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REHABCON IPS-2000-00063

ANNEX E
Corrosion inhibitors

EC DG ENTR -C-2
Innovation and SME Programme
IPS-2000-0063
________________________________

REHABCON
Strategy for maintenance and
rehabilitation in concrete structures
________________________________
ANNEX E Corrosion inhibitors 1 (9)

CONTENTS

1 DESCRIPTION 2

2 DESIGN 3
2.1 The process of corrosion inhibition 3
2.3 Some considerations for the designer 5
2.4 Global performance requirements and issues 6

3 EXECUTION 6

4 QUALITY CONTROL 7

5 REFERENCES 7

Prepared by: Centre for Concrete Construction, BRE Ltd, Watford, UK 15/04/2004
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1 DESCRIPTION
This annex deals with reinforcement corrosion inhibitors. The use of inhibitors is one of the techniques
that can be employed in reinforced concrete structures to prevent reinforcement corrosion. It falls
within one of the five “Principles” which are the basis of “Methods” known to control reinforcement
corrosion (Method 11.3) in EN 1504:Part 9 - “General principles for the use of products and systems” .
(See Chapter 5, Repair options of this Manual.)
Currently, existing parts of the EN1504 series, including the general Parts 8, 9 and 10, do not explicitly
deal with corrosion inhibitors. It is not known whether the currently unpublished Part 7 of the standard,
which deals with reinforcement corrosion prevention, will cover inhibitors explicitly.
There are two generic types of inhibitors, viz.
1. cast-in (admixture) inhibitors used for new build structures as a preventative measure, and

2. surface-applied (retro-applied) inhibitors used predominately for existing structures as a


curative or preventative measure.

Admixture (cast-in) inhibitors: Admixed inhibitors are used to help retard the onset of corrosion (i.e.
increase the period of corrosion initiation shown in Figure 1). They are generally added to the concrete
mix in sufficient, but preferably small, concentrations prior to casting. They have been shown not to
significantly affect the physical properties of the concrete (e.g. compressive strength, setting time and
microstructure). Admixed inhibitors have also been used in conjunction with concrete repair materials
and applied to existing structures as part of a rehabilitation strategy. However, there is some
uncertainty about how effective admixed inhibitors are in providing protection against the formation of
incipient anodes.
Cast-in inhibitors too are relevant to the REHABCON Manual as they may be added to the repair
material to be used in patch repair where existing concrete is removed and replaced with new
material.

Surface Applied (retro-applied) Inhibitors: Surface applied inhibitors are predominantly used as a
rehabilitation or curative measure for reinforcement corrosion in existing structures. However, it is
increasingly used also as a proactive corrosion intervention measure to delay the onset of corrosion.

These inhibitors are either applied directly to the surface of existing concrete structures or are placed
in drilled holes within the parent concrete at discrete locations. They are designed to penetrate the
concrete matrix and suppress or control the corrosion rate of the embedded steel reinforcement. The
various mechanisms by which the inhibitors ingress the concrete matrix are still not entirely
understood, and so is the exact concentration of inhibitor required at the steel/electrolyte interface in
order to suppress corrosion.

Inhibitors are available as liquids, gels or powders. Based upon how they inhibit corrosion, they fall
into three catogories:

• anodic inhibitors which control the anodic reaction in the corrosion cell;
• cathodic inhibitors which control the cathodic reaction;
• ambiotic (or mixed) inhibitors which control both the anodic and cathodic reactions.

Anodic and ambiotic inhibitors are the most common.

With a few notable exceptions most of the commercially available inhibitors are complex chemical
blends and mixtures containing several active components and it is probable that more than one
inhibition mechanism is operating in order to interfere with the corrosion processes. However, due to
the commercial sensitivity of many of the inhibitor formulations, much of the manufacturer’s published
literature lacks quantitative data concerning the active components and mechanisms of inhibition.
ANNEX E Corrosion inhibitors 3 (9)

Although the degree of information regarding the benefits of inhibitors is increasing (from
manufacturers' data, laboratory studies and real world applications) there are still some very important
fundamental questions that need to be addressed before the technology as a whole can used reliably.
For example, there is a need to understand and define the mechanisms of inhibition associated with
the various commercial products and also specify the concentrations of material that are required at
the level of the reinforcement in order to bring about an effective level of inhibition. In addition, robust
methodologies to measure this concentration and to assess the level of long-term protection provided
by the various inhibition mechanisms are required.

2 DESIGN
For the proper design of corrosion of inhibitors a thorough understanding of the inhibition process is
required.

