CORROSION AND GALVANIC CORROSION OF DIE CASTED MAGNESIUM ALLOYS Senf, J.: Broszeit, E.; Gugau, M.

; Berger, C.; Darmstadt University of Technology, Institute of Materials Technology, Grafenstr. 2, 64283 Darmstadt, Germany Keq words: Corrosion, Galvanic Corrosion, Magnesium,

Abstract The corrosion and galvanic corrosion behaviour of four magnesium alloys (AZ 91 hp, AM 60 hp, AS 41 hp, AE 42 hp) are studied by using the salt spray test, electrochemical methods and a gaivanic corrosion test. Looking at the results under the salt spray conditions, one can make a clear ranking. AE 42hp shows the best corrosion behaviour, followed by AZ 91 hp and AM 60 hp. The corrosion attack at the samples made of AS 41 hp is under this conditions tremendous. The differences of the free corrosion potent~alsof the magnesiums alloys are significant. AM 60 hp is tlic noblest. AE 42 is the least noble alloy of all. The ~'Iec~.ochemical shows. that even slight polarisation of these test inaZnes1uln alloys leads to immense corrosion attack. Increasing the temperature or increasing the NaCI-concentration of the electrolyte increases the corrosion attack. The investigation also illustrates. that the used galvanic corrosion test is a easy handable method to study the galvanic corrosion behaviour of different materials. Within a short time one can make a ranking of suitable and less suitable combinations. Introduction Reduction of weight is one of the main topics for the automobile industry but also in many other fields of the engineering industry. To reduce the weight e.g. of a car, the construction for itself can be changed or "simply9' less heavy materials can be used. Typical light weight materials are plastics, reinforced materials and light metals. Looking at the recycling ability of these materials, usually light metals will be preferred. Aluminium is almost state of the art. but by using magnesium instead of aluminium the weight can he reduced again.

One main disadvantage of magnesium alloys is the chemical and electrochemical reactivity of this group of materials. Consequences of this reactivity are problems in functionality. reliabilitv and life time of machines and vehicles made of these alloys. High purity alloys have reduced corrosion sensltivit). But looking at corrosion behaviour. the corrosion of magnesium alloys for itself is only one part of the corrosion problem. Galvanic corrosion is the other and maybe the main part, especially for machines and vehicles. Typical for the galvanic corrosion of different metallic materials in contact with each other is the enhanced corrosion of the minor noble material. Magnesium alloys are the least noble metallic materials used for machine parts. In this paper results of electrochemical corrosion and galvanic corrosion tests of four pressure die casted magnesium alloys (AZ 91 hp, AM 60 hp, AS 41 hp, AE 42 hp) are presented and discussed. Looking at the galvanic corrosion the magnesium alloys were connected to different aluminium alloys typically used in the automotive industry. Experimental details Materials The corrosion behaviour of AZ 91 hp, AM 60 hp, AS 41 hp and AE 42 hp are studied. The chemical composition of the different alloys are given in table I. Hanawalt [I] shoned almost 60 years ago, that, looking at the corrosion behaviour of magnesium alloys, Fe, Ni and Cu are the most critical elements. High purity alloys like the one used for these tests are the results of the reduction of these critical elements.

Magnesium Technology 2000 Edited by H.I. Kaplan, J. Hryn, and B. Clow The Minerals, Metals & Materials Society, 2000
137

Table I Chemical composition of high purity magnesium alloys [2,3]

Four different aluminium alloys are used as contact partners for the galvanic corrosion tests. AlMn and AlMgSi 0,5 are wrought alloys, GD-AISi9Cu3 and GK-AISi6Cu4 are casting alloys. Differences between the casting alloys are first of all the chemical composition (Table III), but also the manufacturing processes (GD = pressure die casted, GK = permanent mould). Test Equipment and Conditions In industry the salt spray test is the standard test to study the corrosion behaviour of materials and complete components. In this examination the different magnesium alloys are also tested under salt spray conditions (German standard DIN 50 021 SS [5]). Three samples (30 x 100 x 20 mm3) of each alloy, completely covered with special varnish except one side (30 x 100 mm2), are placed for 96 hours in the testing chamber. Afterwards the samples are cleaned with a soft brush and put for 3 min in chromium acid (H2Cr04)at a temperature of 80" C. The quality of the unprotected surface of the samples is the criterium of corrosion attack.

misc.

