CONTENTS

A REVIEW OF CONCRETE

CORROSION INHIBITORS

AM Peek # M.G. Ali* & WK Green*

Taywood Engineering Limited
#Perth WA *Sydney NSW
SUMMARY: The use of corrosion inhibitors for the protection of steel reinforcement embedded in
concrete is a relatively recent innovation in concrete technology. Several systems are available for
use as admixtures in concrete for new construction, or for incorporation into repair materials.
Other systems are available for surface application or injection in remedial works on existing
structures. While admixed inhibitors appear to be generally relatively effective, the efficacy of
surface applied or injected systems remains an area of contention. This paper presents a review of
recent literature on the subject.

Keywords: concrete, reinforcement, admixture, corrosion inhibitor, migrating corrosion inhibitor,

calcium nitrite, amino-alcohol
1. INTRODUCTION
Reinforced concrete provides one of the worlds most durable and versatile construction materials, however
deterioration of structures due to corrosion of the embedded reinforcement is a major source of aesthetic loss and
structural distress. Over the years, civil engineers and concrete technologists have been innovative in combating this
deterioration. Reinforcement corrosion has been addressed by:

Mix design, selection and proportioning of the components of the concrete, curing methods.

Supplementary cementitious materials.

Use of admixtures, including waterproofing admixtures.

Use of coated reinforcement, alloys other than carbon steel, non-metallic reinforcement.

Various cementitious, modified cementitious and non-cementitious patching materials.

Surface coatings and treatments.

Cathodic protection.

Electrochemical desalination and realkalization.

Corrosion inhibitors.

For any given structure a combination of economics, aesthetics, structural requirements, anticipated service life, and a
variety of practical issues dictate the preferred protective and remedial measures to be taken. The use of corrosion
inhibitors, in both new construction and remedial works, is a relatively recent innovation. The field is progressively
expanding, both success and failure are being reported in the literature.
The nature and action of corrosion inhibitors used in concrete have been reviewed and recounted extensively elsewhere.
A brief review is provided below.

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2. CLASSIFICATION AND ACTION OF CORROSION INHIBITORS

A corrosion inhibitor may be defined as a species or compound which, when added to an environment (usually in small
amounts), reduces the corrosion rate of the metal within the environment by influencing the kinetics and/or
thermodynamics of the electrochemical reactions responsible for this process.
It is worth noting here that the products that reduce the permeability of concrete or provide damproofness to concrete
are not considered corrosion inhibitors based on the classification set in ACI 212 Chemical Admixtures for Concrete
[1]. Therefore, damproofing or water permeability admixtures referred to in the literature are not discussed in this
paper.
NACE categorises inhibitors according to their primary protection mechanism: anodic, cathodic, or a combination of
the two [2]. Anodic inhibitors are chemicals that stifle the reaction at the anode, and are commonly used in alkaline
environments where the anodic reaction primarily controls the corrosion process. Cathodic inhibitors act to stifle the
cathodic reaction and are commonly used in acidic environments where the corrosion process is mostly controlled by
the cathodic reaction [2]. Inhibitors may also be classed as inorganic, organic or vapour-phase. They may be further
subdivided in terms of their postulated mechanisms of corrosion protection as:
(i) Anodic Oxidising Passivators act by shifting the electrochemical potential of the corroding metal such that an
insoluble oxide or hydroxide forms on the metal surface [3].
(ii) Anodic Non-oxidising Passivators stifle the anodic reaction without oxidation.
(iii) Cathodic Inhibitors stifle the cathodic reaction, being commonly used in environments where the corrosion
process is primarily controlled by the cathodic reaction [2].
(iv) Precipitation or Conversion Layer Inhibitors form insoluble compounds on metal surfaces without oxidation.
The effect may be anodic or cathodic inhibition.
(v) Oxygen Scavengers inhibit corrosion by preventing the cathodic depolarisation caused by oxygen (i.e.: by
removing oxygen).
(vi) Film Forming (Adsorption-type or Vapour-phase) Inhibitors are organic based materials that strongly adsorb to
the metal surface, forming a layer that interferes with the anodic or cathodic reactions in the area of
adsorption. An effective film forming inhibitor must be capable of forming a relatively stable compound with
the metal surface [4].
A recent literature search produced the following list of corrosion inhibiting admixtures for concrete that have been
researched under laboratory conditions or applied to field structures:

