eni spa

exploration & production division

COMPANY SPECIF ICATI ON

GALVANIC ANODES FOR CATHODIC PROTECTION

SYSTEM OF BURIED STRUCTU RES

27964VAR.COR.SDS

Rev. 0 - October 2012

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REV. DESCRIPTION COMPILED VERIFIED APPROVED DATE

ENGINEERING COMPANY STANDARD

Thi s document is property of Eni S.pA Exploration & Production Division.

It shall neither be shown to Third Parties not used for purposes other than those for which it has been sent

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FOREWORD

Rev.0 14 pages
October 2012
Issue

The present document cancels and replaces the following Company Standard ENI:
- 20306. EQP.COR.FUN Anodi galvanici per la protezione catodica di strutture interne.
- 11556.MAT.COR.SPC Dispersori ad anodi galvanici nel terreno.

In this company specification the set minimum requirements and recommendations for
tolerances, electrochemical characteristics or properties, test procedures and inspection
standards for galvanic anodes in soil are reported.

The basic requirements for the design, materials selection, installation, commissioning,
inspection and maintenance of groundbed anodes for cathodic protection systems of buried
metallic structures are reported in the company specification 27589.VAR.COR.PRG -
Guidelines for Design and Construction of Cathodic Protection Systems.
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INDEX

1. GENERAL.............................................................................................................................. 4
1.1 PREMISE ............................................................................................................................... 4
1.2 SCOPE................................................................................................................................... 4
1.3 REFERENCES....................................................................................................................... 4
1.3.1 ENI Company Standards ....................................................................................................... 4
1.3.2 Codes and Standards ............................................................................................................ 4
1.4 DEFINITIONS ........................................................................................................................ 5

2. GALVANIC ANODE. FUNCTIONAL REQUIREMENTS....................................................... 7

2.1 ANODE MATERIALS ............................................................................................................. 7
2.1.1 General................................................................................................................................... 7
2.1.2 Magnesium anodes................................................................................................................ 7
2.1.3 Zinc anodes............................................................................................................................ 8
2.1.4 Ribbon Anode ........................................................................................................................ 8
2.1.5 Anode core material ............................................................................................................... 8
2.1.6 Packaged anodes .................................................................................................................. 8
2.1.7 Anode electrical cables .......................................................................................................... 9
2.2 ELECTROCHEMICAL PROPERTIES AND SURFACE MORPHOLOGY............................. 9
2.2.1 General................................................................................................................................... 9
2.2.2 Potential ................................................................................................................................. 9
2.2.3 Current capacity ..................................................................................................................... 9
2.2.4 Anode surface morphology .................................................................................................. 10
2.2.5 Electrochemical characteristics of galvanic anodes ............................................................ 10
2.3 ANODE ACCEPTANCE CRITERIA..................................................................................... 11
2.3.1 General................................................................................................................................. 11
2.3.2 Chemical composition .......................................................................................................... 11
2.3.3 Physical properties............................................................................................................... 11
2.3.4 Electrochemical testing ........................................................................................................ 11
2.3.5 Anode core material ............................................................................................................. 12
2.3.6 Anode electrical cable .......................................................................................................... 12
2.4 FORMS ................................................................................................................................ 12
2.5 DOCUMENTATION ............................................................................................................. 12

3. ANNEX A PHYSICAL TOLERANCES TYPICAL ............................................................ 13

3.1 ANODE MASS ..................................................................................................................... 13
3.2 ANODE DIMENSIONS AND STRAIGHTNESS................................................................... 13
3.3 CABLE LENGTH.................................................................................................................. 13
3.4 STEEL INSERT.................................................................................................................... 13
3.5 ANODE SURFACE IRREGULARITIES ............................................................................... 13
3.5.1 General................................................................................................................................. 13
3.5.2 Internal defects and destructive testing ............................................................................... 14
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1. GENERAL

1.1 PREMISE
The purpose of this Company Specification is to set minimum requirements and recommendations
for tolerances, electrochemical characteristics or properties, test procedures and inspection
standards for cast galvanic anodes in soil in order to determine the anticipated performance including
design life of the anodes.

