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Chapter 3

Concrete Repair & Restoration

197
Efficacy of MCI in Existing Concrete Structures (repair and rest)
Corrosion inhibitors can also provide protection to existing concrete structures through
topical coating or repair mortar application. Products in this category generally come in the
forms of A) pure inhibitor solution to be applied on concrete surface the inhibitors will then
be transported to embedded steel rebar via capillary infiltration and vapor phase diffusion; B)
Hydrophobic sealer with MCI component this approach protects by reducing egression of
corrosive species while simultaneously forming barrier layer on rebar surface though the action
of MCI molecules; and C) MCI containing repair mortar that supplies the rebar with the
migrating corrosion inhibitors.

MCI-2020, MCI-2020M, MCI-2020VO is a family of water-based impregnating migrating


corrosion inhibitors. In testing protocol according to G109 that lasted 1500 days and over 200
cycles of 3.5%NaCl ponding/drying, Figure 10, it was found that the inhibitor MCI-2020 had
increased polarization resistance (Rp) (60-80 kohms-cm2 with increasing trends) in the MCI
coated concrete than un-coated concrete, for both low density and high density concretes. The
untreated not only had lower Rp values, but also decreasing trends, Figure 11. Examination of
the embedded steel rebar after corrosion tests showed no corrosion attack for the MCI
treated concrete samples, while un-treated concrete showed corrosion, Figure 12. X-ray
photoelectron spectroscopy (XPS) and depth profiling confirmed that the inhibitor had reached
the rebar surface in less than 150 days. Depth profiling showed an amine-rich compound on the
rebar surface that corresponded with the increase in Rp and improved corrosion protection for
the MCI treated steel rebar even in the presence of chloride ions, Table 1. Based on measured
corrosion rate the life expectancy of a concrete reinforced structure can be improved by more
than 40 years.

Figure 10 Modified ASTM G109 Test Set-Up (continuous submersion)

a) b)
a) Samples prepared per ASTM G109 b) Samples modified for continuous immersion

198
Figure 11 Comparison in Polarization Resistance (Rp) in Low & High Density Concretes
Treated (MCI 2020 & MCI 2020 M) vs. Untreated

199
Figure 12 Rebar at the end of 1500 Days of Testing

a) b)

a) Un-treated concrete, rebar showed localized corrosion attacks. b) MCI-treated concrete,


rebar did not show any corrosion attacks.

Table 2: XPS analysis and spectrum of the rebar surface, untreated and MCI 2020M treated
concrete after 1500 days in 3.5% NaCl

Atomic Conc (%) Mass Conc (%) Atomic Conc (%) Mass Conc (%)
Peak
Untreated Untreated MCI MCI
Fe 2p 0.87 3.32 0.08 0.3
O 1s 30.19 33.06 31.4 35.91
C 1s 62.48 51.37 59.43 48.12
Ca 2p 0.15 0.42 1.08 3.01
Si 2p 4.72 9.08 1.26 4.14
Cl 2p 0.84 2.04 1.11 2.81
N 1s 0.74 0.71 5.64 5.71

Figure 13 - UV spectroscopy analysis of a concrete section 3 below a MCI-2020 treated


surface 5 weeks after the treatment demonstrated the inhibitor presence at that depth

200
Adhesion testing of several traffic coatings applied over surfaces treated with MCI-2020 showed
that MCI treatment had no adverse effect on the adhesion of the traffic coatings that followed .

A more severe test, the Cracked Beam Test modified from ASTM G109, on MCI-2020 showed
that the inhibitor delayed onset of corrosion. The control started to corrode at average of 3.75
cycles while the MCI-2020 treated specimens at average of 9.25 cycles, an improvement of
150%, Table 2. After corrosion initiation, the treated specimens showed reduced amount of
damage. For MCI-2020 treated concrete, the average corrosion was 28% of the control and the
average corrosion current was 53% of the control, respectively, after 20 monthly cycles, Table
3.

Table 3: Time-To-Corrosion of Cracked Beams

Concrete Monthly Cycles before Initiation of Corrosion


Mix
Beam Ave

1 2 3 4

Control 0 0 5 10 3.75

MCI2020 11 8 12 6* 9.25

* Beam had bottom bar corrosion

201
Table 4: ElectroChemical Measurements in Cracked Beams

Concrete Number of Monthly Test Cycles

Mix Ave corr current, Resistance, Half-cell potential, Intergral current,

A ohms negative Volts A-days

1 10 20 1 10 20 1 10 20 1 10 20

Control -37 - - 67 131 135 0.155 0.349 0.379 131 15837 75839
145 228

MCI2020 5 -18 -91 70 130 158 0.103 0.192 0.346 -16 583 21329

Another MCI product in protecting existing structures is MCI-2018, a sealer with MCI
component. Due to the MCI molecules, this sealer not only repels intrusion of corrosive
species from the surface, but introduces migrating inhibitors to the concrete and the embedded
rebar. The Cracked Beam Test shows that the resistance in the treated beam is 55% higher
than untreated at 7th cycle, Figure 14.

Figure 14: Resistance in Cracked Beams (MCI-2018 treated and untreated)

202
Specification of MCI Surface Treatments by Product

MCI surface treatments are designed for use on existing structures. They are designed to be
applied to clean, dry surfaces free of dirt, grease, oils, laitance, presence of other sealers or
coatings, etc.

The most concentrated application of MCI in a surface treatment is in a water-based solution


(MCI 2020, MCI 2020 V/O, MCI 2020 M, MCI 2020 MSC, MCI 2020 M V/O). These products
contain corrosion inhibitor only and are best for use direct to concrete or mortar. They can
be followed by a top coat if desired.

The MCI technology has also been combined with water repellants to create two-in-one
surface treatments with 100% organosilane (MCI 2018, MCI 2018 V/O), 40% silane (MCI
2019, MCI 2019 W), silane/siloxane blends (MCI 2022, MCI 2022 V/O) and silicates (MCI
2021). UV Tracers or fugitive dyes can be added to MCI surface treatments to confirm
application upon request.

Repair and Specialty

MCI admixtures have been combined into repair mortars and grouts (MCI 2023, MCI 2039 SC,
MCI 2701, and MCI 2702). They have also been incorporated into specialty products such as a
gel for injection to embedded reinforcing steel (MCI 2020 Gel), protection for post tensioned
cables (MCI 309, MCI PTC Emitters), concrete cleaners (MCI 2060, MCI 2061), concrete
removers (MCI Super Remover) and concrete curing compounds (MCI CorteCure).

203
Presented at the International Conference for Concrete Under Sever Conditions (ConSec), 2001,
Vancouver, Canada

SURFACE APPLIED MIGRATING


INHIBITORS FOR PROTECTION OF
CONCRETE STRUCTURES
Prof. Dubravka Bjegovic
University of Zagreb, Zagreb, Croatia
Prof. Behzad Bavarian
California State University, Northridge, USA
Masaru Nagayama
General Building Research Corporation of Japan, Osaka, Japan

Abstract
This paper discusses the protection of reinforced concrete using
surface applied Migrating Corrosion Inhibitors (MCI). Concrete
surface could be treated with migration corrosion inhibitor
during maintenance life as the prevention measure to assure the
extension of the structure service life. Migrating Corrosion
Inhibitor could be also added in repair systems as an admixture.
The experimental results are given for both applications from
different independent laboratories in different countries around
the globe.

1.Introduction

Corrosion of reinforcement has been recognized as one of the


most prevalent durability factors, which affects the largest group
of reinforced concrete structures as bridges, parking garages etc.
Corrosion could be brought under such control by application of
the protective measure. One of the possibilities is the topical
application of the migrating corrosion inhibitor. Migrating
corrosion inhibitors (MCIs) are a mixed (anodic /cathodic)
amino-carboxylate based inhibitor (1). The inhibition of cathodic

204
process is achieved by incorporation of one or more oxidizing
anions in an organic (amine) molecule of MCI. Inhibitor
molecules are hydrolyzed when adsorbed on the metal surface.
The nitrogen of the amine group is capable of entering into a
coordinate bond with metals thus enhancing the adsorbtion
process. Adsorption of cations increases the overpotential of
metal ionization and slow down the corrosion. The mixed
monomolecular film serves as a buffer to hold the pH at the
interface in the optimum range for corrosion resistance. The
inhibitor adsorption isnt a momentary process and requires
much time for completion resulting in a chemisorbed layer on the
metal surface. The migrating corrosion inhibitors can be added to
concrete as admixtures during concrete mixing, or topically
applied to the concrete surface, or placed into cracks in concrete
for injection application or inserted in the form of emitting
capsules for easy and renewable corrosion protection of existing
structures (2).
In spite of many published studies a lot of conflicting opinions
exist concerning the effectiveness of these products for corrosion
protection.
In this paper the effectiveness of the migrating corrosion
inhibitor applied on the concrete surface is tested and the results
of the investigation from different independent laboratories in
different countries around the globe are presented.

