Paper No.

441

CORROSIONC.)7

CORROSION BEHAVIOR OF MAGNESIUM ALLOY AZ91 AND ITS MMC fN NaCl SOLUTION

W.M.Chmr*, F.T.Cheng*, L.K,Leung*, R.J.Horylev*, T.M.Yue+ *Department of Applied Physics and Materials Research Centre Department of Manufacturing Engineering The Hong Kong Polytechnic University Hunghom Hong Kong

ABSTRACT The corrosion behaviors of magnesium alloy AZ9 lC and its Al*O~(shott tibre)-reinforced metal matrix composite (MMC) in alkaline solutions (PH 10.5) contsiniig chloride were compared rising potentiodymnnic polarization measurements, electrochemical impedance spectroscopy (EIS) and immersion tests. Dependence of polarization characteristics (corrosion potential and corrosion current density) on chloride concentration was similar for both materials. The corrosion potential E..~ decrensed linearly with the logarithm of chloride concentration, while the corrosioncurrent density i,.m increased rapidly at chloride concentrations larger than 0.1A,with the i... for the MMC consistent Iy higber than that for AZ91C, reaching a factor of about 3 in 3.5Asodinm chloride solution. EIS data indicated that the protective film on the MMC was inferior to that on the matrix alloy. W]tb stirring and at frequencies higher than 5 Hz, the elecfrode/electrolyte interface might be described by the simplified Randles model for both materials. Immersion tests showed that the corrosion rate of the MMC, in terms of weight loss, was about 7 times that of tbe matrix alloy. Thus the present investigation indicated that in alkaline solutions containing chloride ions, the presence of Al~03 shofl tibres in the alloy did not drastically alter the corrosion behavior, but significantly reduced its corrosinn resistance.

Kewvords:magnesium alloy,Al*O~-reinforced metsl mabix composite, effect of chloride concentration, polarization,

cormison potential, corroison rate, electrochemical impedance spectroscopy.

INTRODUCTION The development of metal nmhix composites (MMCS) has been one of the major innovations in materials science and technology in the past 20 years. MMCS have been designed primarily for improvement in mechanical properties such as higher specific stiffrress and specific stiengtb. They may also possess other desirable properties compared with their matrix metals, such as a very low coefficient of thermal expsnsion and a h@r thermal deformation resistance. 12 Thus, MMCS are especially attractive in applications where it is advantageous to employ low density strncturd materials, such as in aerospace, automotive, medical and sports industries. On the other hand, owing to the presence of an addhiofml phase, the corrosion resistance of a metal ma!iixcomposite may be lowered by an amonnt dependent on the composite system and the fabrication route. Among the low density metals, A1-b8sed MMCS are well developed and their properties, inclndmg the corrosion behavinrs, quite extensively stndied. 3,4A firrtber and more ambitious step in weight savings is to replace Al-based materials
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by Mg-bnsed materials, as the density of Mg is 1.74g/cm3 (compared to 2.70g/cm3 for Al ). The Mg alloyAZ91 used in the present study is one of the two major Mg alloy systems available to designers and is probably the most corrosion resistant Mg alloys produced by conventional casting,s The incorporation of short fibres of AlzO~into AZ91C is an attempt to increase the mechanical stiength at a relatively low cost compared with continuous reinforcement. The present investigation aims at comparing the corrosion behavior of a magnesium-aluminum-zinc alloy, AZ91C, and ita alumina-reinforced MMC in alkaline solutions containing chloride. The effect of chloride concentration on the corrosion potential E.Om and the corrosion current density i,m was studied using potentiodynamic polarization tests. Electrochemical impedance measurements were also performed. Immersion tests were carried out to determine the corrosion rates of the materials in 3.50/.NaCl solution,

EXPERIMENTAL PROCEDURE Materials and Specimen Preparation The magnesium-aluminum-zinc alloy AZ91C nnd its short fibre-reinforced MMC were supplied in the form of a cast ingot. The composition of the matrix inwt OA was : Al-8.4, Zn-O.6g, MII-O.2,Si-O.02, Mg-hakmce. All the specimens of the AZ91C used in the present study bad been subjected to T6 heat treatment. The MMC contained 20 vol% A1203short fibres of average dkuneter-5 pmandaverage length-50 pm, rmdomly ofiented witihtie MMC. Alltie MMCspecimens had been subjected to solutionizing at 380C, followed by water quenching, Specimens used for polarization tests nnd impedance measurements were dkc-shaped, of diameter 16 mm and tldckness 3 mm, cut tlom the cast iergot. For immersion tests, rectangular plates of dimension 20nnn x 63mm x 3.5nnn were used. All specimens were polished with SiC paper of 600-grit and cleaned according to ASTM G 1-90 Standard 1)prior to all the tests, using acetone in a ultrasonic cleaner,

Potentiodymmic Polarization Measurements An EG&G potentiostat Model 273 2)wasused for the polarization tests, naing a pair of graphite rods m the counter electrode nnd the saturated calomel electrode (SCE) as the reference electrode. All polarization measurements were performed inaqueous NaClsolutionsatpH 10.5 and200C, with theconcentmtion of NaClva@ngf iomO%to 3.5%. The test solution was deaerated by purging it with nitrogen for one hour prior to measurement. The polarization scnn was started at about 200 mV below EC.*,scanning atarateof O.1mV/sinthe noble duectionuntil 1000 mV(SCE)wasreached.