< 0,Ol

>~

< 0,Ol

< 0,01

Physical and mechanical properties are given in table 11. There are almost no differences in the density, young's modulus and in [hi. linear thermal expansion of these four alloys, but looking at properties like the strength and fracture strain differences become u h ~ i u u sl'o point out the advantages of the different alloys, one can sa?. AZ 9 1 lip has the highest strength and excellent casting properties. AM 60 hp has good casting properties and very good fracture stram of about 10 %. The casting properties of AS 41 hp and especially of AE 42 hp are in contrast to the casting properties of AZ 91 hp and AM 60 hp very poor. AS 41 hp shows the best creep behaviour at high temperature and the alloy AE 42 hp is developed for better corrosion behaviour. Table I1 Physical and mechanical properties of high purity magnesium alloys [2,3]

1
density wm31 Young's moduius [MPa] tensile strength lMPal yield strength ILlPal fracture strain

1
1

AZ 91 hp 1,81

I 1
1

A M 6 0 hp 1,77

1
1

A S 41 hp 1,77

I 1
/

A E 42 hp 1,79

45 240 160

45 210 125 10 60 26,O

45 215 140 6 60 26,l

45 230 145 10 60 26,l

1'X, 1
Hriiwll hardness IHBS 1/51 lin. them. exp. coef. IumlmKI

3 70 26,O

Table 111 Chemical composition of the aluminium alloys 641

Basis of the electrochemical corrosion tests is German standard DIN 50 918 [6]. The computer-controlled test equipment (PGS 81 1 Banks) used for these tests is shown schematically in figure 1. All measurements are done with thalamid electrodes. All parts of the working electrode except the sample are made of PTFE. The surfaces of the samples are polished. 400 ml NaCl solutions (different concentrations) are used as electrolytes for the corrosion tests. The tests are done in two steps. First step (15 minutes) is the measurement of the free corrosion potential. Second step is the measurement of the current density subjected to the potential in the anodic or the cathodic area. Starting value of the second step is the free corrosion potential. The feeding rate of the potential is 1 Vlh. German standard DIN 50 919 [7] is basis of the galvanic corrosion tests. The test set up is shown schematically in figure 2. The reference electrodes are thalamid electrodes. The working electrodes are the same as for the corrosion tests (PTFE) and are positioned in a distance of 50 mm. The distance between reference electrode and belongmg working electrode is about 5 mm. The electrolyte volume (3 % NaCI) is 800 mi. The tests are done in three steps. First step ( 1 5 minutes) is the measurement of the free corrosion potential of anode (magnesium alloys) and cathode

(aluminium alloys). After 15 minutes the switch is closed (second step). During the next 5 hours 30 minutes the mixed potential and the current is measured. Afterwards the switch is opened again and the free corrosion potential at both electrodes is measured for 15 minutes (third step).

Tabel IV Free corrosion potential of different magnesium alloys in 3% NaCl at a temperature of 40 "C I AZ 9 l hp I AM 60 hp I AS 4l hp I AE 42 h p UQlmVl 1 -1296 1 -1269 1 -1335 1 -1399 The trend of the current-density - potential curves (figure 4) of all magnesium alloys are almost the same. Starting from the free corrosion potentials all curves are showing very strong slopes. No alloy shows a passiviation area, so slight shifts of the potential into the anodic area are very critical. It is astonishing, that AS 41 hp shows the lowest values (current density).

RE reference electrode a anode h kathode switch N sample width

Figure 2 Setup for the galvanic corrosion tests (German standard DIN 50 919 [ 7 ] )

Results Salt Spray Test After 96 hours salt spray test, the uncleaned surfaces of the samples made of AZ 91 hp, AM 60 hp and AS41 hp show typical white-gray corrosion products which are expected by magnesium. In contrast to this, the uncleaned surfaces of the samples made of AE 42 hp are dark black. The cleaning process removed the corrosion products from the surfaces and changed the dark layer at the surface of BE 42 hp into a gray iayer. The cleaned samples can be seen in figure 3. One can observe the typical filiform corrosion at the surface of AZ 91 hp, AM 60 hp and AS 41 hp. I.ooking at AE 42 hp the grey layer at the surface seems to be very rc9uia1- Obvious is the different intensity of corrosion attack. . \ l m o s ~ attack can be detected at AE 42 hp, the corrosion attack no at A S 4 1 h p is tremendous. Electrochemical Corrosion Tests influence of alloy Table IV shows the free corrosion potentials of the four magnesium alloys. The differences are significant. AE 42 hp is the least noble alloy (UR = -1399 mV). AM 60 hp is the noblest alloy.