WR Grace DCI and DCI-S Calcium Nitrite Corrosion Inhibitors

MBT Rheocrete 222 Organic Corrosion Inhibitor

Various Cortec MCI Water Based Corrosion Inhibitors

Sika FerroGard 901 and FerroGard 903 Amino-Alcohol Based Inhibitors

Sodium Nitrite

Potassium Chromate

Sodium Benzoate

MFP (sodium monofluorophosphate)

Sodium Tetraborate

Stannous Chloride

Carboxylic Acids

Other less used chemicals which have been claimed to provide corrosion inhibition to steel in concrete include butyl
ester, sodium orthophosphate, sodium chromate, calcium magnesium acetate, azide, p-bromobenzoate, methyl red,
ethyleneimine, calcium nitrate, lead nitrate, zinc oxide and formaldehyde

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3. CALCIUM NITRITE
Calcium nitrite can be described as an inorganic anodic oxidising inhibitor. It has been used as an admixture in
concrete for new construction for many years. Calcium nitrite admixtures have been researched since 1965, and have
been in commercial use since 1978 [5].
Documented use of calcium nitrite, mainly in the form of Grace Construction Products DCI and DCI-S, in marine
structures [6,7] includes some 126 projects in the USA prior to 1995, projects in Europe, and treatment of some
50,000m3 of concrete around the Arabian Gulf. Independent assessments of the performance of such structures have
often been favourable [e.g. 8].
Extensive documentation of favourable laboratory trials is also available. Recent Virginia Transportation Research
Council (VTRC) reports [9,10] have concluded that calcium nitrite (DCI and DCI-S) should remain the only approved
corrosion inhibiting admixtures for use in Virginia at this time.
Various studies [11-15] have shown that the effectiveness of calcium nitrite is dosage dependent, and that the net
practical effect of the inhibitor is to raise the chloride concentration threshold for initiation of corrosion. One of the
issues to arise out of this work is that calcium nitrite is a more effective inhibitor against chloride salts entering from
the environment than against admixed or cast-in chloride. WR Grace have published recommended dosage rates
based on expected chloride thresholds at the design-life initiation of corrosion [16]. No references were located that
indicated acceleration of corrosion if the inhibitor was underdosed.
Studies such as [11,17] have also shown that the performance of calcium nitrite improves with increasing concrete
quality. Published recommended minimum quality for use of DCI [17] includes a minimum cement content of 355kg/m3,
maximum w/c ratio of 0.45 and minimum 38mm cover. In comparison, for marine structures, Australian construction
codes [18] require use of 50-grade concrete (typically 430-440kg/m3 cement content, w/c0.40) and minimum 50mm
cover.
The relatively high level of published knowledge regarding the above features allows the performance expectations for
calcium nitrite treated concrete to be modelled during design of structures. Consequently, some assessment of costbenefit of the use of the inhibitor can be made for a given structure and environment by use of conventional design life
models. Several such models have been published in the literature [19-21].
A number of studies have been published concerning the effects of calcium nitrite on the properties of the produced
concrete. Most suggest [e.g. 3,8] that there is little effect, the only significant adverse effect being to considerably
accelerate setting. This feature can be counteracted in practice by selection of appropriate set retarding admixtures.
Early age strengths are higher as a consequence of accelerated setting, but later age strengths are relatively unaffected.
Several published studies [e.g. 13,22,23] have shown that calcium nitrite is also compatible with common supplementary
cementitious materials such as blast furnace slag, fly ash and silica fume.
As calcium nitrite is highly soluble in water, concerns are sometimes aired that the inhibitor may leach out of a
structure with time, reducing its effectiveness. Studies of treated bridge decks in the USA [5] conducted after 15 years
service showed no diminution of the nitrite concentration. A more recent study of leaching characteristics [61]
indicates that some 85-90% of the nitrite is physico-chemically bound by the cement matrix in a manner analogous to
that observed with chloride ions.
4. ORGANIC INHIBITORS
Although they have been used in packaging and other preservative applications, and in pipeline protection, for many
years, amine and amino-alcohol type corrosion inhibitors were first proposed for use in mitigation of reinforcement
corrosion during the 1980s [24]. The technology has therefore been in the construction industry for a much shorter
time than has calcium nitrite.
Such organic-based inhibitor systems generally act as adsorption film type inhibitors, however claims may also be made
regarding retardation of chloride ingress into the concrete as a component of the overall inhibition mechanism [25
27]. Examples of this type of technology in the market include Sika FerroGard, Master Builders Technologies Rheocrete
222, Cortec MCI 2000, MCI 2005, MCI 2006NS and MCI 2020, Scotch Kote 911 and Armatec A2000.
Extensive searching of published literature concerning the effectiveness of these systems has shown that a significant
body of laboratory based test data is available, but there is currently relatively little information on in-situ use available
in the public domain.
Although Master Builders publications [26,28-30] refer to successful laboratory trials and use in some 50 structures
around the world, little in-situ data has been presented.