2.1 The process of corrosion inhibition


Irrespective of the type of inhibitor (admixture or surface applied) and the mechanism(s) of inhibition, a
simple definition of concrete corrosion inhibitor functionality is that it slows, or interferes with, the rate
of a chemical reaction that produces corrosion. This chemical reaction, which is being slowed or
interfered with, is the dissolution of steel by various mechanisms, resulting from the breakdown (or
depassivation) of the protective film formed on the steel surface in the normally highly alkaline
concrete environment. Many of the commercially available inhibitor materials may interfere with one or
more stages of the corrosion process.

The corrosion process for steel reinforced concrete can be simplified into a two-stage process namely,
the ‘initiation phase’ and the ‘propagation phase’. By definition the initiation phase is the time taken for
conditions to become conducive to corrosion of the reinforcement and the propagation phase is the
period in which the accelerated corrosion of the steel reinforcement itself ultimately leads to rust
staining, cracking and spalling of the cover concrete. Figure 1 shows a simplified model of the
corrosion initiation and propagation phases during the service life of a hypothetical reinforced concrete
structure. Using this model it is easy to demonstrate how the various types of concrete corrosion
inhibitor can be divided into the two categories mentioned above, depending upon their primary use
for either new or existing concrete structures.

Maximum Permissible Co rrosion


Corrosion of Steel
Reinforcement

Intervention Point
(Reactive maintenance)

Intervention Point
(Proactive maintenance)

Time

Corrosion Initiation Phase Corrosion Propagation Phase

Ingress of aggressive s pecies


through cover concrete
e.g. chlorides, carbonation
Accelerated degradation of
steel reinforcement

Total Service Life

Figure 1 Simplified model of corrosion stages for reinforced concrete structures (After Tuttii)
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Figure 2 Simplified model of corrosion for reinforced concrete structures showing simplified anodic and
cathodic reactions common to both carbonation and chloride induced corrosion.

2.2 The efficiency of an inhibitor


Design/selection of inhibitors may be based on their efficiency. However, there is some difficulty
surrounding the definition of ‘inhibitor effectiveness’ or ‘efficiency’. This difficult regarding the ability of
an inhibitor to reduce corrosion is largely due to the use of the classical definition of inhibitor efficiency
in aqueous solutions.

 R - R* 
%inhibition = 100 
 R 

Where R is the corrosion rate without inhibitor addition and R* is the corrosion rate after inhibitor
addition in the same environment. The above definition is applicable to many aqueous systems such
as heating boilers where the impact of the inhibitor can be assessed relatively quickly and the
concentrations of inhibitors can be closely monitored and maintained at the desired operating level.
However, this definition may well be over- simplistic for the complex environment of reinforced
concrete structures, where the control/monitoring of corrosion rates is generally applicable over much
longer periods. The classical definition requires the corrosion rate to be suppressed by up to two
orders of magnitude before the inhibitor is classified as approaching 100% efficiency. In addition, this
ANNEX E Corrosion inhibitors 5 (9)

definition does not include a variable relating to the ability of the inhibitor to remain at a given
efficiency for a specified period.

Empirical models, that used known concrete material properties to define the degree of corrosion
required to cause cracking of the cover concrete to a reinforcement bar of known diameter, have
predicted that a significant increase in the time to first cracking can be achieved with only moderate
reductions in corrosion rate. For example, using these models, a 10 mm diameter steel bar in 25 mm
cover concrete of 30MPa compressive strength is predicted to show signs of cracking in approximately
5 years at a constant corrosion rate of 12 microns per year. A 40% reduction in the corrosion rate
increases the time to first cracking to 8.5 years, whilst a 60% reduction increases this period to 12.5
years.

Based upon the classical definition of inhibitor ‘efficiency’, an effective inhibitor is required to reduce
the corrosion current by close to 100%. Therefore, assuming that the minimum critical inhibitor
concentration can be maintained indefinitely, the above model predicts that a typical concrete
corrosion inhibitor would theoretically increase the time to first cracking to 500+ years. This prediction
is invalid as none of the electrochemical rehabilitation techniques currently available would be able to
meet such a stringent success criterion from a single point intervention strategy.

It therefore follows that, if the success criteria for a rehabilitation technique is to extend the period of
next intervention by 5-10 years, then a technique that reduces corrosion rate by only 40-60% over this
period will be effective in achieving this goal.

Linear polarisation resistance (LPR) has been successfully used in the laboratory for a number of
years to measure the corrosion rate of metals in aqueous solutions. However, at present most site-
based LPR instruments are capable of measurements accurate and reproducible to, at best, within a
factor of 2 (based upon experimental inaccuracies and the limitations of the LPR technique itself).
Therefore, making judgements regarding the efficacy of materials with this technique is very difficult if
the materials themselves are only producing an effective reduction in corrosion rate by a factor of 2.
Naturally, it would be much easier to identify the positive benefits of the materials if their effect on
corrosion rate was closer to the classical definition of efficiency and reductions of two orders of
magnitude were achievable for the corrosion rate in reinforced concrete structures.