2. Experimental Procedures

2.1. Laboratory 1 (University of Zagreb, Croatia)


The concrete with w/c factor 0.7 was used for the preparation of
the test slabs as concrete substrate (2). The reinforced concrete
specimens were made in accordance with ASTM G 109. The
specimens were demolded after 24 hours and kept in a wet
chamber for 28 days (RH = 95%, T = 20+2oC). After 28 days the
upper surface of the specimens was wire brushed and the topical
application by brush was made according to suppliers
specification of 450 g/m 2. After the topical application of the
migrating corrosion inhibitor the specimens were cured for two
weeks at 20C and 65% RH.

205
0,000,501,001,502,002,503,003,504,004,505,00147101316192225283134374043

Fig 1. Total corrosion for untreated and topically treated


specimens with migrating corrosion inhibitor

The measurements of electrochemical potential and corrosion


current in accordance with ASTM G 109 were taken week during
one year. The results are given in Fig.1. The values of total
corrosion activity are significantly lower for migrating corrosion
inhibitor treated concrete in relation to untreated concrete. The
total corrosion activity in coulombs is three to four times less for
MCI treated concrete as compared to untreated specimens after
one year of the testing.

2. 2. Laboratory 2 (California State University, Northridge,


USA
Migrating corrosion inhibitors were investigated over a 400-day
period. These investigations were made on steel rebar in concrete
totally immersed in 3.5% NaCl in ambient temperatures using
electrochemical monitoring techniques. Due to low conductivity
of concrete, the corrosion behavior of steel rebar had to be
monitored using AC electrochemical impedance spectroscopy
(EIS). During this investigation, changes in the resistance
polarization and the corrosion potential of the rebar were

206
monitored to determine the degree of effectiveness for the
migrating corrosion inhibitors.
The reinforced rebars (class 60, rebar #4 steel wire, 12.7mm
diameter bar) were cast in concrete at one and two inches from
the surface and allowed to cure for 28 days. After 22 days, the
concrete blocks were sand blasted to remove loose particles,
debris, and rust deposited on the metal. This process left the
concrete with a marginally smoother surface. Red shrink-wrap
was placed on each of the exposed rebars to prevent additional
corrosion.
Three combinations were made: control concrete specimens,
concrete specimens with repair mortar applied on the specimen
surface and repair mortar with migrating corrosion inhibitor
applied on the concrete specimens surface.
The samples were then submerged in 3.5% NaCl solution for the
duration of the experiment.
During this investigation, samples were tested once a week to
measure the open circuit potential and resistance polarization
(Rp). Corrosion potentials were recorded at the beginning of
each AC impedance test. The Rp values obtained by curve fitting
data from the Nyquist plots in the EG&G M398 corrosion
software were used to estimate corrosion. The Rp values are
Unprotected Concrete/Rebar (Reference)
25.4 mm (1 Inch) Rebar Concrete Coverage
AC Impedance Tests
1.00E+05
Day 4 Day 55
Day 64 Day 71
1.00E+04
lZl (OHMS)

Day 115 day 187


day 253 day 324
1.00E+03 day 378

1.00E+02

1.00E+01
1.00E-04 1.00E-02 1.00E+00 1.00E+02 1.00E+04

FREQUENCY (Hz

Fig. 2. AC Impedance test for reference concrete

inversely proportional to the rate of corrosion. A high Rp value


could be an indication of a low corrosion rate. The Bode plots

207
were also obtained from this software to verify the Rp value for
each sample.
Base Coating
25.4 mm (1 Inch) Rebar Concrete Covera
AC Impedance Tests
1.00E+05

Day 3 Day 36
1.00E+04 Day 63 day 185
day 251 day 323
day 375
1.00E+03

1.00E+02

1.00E+01
1.00E-04 1.00E-02 1.00E+00 1.00E+02 1.00E+04

FREQUENCY (Hz)

Fig. 3. AC Impedance test for repair coating applied on specimen


surface
Base & MCI Inhibitor
25.4 mm (1 Inch) Rebar Concrete Cover
AC Impedance Tests
1.00E+05

day 3 day 43
day 57 day 78
1.00E+04
day 85 day 121
day 143 day 186
day 252 day 324
day 375
1.00E+03

1.00E+02

1.00E+01
1.00E-04 1.00E-02 1.00E+00 1.00E+02 1.00E+04

FREQUENCY (Hz)

Fig. 4. AC Impedance test for repair coating and MCI inhibitor


applied on specimen surface

208
The migrating corrosion inhibitor tested in this investigation
successfully inhibited rebar corrosion, Fig. 2-4. Also, the steel
rebar corrosion potentials were maintained at approximately -120
mV, and rebar resistance polarization reached as high as 250,000
ohms. All results indicate excellent corrosion resistance
performance.

2. 3. Laboratory 3 (General Building Research Corporation,


Japan)
Reinforced concrete specimens with the 0.6 w/c ratio were
prepared with two polished rebars of 13 mm in diameter and 100
mm long embedded horizontally with a concrete cover of 20 and
30 mm. For corrosion monitoring, mini sensors were embedded
in the vicinity of rebars in concrete specimens prepared with 0
and 3 kg/m3 chloride ions (3). After the 60-day initial curing the
specimens were permeated with migrating corrosion inhibitor
(MCI). The treated and non treated specimens were subjected to
alternately wet (40C and 100%RH) and dry (50C and 30%RH)
cycles during one week period.

Fig.5. Rebar and mini sensors arrangement in a mold

After 1311 days of testing non-treated test specimens showed


severe cracking and high corrosion rate of 73-92m/year in the
case of 3 cm concrete cover. The test specimens protected with

209
MCI showed only minor cracks and low rate of corrosion of 10-
12 m/year.

Fig. 6. Weight loss vs. time for untreated and treated with MCI
specimens

The potential, the polarization resistance, the electrolyte


resistance measurements and destructive test results (weight loss)
showed the effectiveness in decreasing rebar corrosion in
chloride contaminated concrete, Fig. 6. The appearance of the
concrete surface of the specimens after 1311 days under the
investigation is given in (3).

210
3. Conclusion

The migrating corrosion inhibitors for topical application were


investigated in two methods of application: as topical treatment
in an aqueous liquid carrier or as an MCI inhibited repair mortar.
In both cases the experimental results indicate that migrating
corrosion inhibitor offers an effective inhibiting system for
protecting reinforced concrete. These results are reported by
three independent laboratories and are in general agreement with
works by other researchers shown in references.

4. References:

1. Miksic B., Gelner L., Bjegovic D., Sipos L.: Migrating


Corrosion Inhibitors for Reinforced Concrete, Proceedings of
the 8th European Symposium on Corrosion Inhibitors, 18-22.
Sept. 1995. University of Ferrara, Italy, 569-588
2. Bjegovic D., Miksic, B.,: Migrating Corrosion Inhibitor
Protection of Concrete, Materials Performance, USA,
November 1999, pp. 52-56.
3. MCI 2020 Long Term Test Protection of Rebar in Concrete,
Interim Report General Building Research Corporation of
Japan, October 1998.
4. Martinola M., Viaduct N2 de Melide (T1): Assainissement
des bordures, SIA , No. 18, Vol.122, Aug.21,1996, 320-324.
5. Soerensen H., Poulsen E., Risberg J., On the Introduction of
Migrating Corrosion Inhibitors in Denmark - A Review of
Documentation Tests and Applications, Proceedings of
International Confrence Infrastructure Regeneration and
rehabilitation Improving the Quality of Life Through Better
Construction, Sheffield 28 June-2 July, 1999, pp. 1019-1029.
6. Bjegovic D., Miksic, B., Stehly R.: Effect of Migration
Corrosion Inhibitor on Corrosion of Reinforcing Steel,
Proceedings of the International Conference Creating with
Concrete, held at the University of Dundee, Scotland, UK,
September 1999, Vol. Controlling Concrete Degradation, pp.
81 91.

