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A CASE HISTORY:
WHEN ANODES AINT ANODES
B. Gerittsen1, B. Linde2
1
Australasian Corrosion Consultants, 2Cathodic Diecasting
SUMMARY: A domestic hot water unit supply company had distributed a large number of hot water
service units that were experiencing high gas levels at installation, and in one instance a shower head was
propelled across the bathroom. Further investigation showed the anode was being consumed within 2-3
months. This paper details the steps followed in investigating the problems experienced, including analysis
of the water quality at several sites, as well as the anode consumption rates. This lead to the anode alloy
being analysed using an Arc Spark Spectrometer as well as Atomic Absorption Spectroscopy. The testing
revealed that the Magnesium alloy did not meet any recognised Australian or international anode
specification as it contained low levels of Manganese. The paper gives a brief discussion of the reasons for
the extremely high consumption rate.
Keywords: Cathodic Protection, Magnesium Anode, Chemical Analysis, Manganese, Iron.
1. INTRODUCTION
The sacrificial anodes in domestic hot water services installed in Queensland and Victoria were reported as being consumed
well under their expected service life and produced copious amounts of gas, to a point in one case in Western Victoria where
a householder when turning on the hot water in a shower reported that the shower rose was blown across the bathroom. These
events were causing the manufacturers loss of consumer confidence in their product as well as setting up a dangerous
situation given that the gases produced are hazardous.
2. REQUIREMENTS FOR SACRIFICIAL ANODES UNDER AS4692.1 [1] AND DIN 4753 PART 6 [2]
The Australian Standard AS4692 Electric Water Heaters Part 1 Energy consumption, performance and general requirements
specifies that, where required, the installation of sacrificial anodes in hot water services mandates that manufacturers provide
for 3 different types of anodes for water heaters in their designs. The anode types are to comply with Australian
StandardAS2239 [3] and use the M1and M2 and A5alloys and shall have a steel core. The composition in accordance with
AS2239 of the 3 anode alloys are shown in table. The standard does not specify where each type of anode is to be used; this is
left to the hot water system manufactures.
The hot water service units supplied as part of this case are manufactured in Europe and the sacrificial anodes supplied were
to adhere to DIN 4753 Part 6. This Standard specifies magnesium anodes are to be used for enamelled containers and they
shall have a minimum maintenance free period of 2 years. The alloying contents are given in the DIN Standard:
3.3.1 Galvanic anodes
For physiological reasons, the total contents of antimony, arsenic, lead, chromium and nickel shall be less
than 0,1 % by mass, and the total contents of cadmium, mercury and selenium less than 0,01 % by mass.
In the case of galvanic anodes made from magnesium and its alloys with aluminium, zinc, manganese and
silicon, the total of the contents of the elements referred to shall amount to not less than 99,79% by mass.
For technical reasons, the total of the iron and copper contents shall in be less than 0,1% by mass.
While DIN 4753 Part 6 does not specify a steel core it does require that the anode shall remain effective for at least two years.

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It is interesting to note that both the Din and Australian/New Zealand Standards warn against the build up of hazardous gas
when water is not drawn from the system for a period of time.
Table 1 AS2239 A5, M1 and M2
Element

Aluminium Alloy Anode

Designation

Cast or Extruded High

Potential

Extruded Low Potential

AS 2239 A5

Designation M1

Designation M2

Min%

Max%

Min%

Max%

0.25

Iron
Tin

Magnesium Alloy Anodes

0.05

Max%

0.03

0.003

0.05

0.05

0.02

0.006

0.25
0.25

Silicon
Copper
Aluminium
Zinc

Min%

4.0

Remainder

0.01

2.5

3.5

5.0

0.02

0.7

1.3

1.3*

0.2

1.5

0.5

Manganese

0.001

Nickel

0.001

0.005

Cadmium

0.04

Calcium
Remainder

Magnesium

0.04
Remainder

Other impurities
0.05

Each
0.15

Total
Theoretical
Density

0.30

2.92

1.79

0.30
1.79

* In the range 0.50 to 0.80%, the percentage of manganese is required to be at least 0.5 + (60% x aluminium)