The Manufacturer shall be responsible for complying with the quality levels specified in this Company
Specification. The extent of the inspection shall be subject to agreement between the Purchaser and
the Manufacturer at the time of the order.

1.2 SCOPE
This Company Specification describes galvanic anodes applicable in soil, and gives the minimum
requirements and recommendations for the physical tolerances, electrochemical characteristics or
properties, test procedures and inspection standards for cast galvanic anodes of magnesium and
zinc based alloys for cathodic protection.

This Company Specification does not address quality assurance.

1.3 REFERENCES
1.3.1 ENI Company Standards
Ref. /1/ MOD.COR.CPS.012 Description of technical documentation for galvanic or impressed
current anodes in soil (DDS).
Ref. /2/ MOD.COR.CPS.021 Data sheet for galvanic anodes in soil (TDS).
Ref. /3/ MOD.COR.CPS.023 Description of checks and tests for galvanic and impressed
current anodes in soil (IDS).
Ref. /4/ MOD.COR.CPS.024 Evaluation technical data for galvanic anodes in soil (EDS).
Ref. /5/ 27589.VAR.COR.PRG Guidelines for Design and Construction of Cathodic Protection
Systems.

1.3.2 Codes and Standards

Ref. /6/ ISO/CD 15589-1 Petroleum and natural gas industries Pipelines transportation
systems Cathodic protection Part 1: Onshore pipelines.
Ref. /7/ EN 12954 Cathodic protection of buried or immersed metallic structures
General principles and application for pipelines.
Ref. /8/ ASTM B418 Standard specification for cast and wrought galvanic zinc anodes.
Ref. /9/ ASTM B843 Standard specification for magnesium alloy anodes for cathodic
protection.
Ref. /10/ ASTM G 97 Standard test method for laboratory evaluation of magnesium
sacrificial anode test specimens for underground applications.
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1.4 DEFINITIONS
Acidity The presence of an excess of hydrogen ions over hydroxyl ions (pH 7).
Anode An electrode at which anodic reaction predominates.
Batch Also mentioned heat, charge or cast. It is the unit that defines molten
metal and identifies the anodes cast from it. A heat is the product that is cast
to a planned procedure in one melting operation in one furnace, without
significant interruption. If the casting sequence is interrupted, the anodes
produced before, between, and after the interruptions constitute batches.
Cast See "Batch".
Cathode Electrode at which cathodic reaction dominates.
Cathodic Protection The means of reducing corrosion by causing direct current to flow from its
electrolyte environment into the entire metal surface.
Cathodic Reaction Electrode reaction equivalent to a transfer of negative charge from the
electronic to the ionic conductor.
Charge See "batch".
Closed Circuit The potential measured on the anode when a current flowing in a galvanic
Potential cell.
Cold shuts Horizontal surface discontinuity caused by solidification of a portion of a
meniscus during the progressive filling of a mould, which is later covered
with more solidifying metals as the molten metal level rises. Cold shuts
generally occur at corners remote from the point of pour.
Core. Also mentioned The form over which the anode is cast and which is used to connect the
insert anode to the structure requiring protection.
Corrosion Potential Potential of a freely corroding metal with respect of a reference electrode in
a given corrosion system.
Corrosion product Substance formed as a result of corrosion.
Crack Fracture of metal along a path producing a discontinuity similar to a ragged
edge. It can occur during the solidification of the anode (hot cracking),
during the contraction of the anode after solidification, or under externally
applied loads. Hot cracking may be associated with the shrinkage
depression that can occur in open-topped moulds.
Current capacity The current capacity is the total amount of electricity that is produced when
one kilogram of anode Material is consumed. The current capacity is
expressed in Ampere-hours per kilogram (Ah/kg).
Current density Current intensity per unit area of the electrode.
Electrochemical Those properties of potential and current capacity that characterise a
properties galvanic anode and can be assessed by quantitative tests.
Equivalent diameter A fictive anode diameter used for calculation of anode resistance. Equivalent
diameter = 2 x (cross sectional area/).
Free running test An electrochemical test where potential and current are not controlled.
Gas holes Blow holes, channels or porosity produced by gas evolution during
solidification. Gas holes can indicate contamination of the mould or insert
prior to casting.
Galvanostatic test An electrochemical test with control of current to a pre-set level.
Heat See batch.
Inter-granular / inter- Preferential corrosion that occur at/on grain boundaries.
crystalline corrosion
Ladle sample A specimen taken from a molten metal stream. Such samples may be taken
at the commencement of pouring and then at regular intervals until a final
sample is taken at the end of the pour.
Non-metallic inclusions Particles of oxides and other refractory materials entrapped in liquid metal
during the melting or casting sequences.
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Passive surface A condition of low surface activity or resistance to corrosion of a metal,