211
The Pentagon Light well Walls
Repair, Rehabilitation, and Protection for the Next 50 Year s

By Rick Edelson Reprinted with Permission by STRUCTURE magazine, January 2007

C onstructed in just 16 months during World


:DU,,WKH3HQWDJRQWKHZRUOGVODUJHVWRI FH
building, is undergoing a complete renovation,
rehabilitation, and modernization program. A
program with the goal of a minimum 50-year design
life has been mandated by Penren (www.pentagon.
r enovation.mil), the governing agency for the
Pentagon renovation. Thats right, it is anticipated
that repairs will last at least 50 years! Taking over
10 years to complete, every componentthe walls,
WKH RRUVWKHURRIVWKHwindows, the mechanical
and electrical systemsis being renovated or
replaced. This article is about one componentthe
most-used component in the Pentagonconcrete.
All structural elements of the Pentagon, except
one, are constructed of reinforced concrete. Sadly,
that concrete is deteriorating. This article explains
how to breathe at least 50 years of new life into
deteriorating concrete.
The one element of the Pentagon not constructed
of reinforced concrete is the outermost peri-
Fig. 1: Typical lightwell wall damage showing spalling and exposed, meter wall, made of limestone. This article
rusting reinforcing bars focuses on the remainder of the 1 million ft 2
(92,903 m 2) of the lightwell walls, which are
now undergoing a complete repair, rehabili-
tation, and protection program.
The Pentagon consists of five separate rings,
each approximately 90 ft (27.4 m) wide with
approximately 30 ft (9 m) between the rings. The
space between the rings is known as the lightwells.
Thus, we call the perimeter walls of each ring the
lightwell walls. The lightwell walls, constructed
of cast-in-place, reinforced concrete, are both
bearing walls and shearwalls.
The problem is corrosion, that is, rusting, of
the reinforcing bars in the lightwell walls and
related spalling damage caused by the expansive
forces created by the rusting bars. As steel rusts, it
expands 4 to 10 times its original size, creating
extreme tensile forces in the surrounding concrete.
From these tensile forces, the concrete cracks and
spalls. The Pentagon program is about the repair
and rehabilitation of the more than 250,000 ft2
(23,226 m2) of spalling. The typical damage is
represented in Fig. 1. The program also includes an
innovative protection system designed to resist the
Fig. 2: Scaffolding constructed to allow direct access to walls damage for the next 50+ years.

22 CONCRETE REPAIR BULLETIN MAY/JUNE 2007

212
Concrete testing prior to the implementation of
the program revealed that the lightwell walls were
constructed of approximately 3500 psi (24 MPa)
concrete. However, the reinforcing bars were often
placed less than 1/2 in. (12.7 mm) from the outer
surface, and testing revealed carbonation extending
into the walls a distance of 3-1/2 in. (89 mm) or
more. Reinforcing bars, normally protected against
corrosion by highly alkaline concrete, lose their
protection as a result of the carbonation process,
which lowers the alkalinity concrete from a
pH of over 13 to less than 11. Without corrosion
protection, approximately 20% to 30% of the walls
have suffered spalling damage; corrosion rate testing
reveals active corrosion in virtually every other
section of walls.
Thus, the goal is to structurally repair and rehab-
ilitate the corrosion-damaged concrete and protect Fig. 3: Jackhammer demolition in progress, exposing corrosion-
the remainder of the walls to resist future damage damaged reinforcing bars
for the next 50 years.
The Structural Engineer of Record for the
concrete repair program designed the concrete
repair work closely following the International
Concrete Repair Institute guidelines for concrete
repair. All damaged and spalling concrete, some
3 to 4 in. (76 to 102 mm) deep, is removed with
15-lb jackhammers, fully exposing rusting
reinforcing bars. Where corrosion has extended
around a bar, the bar is undercut; this allows the
full surface of the bar to be sandblasted clean,
removing all rust. Working closely with U.S.
Concrete Products, Timonium, MD, the manu-
facturer of the repair concrete, a color-matching,
low-shrinkage, pumpable repair concrete was
developed to comply with the specifications,
which require a color and texture match when
viewed from a distance of 30 ft (9 m) (the view
from any window across a lightwell). This is Fig. 4: Close-up view of corrosion-damaged reinforcing bars taken
easier said than done. Although some of the after completion of jackhammer demolition. Note the severe loss of
repairs are as much as 4 in. (102 mm) deep, some cross section at the bottom of the vertical bars in the photo
repairs are less than 1 in. (25 mm) deep, and some
are too small to economically build formwork.
For the minor amount of hand-patching that is
being performed on small repairs, a trowelable
mixture was developed. For the remaining repairs,
86 &RQFUHWH GHYHORSHG D SRO\PHUPRGL HG
plasticized, bagged material that is mixed on site.
7KLVPDWHULDO RZVHDVLO\LQWRWKHIRUPHGUHSDLUV
with extremely little shrinkage cracking. The
mixture allows repairs up to 4 in. (102 mm) deep
without large aggregate extension, and almost no
cracking. Simple external vibration is all that is
needed for good consolidation. In addition, the
concrete obtains at least 2000 psi (14 MPa) in less
than 3 days to allow for early stripping.
Concrete Protection and Restoration, Inc., the
concrete repair subcontractor, developed a form-
work system (Fig. 5) that allows for easy placement Fig. 5: Formwork in place constructed to match original formboard
of the repair concrete, as well as matches the nish on the existing walls

MAY/JUNE 2007 CONCRETE REPAIR BULLETIN 23

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24 CONCRETE REPAIR BULLETIN MAY/JUNE 2007

214
Corrosion-rate reduction, however, is only half
the battle. Without water, corrosion can be halted. The
question arises: how to stop water from absorbing
into the walls for 50 years? Further protection is
provided by a system reducing the absorption of
water into the walls. A 100% solids silane is applied
to the wall surface, after the application of the
corrosion inhibitor, to reduce absorption and to
repel water. Silane repels only water and breaks
down when exposed to ultraviolet light. To further
protect the walls, a much more durable surface is
needed, one which will last 50+ years and will
prevent the breakdown of the silane. To accomplish
this, potassium silicate was selected to enhance the
surface and to protect both the water repellant and
the corrosion inhibitor. Potassium silicate, originally
developed and manufactured in Germany by Keim
over 100 years ago, is reported in their literature to
remain in service 100 years after initial application.
The potassium silicate itself also resists water
absorption by creating a tough, water-resistant
mineral surface on the concrete. With both the
potassium silicate and the silane, water now sheds Fig. 8: Corrosion-rate monitoring of corrosion activity in unrepaired
off the surface of the concrete. In addition, a uniform portion of wall adjacent to exposed corrosion damage
color is achieved with the addition of pigments to
the potassium silicate, further improving the repair integrity and appearance of the lightwell walls,
to meet the required speci FDWLRQRIDFRORUPDWFK and future corrosion damage is resisted with a
as seen across the lightwells. system designed to protect the Pentagon concrete
With four separate products applied to an existing for the next 50+ years.
building, and on top of each other, compatibility
was a major concern. During the design of the
system, compatibility testing was performed by the Rick Edelson is the Vice President
manufacturers of the corrosion inhibitor, the silane, of Tadjer Cohen Edelson Asso-
and the potassium silicate. Each issued not only a ciates and the Principal in charge
joint compatibility statement, but a 20-year warranty RIWKH UPV5HSDLUDQG5HVWRU
for the performance of the system components. a tion Division. He ha s over
Quality control by the Prime Contractor, Hensel 20 yea r s of exper ience in the
Phelps, quality assurance by a third-party inspection evaluation, rehabilitation, repair,
agency, and quality assurance by Penren all ensure and corrosion mitigation for the
a complete installation. protection of concrete structures. Rick can be
The Penren design goal of repairs to last 50 years reached at eedelson@tadjerco.com or through
is achieved. Concrete repair has restored both the www.tadjerco.com.