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Similarly, Cortec data sheets refer to use of some 14,000 litres of corrosion inhibitors in concrete construction in the
Middle East, but no published case studies were located. Published laboratory studies of these products have indicated
that they are effective inhibitors of corrosion rate [3,31,32].
Again, several favourable laboratory studies using Sika FerroGard products are also available in the literature [33-35].
There is limited in-situ data available [33,36], though a simulated weathering test has been claimed to indicate
persistence in concrete in excess of 10 years under Zurich weather conditions [34].
The above provides an outline of the literature that is available to demonstrate the effectiveness of these organic
inhibitor systems in mitigating corrosion of embedded reinforcement. Against these documents, there is also a body of
published evidence where the materials tested have been shown to be of limited effectiveness [9,10,37], or in which the
results are ambiguous or inconclusive [38,39].
Generally the products used in these formulations are claimed to have no or minimal detrimental effect on the produced
concrete [28,29,33]. Extended initial set times can result [57]. Generally, adjustment of the mix design and selection of
appropriate admixtures will compensate for any of the reported adverse effects.
5. OTHER INHIBITOR SYSTEMS
Over recent years, a considerable number of chemicals have been evaluated as potential corrosion inhibitors for use in
concrete. These evaluations have met with varying degrees of success, and sometimes effective inhibitors have proven
undesirable due to other factors such as toxicity or their effects on the placement and setting characteristics of the
concrete. A brief resume of such systems is given below.
Sodium nitrite acts as an anodic corrosion inhibitor that increases resistance to pitting when chloride is present [40].
Laboratory studies [41,42] on reinforced concrete mortar specimens indicate that sodium nitrite provides effective
corrosion inhibition but its effectiveness is dosage dependent. It has also been reported [43] that sodium nitrite reduces
the corrosion intensity for crack widths up to 0.10mm, however the effect was negligible for crack widths >0.10mm.
Several studies [e.g. 42,44,45] indicate that the use of sodium nitrite reduces the compressive and tensile strengths of
concrete by approximately 20%. Also the sodium cation increases the possibility of alkali-aggregate reaction in
susceptible aggregates. No historical data of successful use of sodium nitrite is available in the literature.
Potassium chromate is an anodic oxidising inhibitor that gives the mix a light green colour when added to concrete
[42,46]. A laboratory study [46] on concrete samples indicated that admixed potassium chromate provides corrosion
inhibition to steel reinforcement. However it must be added in sufficient quantity, if added in insufficient quantity
corrosion becomes intensely localised. For effective protection 2-4% potassium chromate by weight of cement is
required when 2% calcium chloride is present. Another laboratory study [47] on concrete samples indicates that
admixed potassium chromate increases the compressive strength and provides limited corrosion inhibition. It has also
been reported [42] that the use of potassium chromate reduces the 28-day compressive strength by approximately 40%
and does not provide corrosion inhibiting properties. Chromates are toxic and are skin irritants [46].
Sodium benzoate is an anodic non-oxidising inhibitor. It inhibits corrosion by forming an organic based protective film
or coating on the reinforcing steel surface. It requires large concentrations to have a beneficial effect [42,46], laboratory
studies on mortar specimens containing lightweight aggregate [41] and concrete [45] indicate that sodium benzoate at
concentration levels of 1-2% by weight of cement provide limited corrosion inhibition. If added in insufficient quantity,
the corrosion becomes intensely localised. Analysis of concrete [41] has shown that sodium benzoate was retained in the
concrete after five years. Sodium benzoate additions of 2% to the mixing water of concrete had no effect on the setting
time of the concrete but lowered its compressive strength [44,45].
Sodium monofluorophosphate (MFP, Na2PO3F) acts as an anodic non-oxidising inhibitor or passivator [48]. MFP
can be added to concrete during mixing, or may penetrate through the pores of hardened concrete if applied to the
surface [48,49]. A laboratory study [48] indicates that MFP may reduce corrosion of steel reinforcement in concrete.
For effective corrosion protection, the minimum ratio of MFP/Cl- should be 1. A recent survey of carbonated
structures treated with MFP by impregnation [49] has shown that the material remains at least four years in
concrete, concurrent laboratory tests using prepared mortar samples also showed significant resistance to leaching. No
comment on the effectiveness of MFP as a corrosion inhibitor was made in this work. The inhibitive effect of MFP
is pH dependent, MFP appears to be more effective as a corrosion inhibitor for use in carbonated concrete [60] than
in un-neutralised chloride contaminated concrete.
Sodium tetraborate (borax) is an inhibitor that forms a protective layer on the metal surface, through the reaction of
borate and oxygen, which serves as a barrier to metal dissolution [3,23]. This reaction appears to be highly dependent
on the pH of the pore solution. Tests indicate that the borate ion is more mobile in concrete than the chloride ion,
indicating an ability to migrate faster to the surface of reinforcement [3]. Laboratory studies [3,23] using concrete
specimens admixed with sodium tetraborate indicate that sodium tetraborate is ineffective as a corrosion inhibitor.
Laboratory studies of stannous chloride [50,51] indicate that it is not an effective corrosion inhibitor.