2.3 Some considerations for the designer


The ability of concrete corrosion inhibitors to reduce and control the corrosion rate of steel
reinforcement has been heavily contested, both in the UK and internationally, for several years. Many
inhibitor research programmes seem to have provided little or no evidence to support the benefits of
using such materials to control the corrosion rate of steel reinforcement. Conversely, others have
determined inhibitors to be highly effective in controlling the corrosion rate.

There is general agreement in the available literature as to the ability of ‘cast-in’ inhibitors to delay the
onset of corrosion in good quality reinforced concrete structures. However, the long-term positive
benefit of the various types of inhibitors is still being debated. The main area of contention lies with the
‘surface applied’ inhibitors and their ability to reduce and control the rate of corrosion when applied as
a curative or rehabilitative technique.

Through manufacturers' data, laboratory studies and real world applications, the amount of information
regarding the benefits of both types of inhibitors has increased. However, there are still some very
important fundamental questions that need to be addressed before the technology as a whole can
used reliably. There is the need to understand and define the mechanisms of inhibition associated with
the various commercial products and also specify the concentrations of material that are required at
the level of the reinforcement in order to bring about an effective level of inhibition. In addition, robust
methodologies for measuring this concentration and assessing the level of long-term protection
provided by the various inhibition mechanisms need to be developed.
ANNEX E Corrosion inhibitors 6 (9)

For further details and considerations, the reader is advised to refer the BRE IP on the subject
by Morlidge and Sergi [2].

2.4 Global performance requirements and issues

Structural safety and serviceability


The primary, or the higher level, aim of inhibitors is the provision of structural safety and serviceability
to a sufficient level and period of time. By delaying the advent of corrosion or, when it is already
present, by reducing the rate of corrosion, inhibitors increase the time taken for the serviceability and
safety functions to reach either unacceptable levels or the levels for implementing intervention actions.

A current problem with inhibitors is the inability to guarantee their performance due to various reasons
described within the previous sections of this annex. This creates an uncertainty regarding the actual
performance of a structure over long periods of time. This uncertainty can be handled by applying
safety 'factors' when determining the performance levels. For example, these can be the reduction of
predicted effective time for the corrosion initiation, and the use of higher levels of inhibitors than
currently recommended (provided no detrimental effects result by this action).

Durability
Durability may be addressed in two ways. The primary concern is the durability of the structure, which
the inhibitors try to improve. This function is dependent on the durability of the inhibitors' effects. Back-
migration has been recognised as a possible problem. In addition, when used with patch repair
material, there is no guarantee that admixed inhibitors increase durability as incipient anodes may be
formed at the edge of the patches.

Effective inhibition relies on the irreversibility of the adsorption reaction with time even if the
concentration of remaining active inhibitor in the concrete dissipates or is lost with time to the outside
environment. It is therefore reasonable to presume that inhibition can only be effective whilst the
‘barrier’ is coherent with the metal substrate, insoluble to its environment and prevents further access
of aggressive species to the metal surface.

There are concerns regarding the rate at which anodic inhibitors are consumed during the various
corrosion mechanisms, particularly the effect on the corrosion rate when the concentration of inhibitor
falls to a level below the critical concentration required to bring about effective inhibition. That is, to
guarantee the durability of a structure, the remaining inhibitor concentrations should be kept above the
minimum level required.

Environmental impact and sustainability


The environmental impact and sustainability depends on the generic components of the compounds
used.

It is not known what the effects will be if concrete containing admixtures are to be recycled after the
demolition of a structure.

3 EXECUTION
Execution should be carried out according to the manufacturers' instructions. The guidelines available
in EN1504: Part 10 also play an important part during execution and, where applicable, should be
complied with. However, it should be noted that the corrosion inhibitor method has not been dealt with
explicitly by EN1504.

Mixing the cast-in inhibitor into the fresh concrete should allow a uniform distribution of the product
throughout the concrete mix. Many manufacturers advise that their products should only be used in
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‘good quality’ concrete (approximate w/c ratio <0.45). It is suggested by many manufactures that this
‘good quality’ concrete, and hence the characteristic low permeability associated with high
performance systems, should restrict the inhibitor material from being lost to the surrounding
environment (however, as yet, there is no long term study data available to assess this claim).

The execution of tasks related to the provision of inhibitors should comply with the requirements of the
relevant health and safety, environment protection and fire regulations. Where there is a conflict
between the use of inhibitors and compliance with these regulations, alternative methods, principles,
products and systems that avoid such conflict should be used.

One way of guaranteeing safety is to follow the instructions of the manufacturers as they would have
investigated the effects of their particular compounds and are well placed to provide such instructions.

There are stringent environmental regulations covering the use of materials such as nitrites (and
especially chromates) used in anodic inhibitors. (Thus, there are only a few cases of these materials
being used in new build construction within Europe when compared to the USA, Far East & Middle
East).