MAY/JUNE 2007 CONCRETE REPAIR BULLETIN 25

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SPINOFF
National Aeronautics and Space Administration

222
FIGHTING CORROSION

ORIGINATING criteria of the N a t i o n a l A s s o c i a t i o n many shapes. The coating contains parti-


NASA CONTRIBUTION of Corrosion Engineers for complete cles of magnesium and indium, as well as
protection of steel embedded in moisture-attracting compounds that facil-
Reinforced concrete structures such as
concrete. Testing is being continued at itate the protection process. After the
bridges, parking decks, and balconies are
the Kennedy's Materials Science Beach coating is applied to the outer surface of
designed to have a service life of over 50
Corrosion Test Site. reinforced concrete, an electrical current
years. All too often, however, many struc-
is established between the metallic parti-
tures fall short of this goal, requiring
PARTNERSHIP cles and the surfaces of the embedded
expensive repairs and protection work ear-
steel rebar. This electrical current is
lier than anticipated. The corrosion of Cortec Corporation, of St. Paul, Minne- responsible for providing the necessary
reinforced steel within the concrete infra- sota, has licensed the NASA-developed cathodic protection for the embedded
structure is a major cause for this prema- technology and markets it under the brand rebar surfaces. Without this protection,
ture deterioration. Such corrosion is a name company manu- the embedded steel may continue to dete-
particularly dangerous problem for the factures and supplies corrosion protection riorate until failure.
facilities at NASA's Kennedy Space solutions to the petrochemical,
Center. Located near the Atlantic Ocean electronics/electrical, utility, construc- GalvaCorr is a breakthrough technology
in Kennedy is based in one of the tion, military/government, marine, basic with great commercial value for the trans-
most corrosive-prone areas in the world. metals, automotive, and equipment main- portation, infrastructure, marine infrastruc-
tenance markets. GalvaCorr is a compli- ture, civil engineering, and construction
In order to protect its launch support industries. Without this technology, embed-
ment to Cortec's line of Migrating
structures, highways, pipelines, and other ded steel structures will continue to cor-
Corrosion
steel-reinforced concrete structures, rode and deteriorate until failure occurs,
Kennedy engineers developed the costing companies billions of dollars to
Galvanic Liquid Applied Coating PRODUCT OUTCOME
repair their infrastructures. Cortec recom-
System. The system utilizes an inorganic GalvaCorr is a room temperature liquid mends GalvaCorr for parking decks, ramps,
coating material that slows or stops the coating that can be sprayed or hand and garages; commercial and civil engi-
corrosion of reinforced steel members applied to concrete structures. is neered structures; bridges and concrete
inside concrete structures. Early tests applied easily to vertical, horizontal, and piers; offshore platforms; and utility poles
determined that the coating meets the overhead surfaces, and to structures of above water line.
Cortec is a registered trademark of Cortec
Corporation.
GalvaCorr and Migrating Corrosion
are trademarks of Cortec Corporation.

The GalvaCorr liquid coating is applied to


concrete structures such as this bridge in
order to protect the structures from corrosion.

34 PUBLIC SAFETY

223
J. Francikovi, B. Miki, I. Rogan, M. Tomii: PROTECTION AND REPAIR OF REINFORCED CONCRETE
STRUCTURES BY MEANS OF MCI-INHIBITORS AND CORROSION PROTECTIVE MATERIALS

PROTECTION AND REPAIR OF REINFORCED


CONCRETE STRUCTURES BY MEANS OF
MCI-INHIBITORS AND CORROSION PROTECTIVE
MATERIALS
Jure Francikovi*, Boris Miki**, Ivan Rogan**, Mijo Tomii***
*Longus Co. Ltd.
Sachsova 4, 10000 Zagreb, Croatia, email longus@zg.htnet.hr

** Cortec Corporation
4119 White Bear Parkway St. Paul MN 55110, USA, email info@cortecvci.com

** Cortecros Co.Ltd. Production & Supplay of Corrosion Control Systems


Nova Ves 57, 1000 Zagreb, Croatia, email info@cortecros.hr

*** kiljo Gradnja Co.Ltd.


21270 Zagvozd, Croatia

Key words: Migrating Corrosion Inhibitors (MCI)

Abstract: ,QWKLVSDSHUWKHSURWHFWLRQRIUHLQIRUFLQJVWHHOLQQHZDQGH[LVWLQJUHLQIRUFHG
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224
J. Francikovi, B. Miki, I. Rogan, M. Tomii: PROTECTION AND REPAIR OF REINFORCED CONCRETE
STRUCTURES BY MEANS OF MCI-INHIBITORS AND CORROSION PROTECTIVE MATERIALS

1. INTRODUCTION
According to statistical indicators, damages of the reinforced concrete structures caused by
the corrosion of the reinforcing steel make more than 80% of all damages of the reinforced
concrete structures.
Corrosion protection of the reinforcing steel and the protection of the new and the
restoration of the old reinforced concrete structures by means of MCI-corrosion inhibitors
and anticorrosion materials, as well as with the systems, which contain these inhibitors,
represents important contribution and big step forward to the prolongation of the durability
and the lifetime of the reinforced concrete structures, and herewith to the major reduction
of the maintenance costs, as well as to the effectiveness of the building use. MCI-corrosion
inhibitors and anticorrosion materials and the systems, i.e. those, which contain these MCI-
inhibitors for the protection of the reinforcing steel and the protection of the new and the
restoration of the old reinforced concrete structures, have been used successfully around
the world for over 25 years.
3URGXFWRIWKHLURQFRUURVLRQ)HLVLURQR[LGH)H[2\
2 Fe + 1 O2 + H2O + heat 2 FeOH
1 vol ca. 2,5 vol
-Pure iron oxide has ca 2,5 times bigger volume than metallic iron.
-Reinforcing steel is not pure iron, but its alloy: steel.
-Products of corrosion are iron oxide mixture, depending on the compound and
concentration of the reactants, and on the thermodynamic conditions at which the
electrochemical corrosion reaction unfolds, and the volume of the developed corrosion
products is ca 3-12 times bigger than the initial volume of the reinforcing steel/iron.
-Corrosion occurrence on the surface of the reinforcing steel causes not only decrease of
adhesion/adherence between the reinforcing steel and the concrete, as well as the reduction
of the reinforcing steel section, but also due to the big increase of the volume of the
corrosion products in relation to the initial reinforcing steel volume huge pressures,
which cause appearance of the fissures, setting apart, cracking and scaling of the concrete
protection layer above the reinforcing steel.

2. MIGRATORY CORROSION INHIBITORS


Migrating corrosion inhibitors are chemical compounds on the amine basis (e.g.
aminocarbocsylates, amino alcohols, and o.), which through the process of chemical
adsorption, so called chemisorptions, bind/adsorb on the surface of the reinforcing
steel/iron (and other metals), making on the surface an firm and resistant micro layer thick
ca 20 m, resistant to many aggressive substances from the environment, primarily to the
impact of the chloride, in the nature omnipresent, and simultaneously very aggressive
against the iron oxides, which it chemically destroys.
0&,FRUURVLRQ LQKLELWRUV protect the reinforcing steel against the corrosion in both
oxidation ranges: cathode and anode range, in distinction from some other types of
corrosion inhibitors, such as e.g. nitrites therefore are MCI-corrosion inhibitors also
designate as mixed corrosion inhibitors.
MCI-corrosion inhibitors on the basis of amine compounds belong to the group of so called
cathode, respectively cathode-anode inhibitors, which adsorb (through chemisorptions) on
the surface of the reinforcing steel, preventing diffusion of the corrosion reactants (O2,

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J. Francikovi, B. Miki, I. Rogan, M. Tomii: PROTECTION AND REPAIR OF REINFORCED CONCRETE
STRUCTURES BY MEANS OF MCI-INHIBITORS AND CORROSION PROTECTIVE MATERIALS

H2O) to the do reinforcing steel, and in this way they protect it against the oxidation
processes, in distinction from anode inhibitors on the nitrites and/or chromates basis, which
protect the reinforcing steel from the corrosion through the anode passivisation, so that
they themselves participate in the anode process, i.e. oxidize instead of main metal.
Only the mechanically deteriorated concrete layer is removed, until the internal adhesion
and the adhesion to the reinforcing steel of 1,5 N/mm2 is reached, and upon that:
1. Cleaned and made rough substratum is impregnated by means of MCI-inhibitor,
2. Concrete surface is reprofiled and open reinforcing steel closed by means of repair
mortar, which contains MCI-inhibitor and
3. The concrete surface is finally worked out with the protective-decorative coat or
hydrophobic impregnation, both containing MCI-inhibitor aiming at the protection of the
reinforced concrete structure against moistening, impact of the atmospheric agents,
freezing, salts and other aggressive impacts in the environment.
It is important to stress that the protection of the reinforcing steel against the corrosion and
the protection of the new, respectively old reinforced concrete structures needs to be
performed applying complete protection system, as stated and not only partial, because
only full protection system protects the reinforcing steel enduringly and efficiently against
the corrosion and the reinforced concrete structure against the deterioration /damage.