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Carboxylic acids can act as film forming adsorption type inhibitors [52]. Compositions trialed include formic
(HCOOH), acetic (CH3COOH), propionic (CH3CH2COOH) and malonic (CH2(COOH)2) acids [52]. A laboratory study
[52] indicates that 2.5% carboxylic acid by weight of cement reduces the corrosion current by forming a film around
the steel. Malonic acid is an effective corrosion inhibitor in the presence of 2.5% weight of chloride. An initial
retarding effect on the set of Portland cement was noted [52].
A one-year laboratory study [53] indicates that Butyl Ester is a damp proofer and not effective for inhibiting
corrosion.
Sodium orthophosphate, sodium chromate and calcium magnesium acetate (CMA) have been studied, but did not
show effective inhibition properties [43].
Formaldehyde has been reported to provide some inhibition, however it was detrimental to the compressive strength of
the concrete [47].
Calcium nitrate, zinc oxide, and lead nitrate have been studied, but found not to be effective corrosion inhibitors in
concrete [4].
Azide, ferrocyanide, ferric EDTA, p-bromobenzoate, methyl red, and ethyleneimine have also been found not to be
effective as corrosion inhibitors [4].
6. MIGRATING INHIBITORS
One of the most contentious areas of corrosion inhibitor technology as applied to reinforced concrete is the issue of
migrating inhibitors. Such materials are intended to be applied in one of three ways:
As a surface applied (topical) treatment from which the active constituent moves through the concrete cover to
establish protection of the embedded reinforcement.
As a treatment injected into the concrete, where again the active constituent moves through the concrete to establish
protection of the embedded reinforcement.
As a component of patch repair materials, where the active constituent moves out of the patch or overlay and through
the adjacent parent concrete to establish protection of the embedded reinforcement.
The central issues are firstly whether the inhibitor species can migrate within the concrete, and secondly whether they
can do so at a rate that will result in an effective concentration at the reinforcement surface within a suitable
timeframe. A further consideration is the issue of back migration and loss to the environment, with the attendant
possibility of loss of protection.
Product literature for Sika FerroGard 903 [58], a solution of migrating organic inhibitors formulated for surface
application, claims penetration rates of 2.5-20mm per day. The mechanism of transport is said to be mainly by
capillary suction, though liquid and vapour phase diffusion also contribute. Testing [34] that compares capillary rise
measurements with empirical concentration profiles indicates that the rate of migration is faster than allowed by
capillary suction alone. Hence the postulation of vapour-phase migration which would be a relatively rapid mass
transfer process if the species is volatile.
In the case of organic inhibitors, the concentration required at the surface of the reinforcement may be relatively low.
In the case of Sika FerroGard 903 the required concentration for maintenance of an effective film on the steel surface
has been estimated to be in the order of 0.1mg/kg of concrete [34]. If this is the case, rapid mass transfer of inhibitor is
more important in terms of time to achieve protection than time to achieve a significant concentration of inhibitor in
the vicinity of the reinforcement. As the method used in this study had a detection limit of 0.9mg/kg, it has been
contended that any measurable quantity of the product at the reinforcement is sufficient to provide protection [34].
A recent VTRC study where chloride contaminated concrete slabs were repaired using surface applied inhibitors
concluded after one years testing that the topical applications were ineffective [37]. The publication referred to here