-2000

-1500

-1000

-500

500

1000

potential IrnVHI

Figure 4 Current density - potential curves of different C magnesium alloys in 0,3 % NaCl at 40 O

Influence of concentration of electrolyte One can see at figure 5 the influence of different concentrations of a NaC1-solution to the corrosion behaviour of AZ 91 hp. Only the anodic part of the current-density - potential curve is measured. Increase of the NaCI-concentration leads to higher current densities, which is equivalent to increased corrosion attack, A concentration of 0,003 % NaCl corresponds to 18 ppm CI- and is about the same as tap water of the city of Darmstadt.

Figure 3 Cleaned surfaces of different magnesium alloys after 96 hours saltspray test, German standard DIN 50 021 SS
139

potential [mV/HI

potential ImVHl

Figure 5 Influence of the electrolyte concentration (anodic area) Influence of temperature Figure 6 illustrates the correlation of temperature and corrosion attach Increasing the temperature leads to increased corrosion a ~ t a c hand looking at the free corrosion potential, decreasing lcmperature means decreasing the potential. Galvanic Corrosion Tests As mentioned before, the galvanic corrosion test is divided into three phases. Figure 7 shows the three phases and schematically the belonging result. Characteristic values for phase 1 are the free corrosion potential URaland URkl(a = anode, k = cathode). During this phase the two electrodes / samples do not influence each other. The free corrosion potential (table V) corresponds to the free corrosion potential measured at the electrochemical corrosion tests. Phase 2 starts as soon as the two electrodes (samples) are connected to each other (closed switch, see figure 2). The mixed potentials (U,; Uk) and the current I, between anode (magnesium alloy) and cathode (aluminium alloy) is measured during this phase. Both potentials shift towards each other. Phase 3 is equal to

Figure 6 Influence of electrolyte temperature (anodic area) phase 1, anode and cathode are disconnected. Differences between phases 1 and phases 3 occur, because conditions ( e g electrolyte, surface of samples) are different.

Table V Free corrosion potential of different magnesium and aluminium alloys in 3 % NaCl at room temperature

GD-

GK-

I AIMgSi0,S I

AlMn

Looking at galvanic corrosion phase 2 is the most important phase. Characteristic value for the corrosion attack is the current I,.

phase 1

phase 3 ,

+ E
3
m
u u 0

.5
a
time t [s]
kontakt-pnnz dst

Figure 7 Result of the galvanic corrosion test (schematically)

I
I

AlMgS10.5
I

I gdlvanic cotmsion contact prtner ,4291 hp

I
Alkltl

p l i s hed electrolyte: teay?erdture:

456,3

3% NaCl mom teny.

1
1710,l telrqerxture: monl temp

Figure 8 Galvanic corrosion of AZ 91 hp contacted with different aluminium alloys in 3% NaCI-solution at room temperature.

Figure 9 Galvanic corrosion of GK-AISi6Cu4 contacted with different magnesium alloys in 3% NaC1-solution at room temperature. Tabel VI Average mixed potentials of different magnesium and aluminium alloys in 3% NaCl at room temperature
LLdlUk -

Taking the law of Faraday [8] AmlAt=eI m = mass t = time e = electroch. equivalent I = current there is a correlation between the reaction rate and the current. lhi: zlectrochemical equivalent is a material depending value. l'dlucs for the electrochemical equivalent are only known for pure n~atzrials(e.g. e ( ~ , ,= 24,32 glmol). Electrochemical equivalents for alloys are unknown. Transforming Faraday's equation into

2 AZ 91 hr,

GDAISi9Cu3

GKAlSiGCuJ

AIMgSi0,S (6060)

AlMn (3103)