3. QUALITY CRITERIA FOR THE CORROSIVE REPAIR-


PROTECTIVE MATERIALS AND SYSTEMS
3.1. Quality criteria of the cleaned concrete
Quality criteria of the cleaned concrete substratum and of the reinforcing steel of the
reinforced concrete structures for the application of the Ac-repair-protective systems
containing MCI-inhibitors:
1-Tensile strength of concrete substratum and adhesiveness of the concrete and reinforcing
steel: 1,5 N/mm2
2-Surface roughness depending on the repair mortar layer thickness: ca 5mm for layers
with thickness ca 10-50 mm and ca 1mm for layers with thickness 2-10 mm
3-pH: alkaline range, >9
4-Chlorides concentration: without limit (some authors state max 1%)
5-Openness of the concrete surface structure: >50% visible aggregate grains, degree of
coverage of the grains with the cement matrix ca 2/3 grain volume 6-Cleaness grade of the
cleaned reinforcing steel: min SA 2 resp. St3 (according to international standards ISO
8501-1, SIS 05 59 00 1967, DIN 55 928-Teil 4, ASTM D 2200-67, SSPC VIS) depending
on the cleaning method: sandblasting, shot blasting, hydro dynamically, manually.

3.2. Quality criteria of corrosion protective


Quality criteria corrosive repair-protective system/layer materials above the reinforcing
steel: concrete, resp. repair mortar, protective-decorative coat, resp. hydrophobic
impregnations, all containing MCI-inhibitors:

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J. Francikovi, B. Miki, I. Rogan, M. Tomii: PROTECTION AND REPAIR OF REINFORCED CONCRETE
STRUCTURES BY MEANS OF MCI-INHIBITORS AND CORROSION PROTECTIVE MATERIALS

1-Fluids impermeability: Gases permeability coefficient 1x10-16m2 (EN 993-4)


2-Chlorides diffusion: < 1x10-12 m2/s (GF)
3-Capillary water absorption coefficient: <10-1kg/m2h1/2 (HRN.U.M8.300)
4-Alkalinity: pH > 9,5
5-Anticorrosive reinforcing steel protection expressed in corrosion current
intensity/density:
- Accord. to ASTM STP 1065: < 0,1 A/cm2

4. PROCEDURE OF THE RESTORATION OF THE REINFORCED


CONCRETE STRUCTURE OF THE MODULE NO.3 ON THE
WHARF NO.5 IN THE PORT PLOE CARRIED OUT DURING
THE YEAR 2005
The works were carried out by the company KILJO-GRADNJA, Zagvozd, according to
the restoration project elaborated by the company GEOKON, Zagreb. The quality of the
used materials and of performed works has tested and controlled IGH-Regional centre,
Split.

Figure 1: The module No. 3 in port Plo e

4.1 Preparatory works


Cleaning of the concrete surface and reinforcing steel through hydrodynamic removal of
the deteriorated material with the high pressure water jet (>2000 bar) with a view to
prepare the substratum for the application of the material of the repair-protective system:
from the reinforcing steel separated and deteriorated protective concrete layer was removed
all to the sound, clean and firm substratum (quality criterion: tensile strength of the
concrete substratum and adhesiveness between the concrete and reinforcing steel: 1,5

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J. Francikovi, B. Miki, I. Rogan, M. Tomii: PROTECTION AND REPAIR OF REINFORCED CONCRETE
STRUCTURES BY MEANS OF MCI-INHIBITORS AND CORROSION PROTECTIVE MATERIALS

N/mm2). Corroded reinforcing steel was cleaned with the hydrodynamic water jet to the
cleanness grade min SA2 resp. manually to St3. High pressure pump was placed on the
floating platforms from which the applying of the repair mortar and the final superficial
treatment with the protective-decorative coat, resp. with the hydrophobic impregnation was
performed. Transport of the material and the communication of people were performed
through the openings in the reinforced concrete slab.
Corrosion protection of the reinforcing steel was performed with the polymer cement
coating, containing MCI-inhibitor. Application with the brush in 1-2 layers, consumption
cca 0,2 kg/m 12 mm, for the12 mm diameter reinforcing steel.

4.2 Impregnation
Impregnation of the entire concrete surface was with the water solution (1:4) of the
corrosion inhibitor MCI in powder. Application was with the brush or roller in 2 layer of
the total yield cca 25 m2/kg.

Figure 2.: Impregnation concrete surface

4.3 Reprofilation
Reprofilation of the concrete surface and the covering of the exposed reinforcing steel was
performed with the repair mortar containing MCI-inhibitor, with the manual application in
1-3 layers depending on the total thickness of the mortar layer (on some areas mortar
thickness even to 8 cm). Freshly applied repair mortar needed curing/protection against
to fast drying and loss of technological moisture. On the concrete surfaces of the faces of
the wharf, exposed to the insolation and to the air circulation, freshly applied repair mortar
was protected from the to fast drying by means of the curing on the basis soya oil
containing MCI inhibitor, applied with the brush or roller in one layer, yield ca 5 m2/l.

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J. Francikovi, B. Miki, I. Rogan, M. Tomii: PROTECTION AND REPAIR OF REINFORCED CONCRETE
STRUCTURES BY MEANS OF MCI-INHIBITORS AND CORROSION PROTECTIVE MATERIALS

Figure 3.: Reprofilation concrete surface

4.4. Protection of the entire surface


Protection of the entire surface, i.e. concrete and reprofiled with the repair mortar, from the
impact of the moisture and atmospheric agents was performed with the protective-
decorative coat, or hydrophobic impregnation:
:KDUIIDFHwas treated with the protective-decorative coat (colour light grey) on the basis
of 1-k acrylate binder containing MCI-inhibitor, applied with the brush or roller in two
layers of the total yield ca 8 m2/l and,
- &RQFUHWH VXUIDFHV RQ WKH VRIILW DQG LQ WKH LQWHULRU RI WKH VWUXFWXUH were protected with
treatment with the hydrophobic impregnation on the basis of sylane-syloxane in the water
medium containing MCI-inhibitor, application with the brush or roller in 1-2 layers, treated
surface does not change appearance or colour, yield, ca 3,5m2/l.

229
J. Francikovi, B. Miki, I. Rogan, M. Tomii: PROTECTION AND REPAIR OF REINFORCED CONCRETE
STRUCTURES BY MEANS OF MCI-INHIBITORS AND CORROSION PROTECTIVE MATERIALS

Figure 4.: MCI coating on the concrete surface

4.5 Report by the IGH-PC Split


Report by the IGH-PC Split on the quality control of the built in material and on the quality
of the realised works is positive, so it is stated in:
- it.2.1. Preliminary testing of the quality of the chosen material: on the basis of the
obtained test results, it was concluded that the restoration corrosive repair mortar conforms
to the criteria stated in the Working project of the design company GEOKON
- it.2.2. Preliminary testing of the quality of the readiness of the substratum: tensile strength
of the concrete substratum pull off comes to > 1,5 N/mm2, through which fact it
conforms to the required criterion, as well as chlorides concentration, which comes to
<0,4%
- it.2.3. Control testing of the quality of the built in material: on the basis of the obtained
continuous test results in relation to the repair mortar quality, it was concluded that the
repair mortar built in at the wharf no.5, module no.3, in the port Plo e conforms to the
conditions and criteria stated in the Working project
- it.2.4. Control testing of the quality of the realised restoration system: on the basis of the
daily obtained continuous test results in relation to the repair mortar quality, it was
concluded that the repair mortar built in the every porthole of the module no.3, in the port
Plo e conforms to the conditions and criteria stated in the Working project
- it.3. Final evaluation of the continuous control quality: it was confirmed that the quality
of the materials and works was proved through prescribed and documented testing and that
it is in accordance with the conditions and criteria given in the Working design
Restoration of the soffit and the face of the reinforced concrete structure of the wharf
no.5 elaborated by the company GEOKON, Zagreb.