does not indicate whether this was a failure of the inhibitor to be effective under the test conditions, or whether the
inhibitor failed to penetrate the depth of cover at sufficient concentration.
Studies that have examined the diffusion rate of organic inhibitors in saturated or near saturated concrete [55,56] have
yielded diffusion coefficients in the order of 10-11-10-12m2/sec. Although the concretes used in these works bear limited
correlation to normal construction concretes, especially those commonly used in Australian construction practice, the
values obtained are consistent with those measured for chloride ions in environmental exposures.
It is therefore evident, and can be readily confirmed by mathematical modelling using models available for chloride
ingress, that diffusion of inhibitor species in saturated concrete is too slow a process for these materials to offer
protection to embedded reinforcement within practical timeframes. It should be noted that the results of such
modelling will be optimistic, as such models assume a constant concentration gradient set by the external environment
as a boundary condition. In practice, rinsing or leaching of the surface, or evaporation of the inhibitor species will
reduce the concentration gradient and consequently the mass transfer rate.
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Sodium monofluorophosphate (MFP) can be applied in solution to a concrete surface as a migrating inhibitor
[48,49,60], for treatment of both chloride contaminated and carbonated concretes. Measurements of penetration rates
[49] obtained by determination of phosphorus concentration profiles indicate that 50mm cover can be penetrated in a
few days, though no indication of concrete quality is given. Migration is claimed to be by liquid phase diffusion,
however the rate of movement is more suggestive of capillary absorption into relatively dry concrete. As MFP reacts
with calcium hydroxide to form an insoluble salt, application to un-neutralised concrete results in significantly retarded
migration [49].
Calcium nitrite solution has been found to be ineffective when applied as a surface impregnation, but can have some
effect when injected into cracks at low pressure [59]. This lack of mobility may be explained by the proposed physico
chemical binding of nitrite ions by the cement matrix [61], analogous to the behaviour of chloride ions.
7. SUMMARY
Development of corrosion inhibitor technology for concrete structures faces many challenges:
The inhibitor must continue to be effective over extended design lives under changing conditions, particularly in the
case of chloride induced corrosion where the environment surrounding the reinforcement continues to become more
aggressive as chloride concentration increases with time.
The inhibitor cannot adversely affect the production, placement or strength development characteristics of the concrete
to an extent that cannot be readily compensated by available mix design technology.
The inhibitor should be relatively safe to handle in batching and placement, and environmentally friendly once in
place in the structure.
The inhibitor system must be competitive or advantageous when compared with other technologies for production of
durable concrete when viewed on a life-cycle cost basis.
When used in repair systems, corrosion inhibitors (especially migrating inhibitors) must offer performance and/or cost
advantages when viewed on a life-cycle cost basis.
In particular structures, the presence of the inhibitor cannot interfere with placement of other decorative or protective
treatments such as rendering/plastering, tiling or coating.
For the above reasons research into corrosion inhibitors for use in concrete structures, and assessment of their
suitability for use in a particular situation, is a truly multi-disciplinary field. It requires not only knowledge of
corrosion, electrochemistry and inhibitor chemistry; but also concrete technology, concrete production and placement