AC fmpedance Measurements AC impedance measurements of AZ91C rmdthe MMC were performed br 3.5% NaCl solutions at pH 10.5 and 20C, using animpednnce analyzer Mode16310 (3).llesolutionwna not deaerated aadksolved oxygen hasnosignificnnt effect on thecorrosinn of Mgalloys! The solutinn wnagently stirred in subsequent measurements toensure uniformity withii the solution. The open-circuit potential EOC was monitored until a steady value was reached, AC impedance measurements were then made at this steady Ew from 100 ldfz to 1 MHz, with an amplitude of 7 mV.

Weight Loss Measurements Weight Iossmermrementsb yinnnersiontest were cnrried out in3,5%NaCl solution atpH 10.5 and20C, The snlution wasopen toairand theduration of the test was 3 days. The solutionvnhune-to-specinrenar earatio used was40 ml/cm2. At the end of the immersion test, corrosion products were removed using chromium trioxide according to ASTM G 1 Standard~4)

RESULTS AND DISCUSSIONS Potentiodymmric Polnrizatinn Menaurements The potentiodynnmic polarization curves of AZ91C and A1*OJAZ91C MMC in alkahne solutions at selected chloride concentrations are shown in Fig. 1. The polarization characteristics of the two materials were simh. It can be observed that as the chloride concentition increaaed from 076to 3.5A, the current density increased by 5 orders of ] AwrtiMSc4e!yf.r Tm@#,dtJa,aM$ 1)<41 EG&GIm.mcn!,CorW atbn 44112

magnitude at correspondhg potentials. Thus it may be concluded that the protective film was easily broken down by chloride ions even at a favorable pH of 10.5. Values of the corrosion potential Ewmand the corrosion current density i,Omextmcted from the polarization cnrves, were plotted against chloride concenbation and shown in Fig. 2 and Fig. 3 respectively. Variations of E- with chloride concentration were almost identical for both materials. In both cases, the variations obeyed a simple logarithm relationship, =a-blog E.OII with a= -1,48 = -1.52
and

[Cl]

where [Cl- ] was the chloride concentration in W%

for AZ91C for MMC for both AZ91C and MMC,

b = -0.12

The shitl of E... towards more active values as [Cl-] incrensed can be attributed to the adsorption of chloride ions on the electrode surface, thus changing the corrosion potential. At low chloride concentitions (below 0.1%), the corrosion cnrrent density was small, but at higher concentrations i~. incre~ed rapidly, bOtb fOrthe ~C md the matrix alloy. This can be attributed to the adsorption of chloride ions on the specimen surface, leading to film breakdown and formation of active sites. The cnrrosion current density of the MMC was consistently higher Omnthat of the matrix alloy, and more apparently so at higher chloride concentrations. At 3.50/,, the im. for the MMC was about three times that for the ma!rix alloy. Thus it nmy be concluded that in the case of the MMC, the protective film hss greater diff]ctdty in repairing itselt

AC Impedance Measurements Nyquist plots of AZ91C nnd A1203(short tibre)/AZ91C in alkaline solutions with 3.5% NaCl are shown in Fig. 4. Absence of the Warburg impedance indicated that the corrosion process was not controlled by difision through corrosion products on the specimen surface, while the contribution of ditlision of the reacting species through the solution was obviously insignificant, as stirring was present. Low-frequency (fs 5Hz) inductive loops were present in the Nyquist plots of AZ91C and its MMC. This might nrise from the adsorption and rapid desmption of reaction intermediate. The discussions above suggest that for~> 5Hz, the electrode/electrolyte interface can be modeled by a resistor ~ ( the polarization resistance) and a capacitor Cd ( the double-layer capacitance) in pnrallel. By using plots of& versus -c&, where ~. and -Zti are the real and imagimmypans of the AC impedance, ~ and C.Jwere determined. Values nf 1$ and Cd for AZ91C and its MMC are shown in Table 1. The relative values of ~ are consistent with the relative vnlues of i,m obtained horn polarization measurements, both benring a ratio in the range 3-4. The value of Cd for the MMC was larger than that for the matrix. The difference in i,.. and Cd between the AZ91C and its MMC might arise tlom two causes. Fust, the protective film on the MMC might be less protective than that on the matrix alloy*, Secnndly, the wetted area might be larger in the case of the MMC due to the presence of the A120Jrnatrix interfaces.