4 QUALITY CONTROL
Where relevant, quality control measures with respect to the inhibitor materials should comply with
those of EN1504: Part 8.

As with any other repair method, quality control and supervision play an important role in the
introduction of inhibitors to a concrete structure.

If inhibitors are to perform as required, then the existing structure should be properly identified and
diagnosed with respect to its material properties and the agents of deterioration, respectively.

The quality of the implementation of inhibitors should be such that there is no concentration of the
inhibitor in local regions, but is spread as intended.

5 REFERENCES

1. BRE DIGEST 434, “Corrosion of Reinforcement in Concrete: Electrochemical Monitoring”, November, (1998).

2. Morlidge J.R. and Sergi, G., BRE IP xxx, Corrosion Inhibitors for Reinforced Concrete, Draft, February 2003.

3. EN 1504: Part 7 - Reinforcement corrosion prevention. (Not yet available.)

4. EN 1504: Part 8 - Quality Control.

5. EN 1504:Part 9 - “General principles for the use of products and systems”.

6. EN 1504: Part 10 - Site application of products and systems and quality control of the works.

7. Quillin, K., “Modelling degradation processes affected concrete”, BR434, (2001).

8. Degradation of Materials in Aggressive Environments, corrosion rate measurements of reinforced concrete


(handbook), DME5.1,(2001).

9. BBA certificate 96-3232, DCI/DC-S Corrosion Inhibitors.

10. HOPE, B.B. & THOMPSON, S.V, ACI Materials Journal, (1995), Sep-Oct, 92, No 5, 529.

11. ROSENBERG, A.M. & GAIDIS, J.M., Materials Performance, (1979), 18, No. 11, 45-48.
ANNEX E Corrosion inhibitors 8 (9)

12. EL-JAZAIRI, B. & BERKE, N.S., in Corrosion of Reinforcement in Concrete, Ed. PAGE, C.L., TREADAWAY,
K.W.J. & BAMFORTH, P.B., (1990), Elsevier.

13. PROWELL, B.D., WEYERS, R.E. & AL-QADI, I.L., in Concrete 2000, Eds DHIR, R.K & JONES, M.R., SPON
(1993), 1223.

14. ELSNER, B., BÜCHLER, M. & BÖHNI, H., European Federation of Corrosion (Event 208), Eurocorr ’97,
Trondheim, Norway, (1997).

15. ALONSO, C. & ANDRADE, C., ACI Materials Journal, (1990), March-April, 130.

16. MAEDER, U., Corrosion & Protection of Steel in Concrete, Ed. Swamy, Sheffield Academic Press (1994), 878.

17. LAAMANEN, P.H. & BYFORS, K., Nordic Concrete Research, (1996), No19/2, Norsk Betongforening, Olso.

18. MIKSIK, B.A., TARVIN, M. & SPARROW, G.R., Corrosion 89, (1989), Paper 607, 10, National Association of
Corrosion Engineers, Houston, Texas.

19. BRUNDLE, C.R., GRUNZE, D., MADER, U. & BLANK, N., Surf. Interface Anal., (1996), 24, 549.

20. BJEGOVIC, D., SIPOS, L., UKRAINCZYK, V. & MIKSIC, B., in Corrosion & Corrosion Protection of Steel in
Concrete, Ed SWAMY, (1994), Sheffield Academic Press, Vol II, 865.

21. ELSNER, B., Materials Week - Int. Congress on Advanced Materials, ICM International Congres Centre, Munich,
(2000).

22. Concrete Bridge Protection & Rehabilitation: Chemical & Physical Techniques, SHRP-S-665, National Research
Council, Washington DC, (1993).

23. Concrete Bridge Protection & Rehabilitation: Corrosion Inhibitors & Polymers, SHRP-S-666, National Research
Council, Washington DC, (1993).

24. SHAW, M., Proceedings of the 7th International Conference on Structural Faults & Repair, (1997), 2,317.

25. MIKSIK, B.A., Reviews on Corrosion Inhibitor Science & Technology, Eds. RAMAN, A. & LABINE, P., (1993),
National Association of Corrosion Engineers, Houston, Texas.

26. HAYNES, M.D. & MALRIC, B., Proceedings of the 7th International Conference on Structural Faults & Repair,
(1997), 2,307.

27. ALONSO, C., ANDRADE, C., AGRIZ, C. & MALRIC, B., Cement & Concrete Research, (1996), 22, 869.

28. ANDRADE, C., ALONSO, C., ACHA, M. & MALRIC, B., Cement & Concrete Research, (1996), 26, 405.

29. MULHERON, M., Emerging Technologies for Detecting and Mitigating Corrosion Induced Delaminations, ACI Fall
Convention, Toronto, Canada, (2000).