lower generalized corrosion\ preferentially the corrosion is in pit form\ which has a depths between 1959 mm[ Samples with annealing and over!aged heat treat! ments show a higher corrosion behaviour\ which is normally in generalised form[ In these cases\ the pits have a depth between 59029 mm[ In their surfaces appear holes and free alumina particles\ which show their typical facets Fig[ 01[ This mechanism is available for the corrosion behaviour of the AA5950:Al1O2 composites\ but in the case of the AA6994:Al1O2 ones\ the pitting corrosion is less marked due to its lower proportion of spinel phase in relation with the AA5950:Al1O2 composites[ This fact provokes a lower Mg depletion and\ even if it appears\ the presence of Zn in the matrix will minimise this e}ect[ In the AA6994 matrix\ the MgZn1 intermetallic has been detected\ but this phase has a similar Ecorr to the matrix

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ones[ For this reason\ it does not have any in~uence in pitting corrosion behaviour 00[

4[ Conclusions 0[ The open circuit corrosion potentials "Eoc# that have been obtained from the AA5950 metal matrix composites reinforced with alumina particles "09)p and 19)p# do not present important variations in relation to the unreinforced alu! minium alloys with the same heat treatment[ 1[ The heat treatments carried out on the aluminium matrix composites do not a}ect the Ecorr obtained from the polarization curves for the AA5950:Al1O2:09p[ However\ these heat treatments "i[e[\ annealed# present a higher in~uence on the Ecorr in the case of the AA5950:Al1O2:19p composite[ 2[ The pitting corrosion mechanisms for the AA5950 metal matrix composites reinforced with alumina particles "09)p and 19)p# are a}ected by the heat treatments applied[ The number of holes "pits# increases according to the next sequence] T5\ T3\ annealed and over aged heat treatments[ The pitting corrosion is always higher for the AA5950:Al1O2:19p than for AA5950:Al1O2:09p composite[ 3[ AA6994:Al1O2:09p composite presents lower Ecorr and Eoc with respect to the AA5950 MMCs "below 199 mV#[ The Epit has the same behaviour as the Ecorr and does not present a higher pitting corrosion susceptibility in the tested aqueous solution[

Acknowledgements The authors wish to thank the CICYT for supporting the present research "Project[ MAT85!9875!C91!90#[

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