In comparing the three magnesium alloys i.e. DIN 4753 Part 6, M1 and M2 some simple arithmetic shows the minimum
magnesium content for each magnesium anode type is:
DIN 4753 Part 6

99.79% by mass

AS2239 M1 (High potential)

98.229% by mass

AS2239 M2 (Low potential)

93.34% by mass

Further, both M1 and M2 alloys call for minimum quantities of manganese while the DIN anode does not specify a minimum
but allows for aluminium, zinc and manganese in their anodes.
3. ANODE SELCTION
The selection of anode types under the Australian/New Zealand Standard is the prerogative of the manufacturer and appears
to form part of their warranty conditions. A typical anode selection chart is given in figure 1. The chart is taken from the
Owners Guide and Installation Instructions Electrical Heavy Duty Water Heater issued by Rheem [4].

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Figure 1 Water Quality Chart

The left column of figure 1 has been summarised by Rheems manual as shown in table 2.

Table 2 Summary of Water Quality Chart

The anode colour code given in both figure 1 and table 2 relates to the type of anode used. Table 3 has been produced by
Cathodic Dicasting and shows the anode colour coding used by Rheem against the water quality and anode types as specified
by AS 2239.
Cap Colour Code

Material/Potential

Green

Magnesium High Potential

AS2239-M1

0 40 mg/L

Orange or Black

Magnesium Low Potential

AS2239-M2

40 600 mg/L

Blue

Aluminium AS2239-A5

600 2500 mg/L

Table 3 Anode Colour Coding

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Total Dissolved Solid

(TDS) Content

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4. POTABLE WATER TESTS

From the guidance information given for Australian conditions the type of galvanic anode to be used in hot water services has
been well documented. Therefore in this case the first investigation was to check the water quality at the location in which the
service was to operate. A total of three tests were conducted the first is a laboratory test conducted by Wide Bay Water
Corporation (QLD). Two tests on Victorian water samples were carried out by Australasian Corrosion Consultants.
4.1 Queensland Laboratory
The Queensland water test results in terms of relevant parameters for the selection of a galvanic anode indicated the
Conductivity was 400S/cm (2500 ohm cm). The type of anode to be used in this situation therefore is the black cap i.e.
AS2239-M2 low potential anode. It was further noted that the level of magnesium was very high at 9.28mg/L, while the
optimum level is less than 0.05md/L.
The calculation of the Saturation Index would give an indication of the corrosivity of the water contained in the hot water
service. While the total dissolved solids (TDS) were not given in the water analyses an approximation for the TDS can be
made as the conductivity is directly proportional to the TDS content of the water and that the TDS in mg/L is approximately
70% of the conductivity in S/cm. Then using an approximated TDS of 280 mg/L, an assumed temperature of 20oC,
measured pH of 5.2, measured Total Hardness of 32 mgCaCO3/L and measured Total Alkalinity of 8 mgCaCO3/L a Langelier
Saturation Index of -4.42 results indicating the water is corrosive and not subject to scaling.
4.2 Victorian Off Site Tests
The tests carried out on the two Victorian water samples were limited to water resistivity, temperature and pH. The same test
was conducted on the sample of Melbourne tap water for comparison. The results are given in Table 4.
Test

Sample 1

Sample 2

Melbourne tap water

Water resistivity (ohm cm)

13220

17640

6420

pH

7.29

5.97

7.72

Temperature (oC)

19.8

21.4

23.5

Calculated conductivity (S/cm)

75.64

56.69

155.76

Table 4 Potable Water Test Results (Victoria)

4.3 Water quality discussion
The water quality tests when applied to figure 1 indicate Green cap (high potential) anodes should be used in the Victorian
hot water services at the sites from which the water samples were supplied and Black capped (low potential) anodes in the
Queensland hot water services at the water sample site.
We understand that all anodes were of the black cap type (low potential) which by inference indicates the output currents
would be low in the Victoria sites and may not provide sufficient protection. The low currents also indicate that if correctly
designed, the anodes would not be consumed in the short period reported.
It should be noted that even in a single location the characteristics of the water can vary significantly with seasonal variations
and rainfall. This can have an effect on the selection of the most appropriate anode alloy.
5. ANALYSIS OF THE ALLOY
Cathodic Diecastings involvement commenced with the analyses of the chemical composition of one of the anodes which
was imported with the hot water service units. The anode came from a brand new hot water service unit which was installed
in the Warnambool area in western Victoria.