practice, civil engineering, prediction of deterioration mechanisms under the service environment, and life-cycle
costing.
From the available literature, several distinct bodies of information are evident.
The use of calcium nitrite in new construction is the best documented of the current technologies. Extensive laboratory
test data and documented ongoing in-situ case histories of over 15 years duration are available for assessment of
potential performance. Published data relating dosage rates to chloride thresholds allows a significant degree of
lifetime prediction modelling and cost-benefit analysis to be performed.
A range of organic chemical based inhibitor technologies has been shown in laboratory studies to provide corrosion
protection, and commercial products are available in the market for use in new construction. At this stage
documentation of long-term studies and in-situ case studies is not as advanced as is the case for calcium nitrite, and
appears inadequate for conduct of lifetime prediction modelling and cost-benefit analysis.
Some studies, particularly related to organic inhibitors, have yielded negative or ambiguous results. Often the concrete
technology and environmental issues surrounding these studies are not fully reported, so the reasons for the failure
are difficult to assess. This literature indicates that corrosion inhibitors are not a universal panacea for structural
concrete, and that application must be on an informed case by case basis.
Many potential systems have been assessed and dismissed on the basis of limited effectiveness or some other undesirable
characteristic. No doubt this body of information will continue to grow over time.
The use and effectiveness of migrating inhibitors in rehabilitation of existing structures remain contentious issues. Both
success and failure are reported, though the experimental conditions are often relatively poorly documented in the
publications. Studies of migration rate disagree on primary transport mechanisms, and often the concretes used in the
studies have limited relevance to Australian construction practice. Data is available to confirm that liquid phase
diffusion is too slow to be practicable. Capillary suction and, in certain cases, possibly vapour phase diffusion are most
likely to be the primary transport mechanisms. It follows from this that the technology is most likely only applicable to
relatively dry structures of relatively low quality concrete. A simple means of assessing concrete quality, in terms of
porosity and continuity of pores, for prediction of likely penetration rates is required. Some evidence of persistence of
these inhibitors in concrete is available, but more is required.
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8. CONCLUSION
Acceptance of corrosion inhibitors by the construction and repair industries is growing, as evidenced by the increasing
publication of case studies. There is no doubt that the technology is a viable option in control of reinforcement
corrosion.
What is now required is a coordinated multi-disciplinary approach to research, and to the development and reporting
of case studies. There will always be successes and failures in application, but only comprehensive analysis of the
contributing factors will expand the knowledge base in a manner that allows accurate assessment of the suitability of
the technology to a given application, and the conduct of design life modelling and cost-benefit analysis. This approach
is particularly important if remedial use of migrating inhibitors is to gain in credibility.
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Li, L.F., Sags, A.A., Poor, N.: Cement and Concrete Research Vol. 29 No. 3, 1999, pp315-321.

10. ACKNOWLEDGMENT
The Authors wish to thank the Directors of Taywood Engineering Limited for permission to publish this paper.

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