230
J. Francikovi, B. Miki, I. Rogan, M. Tomii: PROTECTION AND REPAIR OF REINFORCED CONCRETE
STRUCTURES BY MEANS OF MCI-INHIBITORS AND CORROSION PROTECTIVE MATERIALS

5. REFERENCES
[1] Bjegovi D., Miki B., Ukrainczyk V., Corrosion protection of the reinforcing steel
through migratory inhibitors
[2] Bjegovi D.., Designing of the lifetime of the reinforced concrete structures on roads,
Scientific-research project
[3] Haynes M., (1997), Use of migratory corrosion inhibitors, Construction Repair
July/August
[4] Miki B., Gelner L., Bjegovi D., Sipos L., Migrating Corrosion Inhibitors for
Reinforced Concrete, Proceedings of the 8th European Symposium on Concrete Inhibitors,
University of Ferrara, Italy, 1995
[5] Broomfield J., The pros and cons of corrosion Inhibitors, Construction Repair
July/August, 1997
[6] Alonso C., Andrade C., Effect of Nitrite as a Corrosion Inhibitor in Contaminated and
Chloride-free Carbonated Mortars, American Concrete Institute Materials Journal, 1990
[7] Yongmo, X.; Hailong, S: Comparison of Amin- and Nitrite-Inhibitorsin Carbonation-
Induced Corrosion; China Building Materials Academy, Materials Performance, Jan.
2004., p 42-46
[8] Berke N., Corrosion Inhibitors in Concrete, Concrete International 7, 1991
[9] Technical documentation of the company CORTEC Corporation, Minnesota, USA
[10] Report IGH-PC-Split on the testing results of the quality of the built in materials and
on the quality of the realised restoration works in 2005., No.3617/340-05/VN, November
2005.

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Paper
04323

IMPROVING DURABILITY OF REINFORCED CONCRETE STRUCTURES USING


MIGRATING CORROSION INHIBITORS

Behzad Bavarian and Lisa Reiner


Dept. of Manufacturing Systems Engineering & Management
College of Engineering and Computer Science
California State University, Northridge, USA

ABSTRACT

Steel corrosion poses formidable concerns for long term reliability of reinforced concrete
structures. In the United States, with its vast infrastructure of concrete and steel bridges, superhighways,
and reinforced concrete buildings, billions of dollars have been spent on corrosion protection. Among
the commercial technologies available today, migrating corrosion inhibitors (MCIs) show versatility in
their use as admixtures, surface treatments, and in rehabilitation programs. The effectiveness of two
commercial inhibitors applied to the reinforced concrete surface was evaluated. The corrosion behavior
of the steel rebar was monitored using AC electrochemical impedance spectroscopy (EIS). Corrosion
potentials and polarization resistance values corroborated the inhibiting effects of the amine carboxylate
and amino alcohol chemistry in an aggressive environment. The MCI products have successfully
inhibited corrosion of the rebar in a 3.5% NaCl solution for duration of testing. MCI protected samples
showed an average corrosion rate of 0.34 compared to untreated samples that were 1.50
This will increase the life expectancy by more than 15 years. XPS analysis demonstrated the
presence of inhibitor on the steel rebar surface indicating MCI migration through the concrete.

Keywords: steel rebar, migrating corrosion inhibitors, electrochemical monitoring techniques

INTRODUCTION

Corrosion is one of the main concerns in the durability of materials and structures. Much work
has been done to develop a corrosion inhibition process to prolong the life of existing structures and
minimize corrosion damages in new structures. Carbon steel is one of the most widely used engineering
materials despite its relatively limited corrosion resistance. Iron in the presence of oxygen and water is
thermodynamically unstable, causing its oxide layers to break down. Corrosion undermines the physical

259
integrity of structures, endangers people and the environment, and is very costly. Because carbon steel
represents the largest single class of alloys used [1], corrosion is a huge concern. The billions of dollars
committed to providing protective systems for iron and steel have provided new ways of combating
corrosion. Migrating corrosion inhibitors (MCIs) are one means of protection for reinforced concrete
structures. Previous studies have established the benefits of using migrating corrosion inhibitors, the
importance of good concrete, and the significance of the ingredients used to make the concrete [2-6].
Reinforcing steel embedded in concrete shows a high amount of resistance to corrosion. The cement
paste in the concrete provides an alkaline environment that protects the steel from corrosion by forming
a protective ferric oxide film. The corrosion rate of steel in this state is negligible. Factors influencing
the ability of the rebar to remain passivated are the water to cement ratio, permeability and electrical
resistance of concrete. These factors determine whether corrosive species can penetrate through the
concrete pores to the rebar oxide layer. In highly corrosive environments (coastal beaches and areas
where deicing salts are common), the passive layer will deteriorate, leaving the rebar vulnerable to
chloride attack, thereby requiring a corrosion prevention system.

Migrating Corrosion Inhibitor (MCI) technology was developed to protect the embedded steel
rebar/concrete structure. Recent MCIs are based on amino carboxylate chemistry and the most effective
types of inhibitor interact at the anode and cathode simultaneously [2]. Organic inhibitors use
compounds that work by forming a mono molecular film between the metal and the water. In the case of
film forming amines, one end of the molecule is hydrophilic and the other hydrophobic. These
molecules will arrange themselves parallel to one another and perpendicular to the reinforcement
forming a barrier [3, 7]. Migrating corrosion inhibitors are able to penetrate into existing concrete to
protect steel from chloride attack. The inhibitor migrates through the concrete capillary structure, first by
liquid diffusion via the moisture that is normally present in concrete, then by its high vapor pressure and
finally by following hairlines and microcracks. The diffusion process requires time to reach the rebar's
surface and to form a protective layer. MCIs can be incorporated as an admixture or can be surface
impregnated on existing concrete structures. With surface impregnation, diffusion transports the MCIs
into the deeper concrete layers, where they will inhibit the onset of steel rebar corrosion. Laboratory
tests have proven that MCI corrosion inhibitors migrate through the concrete pores to protect the rebar
against corrosion even in the presence of chlorides [4, 5].

EXPERIMENTAL PROCEDURES

The main objective of this investigation was to study the corrosion inhibiting properties and to
determine whether these inhibitors protect the steel rebar in concrete. Electrochemical monitoring
techniques were applied while samples were immersed in 3.5% NaCl at ambient temperatures. Due to
the low conductivity of concrete, the corrosion behavior of steel rebar was monitored using AC
electrochemical impedance spectroscopy (EIS). Effectiveness of this MCI product was based on changes
in the polarization resistance and the corrosion potential of the rebar, measurements that can be
performed without destroying the sample. This data can provide early warning of structural distress and
evaluate the effectiveness of corrosion control strategies that have been implemented. Once rebar
corrosion has proceeded to an advanced state, where its effects are visually apparent on the concrete
surface, it is too late for minor patchwork. The key to fighting corrosion is in preventative measures.

Prior to investigating the performance of two inhibitors, MCI 2020 and MCI 2020M, their
potentiodynamic behavior was assessed. Studies were conducted in a saturated Ca(OH)2 solution with

260
and without chloride ions using EG&G M352 DC corrosion test software. Comparisons of the
polarization behavior were made for the steel rebar in solution with varying concentrations of inhibitor
and the introduction of a corrosive species (2000 ppm NaCl). The effects of the mixed inhibitor in an
alkaline environment similar to the concrete medium were observed.

In this investigation, the steel rebar/concrete combination is treated as a porous solution and
modeled by a Randies electrical circuit [8]. EIS tests performed on a circuit containing a capacitor and
two resistors indicate that this model provides an accurate representation of a corroding specimen. EIS
tests, by means of a small amplitude signal of varying frequency, give fundamental parameters relating
to the electrochemical kinetics of the corroding system. The values of concern in this study are Rp and
The RP value is a measure of the polarization resistance or the resistance of the surface of the
material to corrosion. is a measure of the solution resistance to the flow of the corrosion current. By
monitoring the RP value over time, the relative effectiveness of the sample against corrosion can be
determined. If the specimen maintains a high RP value in the presence of chloride, it is considered to be
passivated or immune to the effects of corrosion. If the specimen displays a decreasing Rp value over
time, it is corroding and the inhibitor is not providing corrosion resistance.