Weight Loss Measurements In 3.5% NaCl solutions at pH 10.5 and 20C, the corrosion rate, obtained tiom a 3-day immersion test, were -4g/ml/d for AZ91C and -30g/m2/d for the MMC, Tbus the corrosion rate of the MMC was about 7.5 times that of the matrix alloy. To compare WISratio with the ratio of the i,.mfrom pokuizatinn measurements, conversion is required. one has to take into consideration of the fact tba~ (i) the conducting nrea on the MMC specimen was less than the 1 cmz nominal electrode area due to the presence of the non-conducting AIZ03 ; (ii) weight Inss due to fall out of Al~03 when the matrix corroded was not reflected in the corrosion current; and (iii) the MMC and the matrix had a density ratio of 1.26, Assuming the area ratio and the volnme ratio of A1103in the matrix to be 0.2, ratio of calculated weight loss = ratio of icmm x ((1+0.2)/(1-0.2)) X 1.26 = 1.89 x ratin of ic.r =5.86, which is comparable to the measured weight loss ratio,

44113

CONCLUSIONS
1,

For Mg alloy AZ91C and its Al~03 (short fibre)-reinforced MMC, variation of the polarization characteristics with chloride concentration followed the same trend. Thecomosion potentials for botimaterials decreased linemly wititie logtiti oftiechloride concentition.

2. 3.

Atchloride concen@atiom smaller thm O.l%, tiecomosion rate, asrepresented bythecorrosion current density, was negligibly small. Above that concentmdion,th ecorrosionrate increased rapidly, with tbe MMCcorroding atahigber rate timtienon-rehforced matiixmeWl. In3.5%NaCl solution atpH 10,5 and 20C, tbei,.m forthe MMCwasaboutthree times that for the matrix alloy, indicating inferior corrosion resistance of the MMC. ~eEISdati at6equencies M@ertim 5Hzshowed thattie elec@ode/elec&ol~e htetiace for botimaterials mi@tbe characterized by the simplified Randles model. Values oftiedouble-layer capacitmce C~lmdtie comosion cmentdensi& i..~inticated tiat(i) tieprotective fib on the MMC was inferior to that on the matrix alloy and (ii) the wetted area on the MMC was larger due to the presence of the A1,O,/matrix interfaces. lntemsofwei@t loss, tiecomosion rate oftie MMCwasabout seven times thatoftie ma~ixalloy. reduced

4.

5.

6. 7.

Thepresence of AIZO, shofifibres htiealloy tidnot&astically its corrosion resistance by a factor of about six to seven,

alter tiecomosion behavior, butsi~ificmtly

REFERENCES 1. W. A. Femmdo, JomalofMaterials Engtieetig,l 1,4(1989) p.299-3l3.

2. R. G. Wendt, W. C. MosMer, B. Shaw, P. Miller, mdD. L. Oslon, Comosion, 50, l1(l994):p.8l9-826 3. K. A.Lucas, H. Clarke, Corrosion of Alwntilum-based Metal Matrix Composites, (New York, John Wiley and Sons, 1993) 4. H. K. Mak, F. T. Cheng, L. K. Lemg, T. M. Yue, ''Comosion Behavior of~8090 Paper 515, (Nate International, Houston Texas 1996) 5. A. F. Chmmasco, T. K. Aune, D. Hawke, W. Unswmth,J. Hills,ASMHandbook,V13,C International, 1990) p. 740-754. 6. M. G. FontiAComosion Engheerhg,3rd ed. ~ew York, McGraw-Hill, 1987), p.239. mdiSSiC MMC'', Comosion'96

orrosion,

10th ed. (Ohio, ASM

7. C, Gabrielli, Identification of Electrochemical Process by Frequency Response Analysis, (Solution Group, 1980); Ref(5), ASTM Standard G106. 8. M. Dattilo, Materials Perfommnce,25, ll(1986):p. l8-22.

TABLE 1 VALUES OF ~ AND Cd EXTRACTED FROM AC IMPEDANCE MESAUREMENTS 3,5% NaCl solution
AZ91C

&/(

Qcm2)
226

Cdll(fl

Icd

11.9

MMC

51

13,6

44114

.L5(
.,,,
1
0 % NaCl -12 AZ91C --

.1.0 MMC

.,.1 .1.2 .,.3. .1,4 .1.,.

I.u

x .

AZ91C WAC

.,., -

:~
Current Density (/+/cm*)
Fig. d. Polwlzatlon C.WW of A291C and lb Al,O,-relnfom,6d MMC in r.lkdlne solutions (PH 10.5) at various chlorlde Concentration.

\.

-17,~
Chloride Concentration in WY.

,0$

Fig. 2. Varhtlon of corro$ lo. rmtentlal In alkaline solutions (DH with chloride c.mcentratlon

x .AZ91 c 3.1+

MMC

/1

a
\

.W.84nlH

,:.3 ,&

10 Chloride concentration in wt% dmeny in

alkaline

,;.4

I
?0

~
Z,, ( Q cmz )

Fig. 3. Variation of .mrroslon mmunt

solutions

Fig, 4. Nyqulst plots of &?91C and its A120,-rein forced MMC in 3,5% NaCl s.alti.a at PH 10.5.

(pH 10.6) with chloride concentration.

44115