5.1 Consumption Rate

After 3 months of service the anode was removed. In that time it had lost 30% of its mass. Clearly the anode does not comply
with the DIN 4753 Part 6 standards requirement for the anodes to have a minimum maintenance free period of 2 years.

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5.2 Alloy Composition

Figure 2 Case Study Anode

Examination of the corrosion

pattern shows pronounced layers
of anodic and cathodic areas
adjacent to each other almost in
bands around the anode.
We cut 3 samples from the anode
and analysed each on our Optical
Emission Spectrometer.

Figure 3 Case Study Anode Close-Up

The results were as follows.

Table 5 Optical Emission Spectrometer Analysis
Sample

Aluminium
(Al)

Iron
(Fe)

Copper
(Cu)

Manganese
(Mn)

Lead
(Pb)

Nickel
(Ni)

Zinc
(Zn)

Cadmium
(Cd)

Calcium
(Ca)

Silicon
(Si)

Magnesium
(Mg)

2.44

0.003

0.0016

0.0

Not

0.0012

0.68

Not

Not

0.02

Remainder

2.25

0.005

0.0024

0.0

Tested

0.0014

0.65

Tested

Tested

0.02

Remainder

2.41

0.005

0.0026

0.0

0.0014

0.71

0.02

Remainder

These results were verified by Atomic Absorption Spectroscopy.

Table 6 Atomic Absorption Spectroscopy

Sample

Aluminium
(Al)

Iron
(Fe)

Copper
(Cu)

Manganese
(Mn)

Lead
(Pb)

Nickel
(Ni)

Zinc
(Zn)

Cadmium
(Cd)

Calcium
(Ca)

Silicon
(Si)

Magnesium
(Mg)

2.4

0.005

0.002

0.039

0.002

<0.001

0.67

<0.001

0.002

Not

Remainder

2.5

0.004

0.002

0.040

0.002

<0.001

0.71

<0.001

0.001

Tested

Remainder

2.5

0.004

0.003

0.040

0.002

<0.001

0.70

<0.001

0.003

Remainder

There are some minor variations between the 2 analysis methods, but essentially for our purposes the readings are consistent.
For the purposes of comparison we have averaged the Atomic Absorption results (+ added the Optical Emission Spectrometer
results for Silicon), see table 7.

Table 7 Atomic Absorption Spectroscopy AVERAGE

Sample

Aluminium
(Al)

Iron
(Fe)

Copper
(Cu)

Manganese
(Mn)

Lead
(Pb)

Nickel
(Ni)

Zinc
(Zn)

Cadmium
(Cd)

Calcium
(Ca)

Silicon
(Si)

Magnesium
(Mg)

AVE.

2.5

0.004

0.002

0.040

0.002

<0.001

0.69

<0.001

0.002

0.02*

Remainder

*result from Optical Emission Spectrometer Analysis

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5.3 What standard does the alloy comply with?

ASTM Standard AZ31B [5] was the closest match, which is one of the most commonly produced low potential anode alloys
for extruded magnesium. All elements comply; with the notable exception of manganese which was well below the range
specified in AZ31B (refer to table 8).

Table 8 Comparison of ASTM AZ31B and Sample

Aluminium
(Al)

Iron
(Fe)

Copper
(Cu)

Manganese
(Mn)

Lead
(Pb)

Nickel
(Ni)

Zinc
(Zn)

Cadmium
(Cd)

Calcium
(Ca)

Silicon
(Si)

Magnesium
(Mg)

AZ31B

2.5 to 3.5

0.005
max

0.05
max

0.20 1.0

0.005
max

0.6
1.4

0.04
max

0.10
max

Remainder

Sample

2.5

0.004

0.002

0.040

0.002

<0.001

0.69

<0.001

0.002

0.02*

Remainder

The M2 alloy from AS2239 is the Australian equivalent to AZ31B, but has tighter tolerances for some elements. When
comparing the sample with M2, three elements that do not comply. The iron is high, the zinc is low and again the manganese
is extremely low (refer to table 9).