Concrete samples with dimensions 20cm x 10cm x 10cm were prepared using a 20 cm steel rebar
(class 60, 1.27 cm diameter) and a 20 cm Inconel 800 metal strip (for the counter electrode). A concrete
mixture containing commercial grade-silica, Portland cement, fly ash, and limestone (concrete mixture
ratio: 1 cement/2 fine aggregate/4 coarse aggregate) were combined with one-half gallon water per 27.2
Kg (60-lb) bag in a mechanical mixer. The water to cement ratio was varied to achieve the two densities
and the coverage layer was maintained at 2.5 cm (1 inch) concrete for all samples. Compressive
strengths were roughly 27.6 MPa (4000 psi) for the low density and 41.4 MPa (6000 psi) for the high
density concrete cured for 28 days per ASTM C387 [9], All samples were sandblasted to remove loose
particles and provide surface uniformity. The experiments were conducted using an EG&G
Potentiostat/Galvanostat (Model 273A with a 5210 Lock-in amplifier), EG&G M398 and Power Suite
Electrochemical Impedance Software and a Gamry PC4-750 Potentiostat with EIS300 software and
Echem Analyst. Bode and Nyquist plots were created from the data obtained using the single sine
technique. Potential values were recorded and plotted with respect to time. By comparing the bode plots,
changes in the slopes of the curves were monitored as a means of establishing a trend in the Rp value
over time. To verify this analysis, the Rp values were also estimated by using a curve fit algorithm on the
Nyquist plots (available in the software). In these plots, the Rp and combined values are displayed in
the low frequency range of the bode plot and the value can be seen in the high frequency range of the
bode plot. The diameter of the Nyquist plot is a measure of the Rp value.

As outlined in Table 1, there were six (6) concrete samples in total, two were surface impregnated
with several coats of MCI 2020 and two were coated with MCI 2020M. The inhibitor was applied to the
surface of the concrete with a paint brush while partially immersed in a shallow container of inhibitor.
The remaining two samples were left untreated and used as standards for comparison. An additional coat
of MCI 2022 sealer was used to prevent the inhibitor from washing off in solution. Clear silicon was
applied to the concrete/metal interface to prevent easy access for ions. The testing environment was a
solution of 3.5% NaCl and water with roughly 175 mm (7 inches) of each sample continuously
immersed for 360 days. A Cu/CuS04 electrode was used as the reference and each sample was tested
once every two weeks.

261
RESULTS

Many procedures have been developed for monitoring the corrosion of rebar in concrete, each
method attempts to improve a shortcoming of an existing technique. Measuring the open circuit
potential is very easy and inexpensive, but is not considered very reliable since the potential provides no
information about the kinetics of the corrosion process. Linear polarization resistance (LPR)
measurements are influenced by IR effects from the concrete. A significant potential drop in the
concrete makes an accurate determination of the potential of the rebar surface very difficult.
Electrochemical impedance spectroscopy (EIS) is able to overcome the difficulties of the concrete
resistance, yet requires more testing time. The different analytical methods of electrochemical
impedance spectroscopy are capable of giving more detailed information than LPR. The rebar potential,
polarization resistance and current density data can provide information as to whether the rebar is in the
active or passive corrosion state. Estimates made from these parameters for Tafel constants can be input
into LPR analysis or can be used for corrosion rate measurement and cathodic protection criteria.
Evaluation of the effectiveness of corrosion inhibitors and the effects of concrete composition is often
based on these variables. For a more comprehensive approach to the corrosion process, several tests
methods have been implemented in this investigation.

Corrosion Potentials
The corrosion inhibition for the inhibitor identified as MCI 2020 has been investigated over a
period of 360 days using AC electrochemical impedance spectroscopy (EIS). Throughout this
investigation, changes in the corrosion potential of the rebar were monitored to determine the effects of
this commercially available inhibitor. According to the ASTM (C876) standard [10], if the open circuit
potential (corrosion potential) is -200 mV or higher, this indicates a 90% probability that no reinforcing
steel has corroded. Corrosion potentials more negative than -350 mV are assumed to have a greater than
90% likelihood of corrosion. Figure 1 shows that the corrosion potentials for the samples (except the
untreated low density sample) were between the range of 0 mV to -100 mV after 360 days of immersion
in NaCl. Given an open circuit potential of-270 mV and declining, the untreated (low density) sample
appears to suffer corrosion.

Polarization Resistance
This electrochemical technique enables the measurement of the instantaneous corrosion rate. It
quantifies the amount of metal per unit of area being corroded in a particular instant. The method is
based on the observation of the linearity of the polarization curves near the potential Ecorr. The slope
expresses the value of the polarization resistance if the increment diminishes to zero. This Rp value
is related to the corrosion current Icorr by the following Stern-Geary equation: Icorr = Where A
is the area of the metal surface evenly polarized and B is a constant that may vary from 13 to 52 mV.
For the case of steel embedded in concrete, the best fit with parallel gravimetric losses, results in B = 26
mV for actively corroding steel, and B = 52 mV for passivated steel. Figure 2 shows increasing trends
for the samples with polarization resistance values between 60 and 70 The value for the
untreated low density sample reached 40 before rapidly declining to 4 at 350 days of partial
immersion in the aggressive solution.

Bode Plots
Bode plots are not dependent on modeling the corroding system as are polarization resistance
values. The electrochemical impedance spectroscopy data are obtained by applying a single sine wave

262
over a range of frequencies while measuring the corresponding impedance. Since the results are
independent of an assumed model, the technique is highly reliable. Figure 3 shows a comparison of bode
plots for the first day of testing and after 360 days of immersion. There is not much variation in the
curves, except for the low density untreated sample which sharply contrasts with the rest.

Potentiodynamic Behavior
Figure 4 shows a comparison of the polarization behavior from a potentiodynamic test of steel
rebar in a saturated Ca(OH)2 solution. This graph shows the effects of a mixed inhibitor in an alkaline
environment similar to the concrete medium with minor reduction in the corrosion current upon addition
of MCI. Figure 5 shows the polarization results from the steel rebar tested in a saturated Ca(OH)2
solution with 2000 ppm NaCl. The effects of the inhibitor are far more noticeable in the presence of a
corrosive species. The breakdown potential for the rebar tested with no inhibitor was around 350 mV
SCE as compared to 600 mV for the rebar tested with 2000 ppm MCI. Figure 6 shows the
corresponding current density for the various additions of MCI in column format. Consistent with the
graph in Figure 5, the rebar tested in a saturated Ca(OH)2 solution with 2000 ppm NaCl and 2000 ppm
MCI had the lowest corrosion rate. According to the data in Table 2, where a level of corrosion severity
has been associated with a given icorr value, the sample tested with 2000 ppm MCI and having a
corrosion rate of less than 0.34 will have "no expected corrosion damage."

X-ray photoelectron spectroscopy (XPS)


The XPS analysis verified the inhibitor's ability to penetrate through the concrete pores by vapor
phase diffusion, permeation along the microcracks, and capillary effects. Figure 7 shows the XPS
analysis and spectrum for the rebar removed from the MCI treated sample after 320 days. The analyses
show an organic compound carboxylate chemistry similar to the migrating corrosion inhibitor compound
(nitrogen content, carbon and oxygen ratio is attributed to MCI compound). Depth profiling (using 4 kV
Argon ions) measured a 100 nm layer of amine compounds on the rebar surface, confirming surface
adherence after migration. Chloride was also found on the surface of the rebar. The XPS results
demonstrate that both MCI and corrosive species had migrated in through the concrete capillary system,
however, MCI had managed to coat the surface and neutralize the corrosive species (chloride ions and
carbon dioxide) to protect the steel rebar.