normally as a result of protective film formation.
Pit Localised corrosion resulting in pits, i.e. cavities extending from the surface
into the metal.
Polarisation Change in the potential of an electrode as the result of current flow to or
from that electrode.
Potentiostatic test An electrochemical test with control of potential to a pre-set value.
Reference electrode Electrode, having a stable and reproducible potential, which may be used in
the measurement of other electrode potentials.
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2. GALVANIC ANODE. FUNCTIONAL REQUIREMENTS

2.1 ANODE MATERIALS

2.1.1 General
Alloys used for galvanic anodes in soil are based on zinc (Zn) and magnesium (Mg). The
performance, and therefore the suitability of a particular alloy for a specific application, will depend on
the composition and characteristics of both the alloy and the electrolyte, of the operating temperature
and of the anode current density.

The characteristics of an anode alloy may be obtained from the performance data in the given
environmental conditions. The performance data shall include the current capacity in Ampere-hours
per kilogram (Ah/kg), and the closed circuit potential of a working anode measured against a
standard reference electrode.

2.1.2 Magnesium anodes

Chemical composition requirements for magnesium anode alloys are given in Table 2.1, where the
magnesium being the balance [Ref. /6/, Ref. /9/].

Table 2.1 Chemical composition in weight percent for magnesium alloy anodes

COMPOSITION
(% By weight)
ELEMENTS
Low potential High potential

Al 5.3 6.7 0.01 max

Mn 0.15 min 0.5 1.3
Zn 2.5 3.5 absent
Si 0.1 max 0.05 max
Cu 0.02 max 0.02 max
Ni 0.002 max 0.001 max
Fe 0.003 max 0.03 max
Other impurities (each) 0.005 max 0.05 max
Other impurities (total) 0.3 max

Any other type of alloy shall be subject to Company approval.

The typical performance characteristics of the magnesium anode alloys are given in Table 2.3.
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2.1.3 Zinc anodes

Chemical composition requirements for zinc anode alloysare given in Table 2.2, where the zinc being
the balance [Ref. /6/].

Table 2.2 Chemical composition in weight percent for zinc anodes

COMPOSITION
Element
(% By weight)

Al 0.10 0.50
Cd 0.025 0.07
Fe 0.005 max
Pb 0.006 max
Cu 0.005 max
Other impurities (each) 0.02

Any other type of alloy shall be subject to Company approval.

The typical performance characteristics of the zinc anode alloys are given in Table 2.4.

2.1.4 Ribbon Anode

The use of zinc or magnesium ribbon anode shall be agreed with the Contractor.

Since some hydrogen can develop at anode surface, the electrical cable conduit shall not be sealed
to let the gas escape and it shall be protected at the end by a tight net.

For the composition and electrochemical proprieties of the ribbon is possible refer from the Table 2.1
to Table 2.4 in same order as for zinc and magnesium type.