Table 9 Comparison of AS2239-2003 M2 and Sample

Aluminium
(Al)

Iron
(Fe)

Copper
(Cu)

Manganese
(Mn)

Lead
(Pb)

Nickel
(Ni)

Zinc
(Zn)

Cadmium
(Cd)

Calcium
(Ca)

Silicon
(Si)

Magnesium
(Mg)

M2

2.5 to 3.5

0.003
max

0.006
max

0.20 1.5

0.001
max

0.7
1.3

0.04
max

0.05
max

Remainder

Sample

2.5

0.004

0.002

0.040

0.002

<0.001

0.69

<0.001

0.002

0.02*

Remainder

If we compare the alloy composition of the sample with the alloy composition that is designated according to the anode
selection chart and the potable water tests, the sample should have been a high potential anode (green cap). Again the sample
does not comply. The aluminium and the zinc are high and again the manganese is very low (refer to table 10).

Table 10. Comparison of AS2239-2003 M1 and Sample

Aluminium
(Al)

Iron
(Fe)

Copper
(Cu)

Manganese
(Mn)

Lead
(Pb)

Nickel
(Ni)

Zinc
(Zn)

Cadmium
(Cd)

Calcium
(Ca)

Silicon
(Si)

Magnesium
(Mg)

M1

0 0.01

0.03
max

0.02
max

0.50 1.3*

0.001
max

0.02
max

0.04
max

0.05
max

Remainder

Sample

2.5

0.004

0.002

0.040

0.002

<0.001

0.69

<0.001

0.002

0.02*

Remainder

*In the range 0.50 to 0.80%, the percentage of manganese is required to be at least 0.5 + (60 x %aluminium)

It appears likely that the alloy was supposed to be cast as AZ31B, but the manganese was either not added during alloying or
it was added but the alloying temperature was not hot enough to sufficiently dissolve the manganese, resulting in lots of small
globules or pieces of manganese throughout the alloy, rather than being homogenous. Examination of the microstructure
of the sample would determine whether the manganese was added or if it was adequately dissolved. If the manganese is
present in globules it would be visible as small grey particles spread amongst the much lighter coloured magnesium,
indicating that the alloying temperature was too low during extrusion.

5.4 Interpreting the Results

The chemical analysis clearly indicates a very low level of manganese. There are a number of papers that address this subject.
A paper presented by G.T. Parthiban, N. Palaniswamy and V.Sivan [6] shows the importance of the manganese content in
magnesium anodes. The report suggests that the addition of manganese has a marked influence on the corrosion pattern.

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Samples with low manganese have a large grain structure which are subject to severe pitting with pronounced ridges and
craters (similar to the anode we analysed). As the manganese content increases (to a certain level) the grain structure was
observed to become more refined and produced a more even corrosion pattern. The finer grain structure, as a result of the
inclusion of manganese, exhibited reduced self corrosion and higher anode efficiency. The report also suggests that lower
manganese concentrations are unable to suppress the effects of impurities, especially iron.
According to a paper presented by J.G. Kim and S.J. Koo [7], the addition of manganese improved the drive potential and
anode efficiency. The paper also indicates that manganese acts as a scavenger element for controlling the effects of impurities
especially iron. In support of this, the M2 alloy from Australian Standard AS2239 states that In order to minimize selfcorrosion of alloy M2 when used in domestic water storage heater applications, it has been found desirable to maintain the
iron content below 0.003%, with 0.20-0.6% manganese.
These 2 technical papers and the committee that reviewed AS2239 agree that manganese concentration is one of the key
factors in the performance of magnesium anodes.
Also of related interest, we commissioned some testing of magnesium rod at the ETRS laboratories in Melbourne in 2001
using inductively Coupled Plasma Spectroscopy. The report [8] indicated that the compositional profile for impurities such as
iron, silica and nickel varied from the outer surface of the anode to around 3mm below the surface. The report went on to
suggest that this may result in elements such as iron becoming cathodic to the magnesium, which leads to self corrosion, thus
reducing anode efficiency and increased consumption rate, especially when the anodes are first installed.
As our earlier comparison of the AS2239 M2 alloy and the sample indicated, the iron level is above the compositional limits
and the manganese level is well below. This combination of alloys may be the cause of the extremely high consumption rate
of our sample.
Our investigation did not proceed any further, but depth profile analysis may provide more information. There are some
difficulties associated with analysing depth profiles:
1.