-1234 mV

-1 179 mV

-1274 mV

-1283 mV

one can calculate characteristic values for the corrosion process. This product of current and time is marked in figure 7 as a gray colored area. Figure 8 illustrates the results of the galvanic corrosion tests of AZ 91 hp contacted with the different aluminium alloys in 3% NaCI-solution by using the method mentioned before. Figure 9 illustrates the results of the galvanic corrosion tests of GDAlSi6Cu4 hp contacted with the different magnesium alloys in 3% NaCI-solution also using this method. Looking at figure 8 it is obvious, that AZ 91 hp reacts totally different contacted with various aluminium alloys. Contacted with the aluminium casting alloys (GD-AISi9Cu3, GK-AISi6Cu4) the corrosion attack of AZ 91 hp is immense. But there are also o h ious differences between the combinations with the aluminium ~ ' ~ s t i nalloys. The combination AZ 91 hp 1 GK-AISi6Cu4 show g tl-ic \Lorst results. In contrast to this. the corrosion attack of .4%01 hp contacted with AlMn or AIMgSiO,5 is much lower. These are not only results of the calculation, it also can be seen looking at the samples. The differences between AZ 91 hp, AM 60 hp, AS 41 hp and AE 42 hp contacted with GK-AISi6Cu4 in 3% NaCI-solution are less obvious (figure 9). The corrosion attack is always tremendous.

The mixed potentials depend on the combinations of materials (table VI). The differences between U,and Uk are in the range of 20 - 50 mV and are strongly influenced by the exact position of the electrodes. Looking at the average mixed potentials one can see the different polarisation of contact elements. The aluminium - 600 mV). The alloys are strongly cathodic poiarised (AU, magnesium alloys are polarised into the anodic area ( A U=~ 30 to 200 mV). This various polarisation of the magnesium alloys leads to various corrosion attack.

Conclusion The corrosion and galvanic corrosion behaviour of four magnesium alloys (AZ 91 hp, AM 60 hp, AS 41 hp, AE 42 hp) are studied by using the saltspray test (German Standard DIN 50 021 SS), electrochemical methods (German Standard DIN 50 918) and a galvanic corrosion test (German Standard DIN 50 919). Looking at the results under the saltspray conditions (96 h), one can make a clear ranking. AE 42 hg has built up a protective (black colored) surface layer and shows almost no corrosion damage. AZ 91 hp and AM 60 hp are following with local filiform corrosion. The corrosion attack at the samples made of AS 41 hp is tremendous under these conditions. Electrochemical tests lead to the differentiation of the four magnesium alloys by the free corrosion potentials. AM 60 hp is the noblest, AE 42 is the least noble alloy of them. The trend of the current-density - potential curves is almost the same and illustrates, that slight polarisation of magnesium alloys into the anodic area leads to massive corrosion attack.

1 hi: ~ntluence temperature and concentration of the electrolyte of \bas also studied by using electrochemical methods. One can say, increasing the temperature (5 - 60 O C ) or increasing the concentration of the electrolyte (0,003% - 30% NaCI) increases the corrosion attack. This investigation also illustrates, that the used galvanic corrosion test is an easy handable method to study the galvanic corrosion behaviour of different materiais. Within a short time one can make a ranking of suitable and less suitable combinations. Under the specific conditions - 3% NaCl solution, 800 ml electrolyte volume, room temperature - the combinations AZ 91 hp / AlMn or AZ 91 hp I AlMgSi 0,s are much better then the AZ 91 hp with the aluminium casting alloys GK-AISi6Cu4 or GD-AISi9Cu3.

References Hanawalt, J. D.: Nelson, C. E.; Peloubet, J. A,; Corrosions studies of magnesium and it's alloys, Trans. AIME. Vol. 847, S. 273-299, 1942 DIN EN 1753 Blockmetalle und GuRstucke aus Magnesiumlegierungen, (1 997) Selektor fur Magnesium Eegierungen, Hydro Magnesium. ( 1996) Datta, J.: Aluminium-Schlussel, Key to Aluminium Alloys, Aluminium-Verlag Marketing & Komunikation GmbH Dusseldorf. 5. Auflage (1997) DIN 50 021, Spruhnebelprufung mit verschiedenen Natriumchloridlosungen, Beuth Verlag Berlin. DIN 50 918, Elektrochemische Korrosionsuntersuchungen, Beuth - Verlag Berlin, (1978) DIN 50 919, Korrosionsuntersuchungen der Kontaktkorrosion in Elektrolytlosungen, Beuth Verlag Berlin, (1984) Gellings, P.J.; Korrosion und Korrosionsschutz von Metallen; Carl Hanser Verlag Miinchen, (1981)

Acknowledgement The authors like to thank Mrs. B. Strobel for the preparation and documentation of the samples and Mr. Schroder for the expert technical support. The prqject is funded by the FVV c I-'or-schungs~zreinigung Verbrennungskraftmaschinen / Nr. 703 / 211.-1\1r 11507 N i I ) .