2.1.5 Anode core material

Inserts shall be fabricated from weldable carbon steel plate, bar, sections or pipe. The steel used
shall be in accordance with the norm EN-10025, or other applicable standards.

The steel insert shall be blast cleaned to the grade Sa 2 defined in the norm ISO 8501-1 before
casting.

2.1.5.1 Insert for Zinc anodes

For zinc anodes, the steel inserts shall be hot dip galvanized.

When bare steel insert are used they shall be blast cleaned to the grade Sa 2 defined in the norm
ISO 8501-1.

2.1.6 Packaged anodes

Packaged anodes are anodes that have been placed in a water absorbent cotton bag filled with
backfill.

The backfill shall consist of a mixture of:

- hydrated gypsum: 75%
- bentonite: 20%
- sodium sulphate: 5%
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2.1.7 Anode electrical cables

The anode shall be complete with electric connection cable factory-applied.

The cable shall have the following main requirements:

- nominal Voltage Uo/U: 0.6/1 kV;
- conductor: Stranded tinned annealed copper;
- minimum cross-section: 10 mm2;
- insulation and outer sheath: suitable for direct laying underground.

The cables shall be produced with the following characteristics according to CEI/IEC regulations:
- resistance to hydrocarbons;
- fire resistant;
- flame retardant;
- low emission of smoke and toxic gases and corrosive.

Silver brazing must be used to connect the cable to the metallic core. The welded area must be
protected with resin and heat shrinkable tubing.

The electrical resistance of point of contact cable/anode shall not exceed 0.001 .

2.2 ELECTROCHEMICAL PROPERTIES AND SURFACE MORPHOLOGY

2.2.1 General
The performance of a galvanic anode alloy is dependent on its actual chemical composition and
homogeneity, current density and environment of exposure.

In the design calculations of a cathodic protection system the following parameter shall be
considerate:
- potential;
- current capacity;
- anode surface morphology.

The properties of the anode material shall be determined by appropriate tests (see Par. 2.3 in this
document).

2.2.2 Potential
An anode material shall have a closed circuit potential more negative than the protection potential for
cathodic protection. The anode potential shall be stable with time to ensure long term performance.

Anode alloys will polarise, i.e. change potential, when current is delivered, and the anode potential
under operating conditions, i.e. the closed circuit potential, shall be considered and used for design
calculations. The potential of an anode material will also vary with the surrounding environment. The
potential may change with time even when exposed to constant conditions due to corrosion products
being formed on anode surface and due to variations in the current demand. In view of this, tests
shall be carried out to determine the effect of current densities and time on the potential and under
the various operating conditions of the anode.

2.2.3 Current capacity

The current capacity is expressed in Ampere-hours per kilogram (Ah/kg) and is the total amount of
electricity (Ampere-hours) that can be produced when one kilogram of the anode is consumed.

The theoretical current capacity can be calculated for each metal based on the Faraday law.
However, due to self corrosion, anode materials have a practical current capacity lower than that
calculated (i.e. some of the current produced is used for self corrosion of the anode material and is
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not available for cathodic protection). The practical current capacity is important for cathodic
protection design (see Par. 2.2.5). The practical current capacity shall therefore be determined for
anode materials under normal operating conditions.

The practical current capacity decreases with increasing temperature. The practical current capacity
increases with increasing anode current density. At extremely low current densities self corrosion is
more pronounced and may give a significant reduction in the practical current capacity. Practical
current capacity tests shall be carried out to determine the effect of environments, temperature and
anode current density.

2.2.4 Anode surface morphology

When anode materials are consumed, either by self corrosion or by the current used for cathodic
protection, the anode surface morphology will vary depending on the materials and environmental
conditions prevailing. The anode material dissolution morphology shall be examined as the corrosion
pattern can indicate whether active or passive behaviour is likely and it will also indicate any
tendency to undercutting.