The difference between element concentrations in boundary layers are very small and difficult to detect.

2.

The samples would need to be cut using a steel cutting tool. Any fragments, no matter how minute, may skew the
results.

3.

Even if small differences are detected, this may be the result of different cooling rates at the surface compared to
inside the alloy. Another possibility is segregation, which occurs when some elements solidify at different times
while the alloy is cooling.

If depth profile testing indicated variations in the concentration of these elements, the possible cause could be:
-

There was iron contamination during the extrusion process due to pick up from the moulds/dies. This can occur if
the moulds are excessively worn, fabricated from inferior steel or if the steel in not sufficiently heat treated prior to
commissioning.

There is also the possibility that during casting the segregation of the iron (Fe) and silicon (Si) during the
solidification process may have promoted the formation of intermetallic phases in the microstructure at the surface
of the anode. If the ingot/billet is not properly scalped prior to extrusion it may result in segregation. This can
occur at the end of an extrusion batch.

At this point we did not take the investigation any further, but we believe further metallurgical investigation would provide
reasons for the failure.

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6. ANODE CONSTRUCTION
The anode is a stand size, 1200mm long
x 21mm dia with a threaded steel cap for
attachment to the Hot Water Service Unit.
As figure 4 shows, the anode has a pvc
sleeve, a threaded head and a small piece
of rubber with a small copper washer.
This construction is not typical of hot
water service anodes used in Australia or
in most parts of the world.

Figure 4 Case Study Anode with cap removed

When we unscrewed the cap you can see that through water ingress, corrosion has already started on the thread and up onto
the top of the anode. If the thread on the anode continues to corrode, it could drop to the floor of the tank, or the build up of
corrosion by-products (white powder) could break the electrical connection between the anode and the steel cap, making the
anode useless.
Also, the black rubber piece in the cap with the copper washer appears to be used to maintain an electrical connection. Again
given the build up of by-products, as seen in the photo, this method appears floored.
According to the hot water service unit manufacturer the plastic sleeve was added to the anode to act as a shield to prevent
corrosion at the top end, because the inside of the hot water service units are bell shaped so the anode was very close to the
tank in this area.
The biggest issue with the design is that the anode has no steel wire core. Hot water service anodes often corrode at the top,
as they are in closest proximity to the plumbing fittings and are subject to temperature variations and changes in the
submersion level.
Even given the addition of the plastic sleeve, the likelihood of the anode corroding through near the steel cap and breaking
away is far higher than if the anode was extruded onto a steel core. The piece of magnesium sitting in the bottom of the tank
will offer no protection and may even weaken or damage the tank.
As discussed earlier, the Australian standard AS4692 clearly specifies that the anode must have a steel core. The DIN 4753
part 6 has no such requirement. Clearly an anode with a steel core is a far more robust design which also ensures electrical
continuity between the anode and the tank body.

Installation of anode

Nearing end of anode life

Mid life of anode

Plastic sleeve
reduces corrosion
at the top of the
anode to reduce the
chance that the rod
will corrode through

The lack of a robust connection

between the anode and the cap
could lead to a break in the electrical
connection between the anode
and the tank, stopping the anode
from offering protection.

Corrosion

Corrosion

Figure 5 Anode without steel core

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If the anode corrodes faster

at the top, it may eventually fall
to the bottom of the tank.
This may also occur during
replacement of the anode.

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The most common design used in Australia and in most parts of the world is to extrude the Magnesium anode material onto a
mild steel wire, then weld the wire to the cap and pressure test it to ensure the thread and the weld is secure (see figure 6).
Apply tack weld to
bond protruding anode
core to anode cap.
Must be pressure tight
to 1400 Kpa
.