Deep and undercut pits may develop due to an acidic environment formed within the pit because of a
restricted electrolyte access. This may lead to increased self corrosion inside the pits and
consequently a loss in capacity. The pitting can in addition lead to undercutting with loss of anode
material and reduced anode life. Intergranular (or inter-crystalline) corrosion can lead to a rapid
disintegration of the anode material and consequently to a reduced anode life. Metallographic
evidence of any tendency of intergranular corrosion may be a cause for anode rejection.

2.2.5 Electrochemical characteristics of galvanic anodes

Table 2.3 and Table 2.4 give recommended values for electrochemical characteristics for galvanic
anodes of magnesium and zinc respectively.

Table 2.3 Electrochemical characteristic of magnesium alloy anodes at ambient temperature

Potential Practical Capacity

ALLOY
mV Ag/AgCl Ah/kg
Low potential -1450 1100
High potential -1650 1200

Table 2.4 Electrochemical characteristic of zinc alloy anodes anodes at ambient temperature

Potential Capacity
ALLOY
mV Ag/AgCl Ah/kg
Zinc alloy anode -1030 780
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2.3 ANODE ACCEPTANCE CRITERIA

2.3.1 General
The anodes, shall be designed in such a way as to give adequate performance during fabrication,
transport, installation and operation.

2.3.2 Chemical composition

As the performance of galvanic anode is strictly related to chemical composition, a strict control of
the alloying elements and impurities is essential.

All samples shall be suitably identified with the cast number. All anodes shall be similarly identified
with the cast number.

The samples shall be analysed to prove compliance with the agreed chemical composition limits of
the alloy being produced. Additional sample(s) may be taken and stored for future determination of
chemical composition.

Two samples from each het shall be taken for chemical analysis. The samples shall be taken in the
beginning and the end of casting from the pouring stream. For smaller alloying furnaces (max. 500
kg), it is acceptable to take one sample for heat. The sample shall be taken at the beginning of the
first heat and at the end of the second heat, then in the beginning of the third heat and so on. The
samples shall be analysed to verify the required chemical composition.

Anodes from heats whose chemical composition do not meet the required chemical composition shall
be rejected.

For alloys where heat treatment forms part of the specification, details of the heat treatment history
for each furnace charge shall be recorded.

The chemical analysis and the temperature sensing and recording equipment, shall be suitably
calibrated.

2.3.3 Physical properties

The physical and dimensional tolerances determined by the anode design shall be complied with.

The galvanic anode manufactured shall reflect good workmanship. No anode shall have any defect
either on its surface or within its body that will affect the transportation, installation and future
performance of the anode. Values of tolerances are given in Annex A.

2.3.4 Electrochemical testing

2.3.4.1 General
Electrochemical performance testing in a laboratory is mainly directed towards the determination of
anode potential, anode capacity, anode efficiency, tendency to passivation and self-corrosion. The
morphology of the surface of the corroded sample may also give an indication of the service
performance.

The closed-circuit potential and electrochemical capacity shall comply with the following agreed
acceptance criteria:

Zinc anodes:
- Average currant capacity: 780 Ah/kg
- Closed-circuit potential: -1030 mV vs Ag/AgCl
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Magnesium anodes:
- The energy capacity testing shall be conducted according to ASTM G97 [Ref. /10/].
- Magnesium anode low potential shall exhibit a potential -1450 mV vs Ag/AgCl.
- Magnesium anode low potential shall exhibit a potential -1650 mV vs Ag/AgCl.

2.3.4.2 Sampling
One set of tests shall be carried out for each 15 tonnes of anodes produced. The electrochemical
test data shall be reported.

2.3.5 Anode core material

100% visual inspection of the inserts shall be carried out prior to casting.

Rust discoloration and/or visible surface contamination shall not be accepted.

Values of tolerances are given in Annex A.

2.3.6 Anode electrical cable

The electrical resistance of point of contact cable/anode shall be determined.

Values of tolerances of the cable length are given in Annex A.

2.4 FORMS
The following forms are available:
- MOD.COR.CPS.012 Description of technical documentation for galvanic or impressed current
anodes in soil (DDS).
- MOD.COR.CPS.021 Data sheet for galvanic anodes in soil (TDS).
- MOD.COR.CPS.023 Description of checks and tests for galvanic and impressed current
anodes in soil (IDS).
- MOD.COR.CPS.024 Evaluation technical data for galvanic anodes in soil (EDS).

2.5 DOCUMENTATION
The following documentation shall be prepared by the supplier:
- list of all melts numbered in chronological order and showing each anode with its serial number
and gross weight;
- results of the carried out testing;
- mill certificates of the steels used.
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3. ANNEX A PHYSICAL TOLERANCES TYPICAL

Values reported in this annex for tolerances shall be intended as maximum allowed limits. More
restrictive tolerances can be specified in Project Documents.

3.1 ANODE MASS

Individual anodes of each type shall have a weight within 3% of the nominal weight for anodes
above 50 kg of weight. For anodes below 50 kg of weight the tolerance shall be 5%. An agreed
number of anodes of each type (e.g. 10%) shall be weighed, either individually or in small batches, to
confirm general compliance with this requirement.

The total weight of the delivery shall be no more than 2% above nominal contract weight, and no
negative tolerance is permitted.

3.2 ANODE DIMENSIONS AND STRAIGHTNESS

Dimensions shall conform to the following:
1. Anode mean length shall be 3% of nominal length or 25 mm whichever is smaller.
2. Anode mean width shall be 5% of nominal mean width.
3. Anode mean depth shall be 10% of nominal mean depth.
4. The diameter of cylindrical anodes shall be 2.5% of nominal diameter.

The straightness of the anode shall not deviate more than 2% of the anode nominal length from the
longitudinal axis of the anode.

At least 10% of the total number of anodes shall be measured to prove compliance with the above
requirements.

3.3 CABLE LENGTH

Tolerance on the dimension of cable length shall be no more than 2% above the design length, and
no negative tolerance is permitted.

At least 10% of the total number of anodes shall be measured to prove compliance with the above
requirements.

3.4 STEEL INSERT

The cross section dimensions of the anode core shall comply with the appropriate specification.

Except otherwise agreed the tolerances for the position of the insert shall be 5 mm of anode
material thickness covering the insert.

3.5 ANODE SURFACE IRREGULARITIES

3.5.1 General
The anode surface shall be free of surface slag or other embedded material.

Cracks are not acceptable, except in the form of micro (hairline) cooling cracks. Maximum width 1
mm.
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Shrinkage depressions shall not exceed 10% of the nominal depth of the anode, as measured from
the uppermost corner to the bottom of the depression. Any depression which exposes the insert
material shall not be accepted.

In the topping up area the maximum shrinkage shall not be more than 10 mm depth measured from a
straight edge across the topping up face and not more than 0.5% of the gross volume. Any additional
topping up material or casting surface irregularities shall be fully bonded with the bulk anode
material.

All protrusions detrimental to the safety of personnel during handling shall be removed.

Anodes shall be inspected visually to confirm compliance with the above requirements.

3.5.2 Internal defects and destructive testing

The number and method of selection of anodes to be sectioned during a contract shall take account
of insert and anode design. In general, anodes shall be sectioned transversely by single cuts at
25% , 33% and 50% of nominal length.

The cut faces, when examined visually without magnification, shall not have more than:
- gas holes and porosities shall be limited to maximum 2% of the total cut surface area, and
maximum 5% of any individual cut surface area;
- lack of bond (voids) shall be limited to maximum 10% of the total tubular anode core
circumference and maximum 20% of the circumference for any individual cut;
- non-metallic inclusions shall be limited to maximum 1% of the total cut surface area and maximum
2% of any individual cut surface area.

For non tubular cores, where prevention of voids may be particularly difficult, the limits may be
otherwise agreed between the manufacturer and the purchaser.

The insert position within the anode shall be confirmed by measurement on the cut faces.