Anode threaded into cap

Anode pared off to expose wire core
Thread cut into top of anode

Hole drilled in cap to accomodate wire

Figure 6 Common design of Hot Water Service Anode

Anode threaded into cap

Rubber piece with copper connection
Thread cut into top of anode

Plastic sleeve

Figure 7 Case Study design of Hot Water Service Anode

7. CONCLUSIONS
A combination of two problems appears to be the cause of the excessively high consumption rate. Firstly a low potential
anode was used when it should have been a high potential anode and secondly, the alloy composition was incorrect, primarily
with respect to the manganese content.
The anode was also poorly designed. It had no steel wire core, the head of the anode located inside the steel cap was
corroding in the thread, and the anode was not effectively electrically connected to the steel cap and therefore the storage tank
(cathode).
This case study highlights 3 issues when selecting anodes:
1. Ensure that the chemical composition of the anode is suited to the environment in which it will operate.
2. Ensure that the chemical composition of the anode complies with the relevant Australian or International standards.
3. Ensure that the anode design is robust enough to withstand the environmental conditions it will be operating in.

This paper is intended to act as warning to users of galvanic anodes. Safeguard against faulty product by:
-

Requesting certificates of analysis with each purchase. Most reputable foundries will provide this.

Obtain random independent chemical analysis for comparison with the foundry certificates. There are a number of
NATA approved test laboratories with appropriate test facilities.

Take potential readings and check that the anodes are performing according to the prescribed design criteria.

These simple measures not only provide confidence that the anodes will operate according to the design parameters, but may
also provide some measure of legal protection. All relevant information for ordering and design parameters are located in the
relevant Australian and International Standards. Everyone has a duty of responsibility to ensure that the product that they are
representing for sale meets the relevant specifications.

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Beware, you may end up choosing the cheapest anode, which may not actually be an anode, it could turn out to be a piece of
aluminium, magnesium or zinc which causes your hot water service to fail, your boat to sink or your pipeline to rupture.
Remember sometimes Anodes Aint Anodes.
8. ACKNOWLEDGMENTS
Thank you to Ross Gorfine and Lang Semmler for reviewing and editing the contents and especially for their general
assistance with the direction of the paper.
9. REFERENCES
Standard

1.

Australian Standard AS4692.1:2005 Electric Water Heaters - Energy consumption, performance

and general requirements

Standard

2.

DIN 4753 Part 6: 1986 Water heating installations for drinking water and service water

Standard

3.

Australian Standard AS2239-2003 Galvanic (sacrificial) anodes for Cathodic protection

Manual

4.

Owners Guide and Installation Instructions Electrical Heavy Duty Water Heater, Rheem
September 2008.

Standard

5.

Research
Report

6.

B 843 07 Standard Specification for Magnesium Alloy Anodes for Cathodic Protection
(AZ31B)
G.T. Parthiban, N. Palaniswamy and V.Sivan, Effect of managanese addition on anode
charatcteristics of electrolytic magnesium, Anti-Corrosion Methods and Materials Volume 56
no.2 2009

Research
Report

7.

J.G. Kim and S.J. Koo, Effect of Alloying Elements on Electrochemical Properties of
Magnesium-Based Sacrificial Anodes, Corrosion (NACE) April 2000.

Research
Report

8.

M. Johnson, Magnesium Anode Composition Depth Profile MCG01-4175. ETRS, May 2001.

10. AUTHOR DETAILS

Bill Gerritsen has over thirty years of experience in the corrosion industry. He has developed skills that
cover a wide range of structures including cables, pipelines, civil, marine and industry infrastructure. He
also has extensive experience in concrete deterioration investigations and the rehabilitation and protection
of concrete structures.

Brent Linde has been involved with anode manufacturing for over 12 years. He is the Marketing and
Product Development Manager at Cathodic Diecasting. His responsibilities also extend to laboratory based
electrochemical testing of anode alloys. He has been with Cathodic Diecasting since May 2008.

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