CONCLUSIONS

At 360 days of immersion, all samples but one (low density-untreated), seem to have maintained
a stable passivation layer that has protected the steel reinforcement from the corrosive environment. The
MCI products have successfully inhibited corrosion of the rebar in a 3.5% NaCl solution for duration of
testing. MCI protected samples showed an average corrosion rate of 0.34 compared to untreated
samples that were 1.50 This will increase the life expectancy by more than 10-15 years. XPS
analysis demonstrated the presence of inhibitor on the steel rebar surface indicating MCI migration
through the concrete. Depth profiling showed a layer of amine-rich compounds and chloride ions on the
rebar surface; however the neutralizing effects of the inhibitor assured satisfactory corrosion resistance.

263
ACKNOWLEDGEMENT

Thanks go to the National Aeronautics and Space Administration (NASA-IRA program) and
CORTEC Corp. for their sponsorship of this project.

REFERENCES

1. http://www.corrosioncost.com/home.html
2. D. Bjegovic and B. Miksic, "Migrating Corrosion Inhibitor Protection of Concrete," MP, NACE
International, Nov. 1999.
3. D. Stark "Influence of Design and Materials on Corrosion Resistance of Steel in Concrete." R & D
Bulletin, RD098.01T. Skokie, Illinois: Portland Cement Association, 1989.
4. B. Bavarian and L. Reiner, "Migrating Corrosion Inhibitor Protection of Steel Rebar in Concrete,"
Materials Performance, 2003.
5. B. Bavarian and L. Reiner, "Corrosion Protection of Steel Rebar in Concrete using Migrating
Corrosion Inhibitors," BAM 2001.
6. J. P. Broomfield et al, "Corrosion of Metals in Concrete," ACI 222R-96.
7. R. Dagani, "Chemists Explore Potential of Dendritic Macromolecules As Functional Materials,"
Chemical & Engineering News, American Chemical Society, June 3, 1996.
8. D. Jones, Principles and Prevention of Corrosion, 2nd Edition, Prentice Hall, NJ, 1996.
9. ASTM C387 Standard Specification for Packaged, Dry, Combined Materials for Mortar and
Concrete, Vol. 04.02.
10. ASTM C876 Standard Test Method for Half Cell Potentials of Reinforcing Steel in Concrete,
Annual Book of ASTM Standards, Vol. 04.02, 1983.

Table 1. Sample specifications.

Number of Concrete Surface Coating Density Water to cement


samples ratio
1 No treatment-control sample Low = 2.08 g/cm3 0.65
1 No treatment-control sample High = 2.40 g/cm3 0.35
1 MCI 2020 3 0.65
Low = 2.08 g/cm
1 MCI 2020 3 0.35
High = 2.40 g/cm
i MCI 2020M Low = 2.08 g/cm3 0.65
i MCI 2020M High = 2.40 g/cm3 0.35

264
Figure 1: Corrosion Potential vs Time: Various Density Concrete (MCI 2020M, MCI 2020, untreated).

-50

-100

-150

-200

-250

-300
0 SO 100 150 200 250 300 350 400

Time of Submersion (Days)

Figure 2: Polarization Resistance (Rp) Versus Time; Comparison of treated (MCI 2020 & Md 2020M)
low & high density concrete with untreated concrete.

8.0E+04
High denstty-MCI 2020M
Low denslty-MCI 2020
7.0E+04
High density-untreated
High denslty-MCI 2020
Low denslty-MCI 2020M
6.0E+04
Low density-untreated

5.0E+04

4.0E+04

3.0E+04

2.0E+04

1.0E+04

O.OE+00
0 so 100 150 200 250 300 350 400
TIME (Days)

265
Figure 3: AC Impedance Spectroscopy Results (Concrete density H = 2.40 g/cm3, L = 2.08 g/cm3)
Bode Plot Comparison of MCI 2020 & 2020M with Untreated Concrete

1.0E+05

1.0E+04

1.0E+03

1.0E+02

1.0E+01
0.0001 0.001 0.01 0.1 1 10 100 1000 10000 100000
FREQUENCY (Hz)

Figure 4: Polarization Bahavlor of Steel Rabor In a saturated Ca(OH)2 solution


+varlous ppm MCI additions, pH 12.5, 23 C
1.00E-03

1.00E-04

1.00E-05

1.0OE-06

1.0OE-O7

1.00E-08

1.0OE-09
-1000 -500 0 500 1000 1500
Potential, mVsce

266
Figure 5: Polarization Behavior of Steel Rebar In a saturated Ca(OH), solutlon+2000 ppm NaCI
and various ppm MCI additions, pH 12.4, 23 C

1.00E-03

1.00E-04

1.00E-05

1.00E-06

Ca(OH)2
+2000ppm CI- +2000ppm MCI
1.00E-07 +2000ppm CI- +1200ppm MCI
+2000ppm CI- + 1000ppm MCI
+2000ppm CI- + 5OOppm MCI
+2000 ppm CI-

1.00E-08

1.00E-09
-1000 -500 0 500 1000
Potential, mVsce

Figure 6: Polarization Behavior of Steel Rebar In a saturated Ca(OH)2 solution


+2000 ppm NaCI and various ppm MCI additions, pH 12.4, 23 C

267
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349
Paper No.

06347

Current Progress in Corrosion Inhibition of Reinforcing Steel in Concrete using


Migrating Corrosion Inhibitors

Bezad Bavarian and Lisa Reiner

Dept. of Manufacturing System Engineering and Management


California State University, Northridge
18111 Nordhoff Street
Northridge, California 91330-8332, USA

ABSTRACT

Several migrating corrosion inhibitors for reinforced concrete were investigated using ASTM
G109 and Modified G109. XPS depth profiling showed a 90-100 nm amine-rich layer and chloride ions
on the steel rebar surfaces indicating that the modified corrosion inhibitor molecules had suppressed
chloride ion interaction and protected the steel rebar passivation layer. There is no indication of
corrosion after 400 days of testing. The inhibitor treated samples showed improved resistance
polarization (Rp was in the 50 kohm to 60 kohm range, corrosion potentials ranged between -64 mV and
-103 mV) and potentiostatic tests showed a significantly lowered corrosion rate. These findings led to
investigating the adsorption mechanism where comprehensive testing established a Langmuir adsorption
isotherm and verified that chemisorption was responsible for the strong bonding between the inhibitor
monolayer and the steel surface.

Keywords: reinforced concrete, migrating corrosion inhibitors, steel corrosion, XPS, adsorption
mechanism

INTRODUCTION

The US infrastructure is heavily reliant upon construction materials that are vulnerable to
corrosion. Conventional materials like reinforced concrete, prestressed concrete and steel that are used
in bridges, highways and building foundations. Reinforcing steel embedded in concrete, however, shows
a high amount of resistance to corrosion. Concrete is a highly alkaline material with a pH near 12 that
Copyright
2006 NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE International,
Conferences Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of
the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.

350
provides a protective oxide layer for steel when embedded. Under corrosive conditions where oxygen
and moisture can ingress through the pores of the concrete to reach the rebar surface, the alkalinity can
change and cause the passive layer to breakdown. Carbonation of the concrete, where carbon dioxide
reacts with calcium hydroxide or other cement hydrates, and ingress of chlorides are major causes of
steel rebar corrosion in concrete. In the case of reinforced concrete samples placed in contact with a 3%
NaCl solution, the stages for rebar corrosion deterioration would begin with chloride penetration into the
concrete, then corrosion initiation or passive layer breakdown, more progressed corrosion, micro
cracking and eventual spalling. Corrosion is a complex phenomenon with many interactions to consider
(structural, physical, chemical and environmental considerations), for steel in rebar, as the passive film
degrades by chloride ions or the pH drops due to carbonation, the metallic iron at the anode is oxidized
to form ferrous ions. It is this simplified reaction that has to be prevented or at least mitigated. Much
effort has been focused on the design of new structures to reduce or eliminate corrosion through
increased concrete coverage using reduced permeability concrete, admixtures, migrating corrosion
inhibitors and replacing the steel reinforcement with alternative materials.

The commercially available migrating corrosion inhibitors used to surface impregnate the
concrete samples in this investigation are based on amino carboxylate chemistry [1]. They are designed
to provide both anodic and cathodic protection with transport to the rebar surface in roughly 100 days.
Transport begins through the concrete pores and proceeds through the capillary structure by liquid
diffusion, high vapor pressure and by following microcracks to the rebar surface. At the rebar surface,
the inhibitor forms a monomolecular layer of protection against corrosive species [2]. To better
understand how the inhibitor works or by what mechanism it is able to adsorb to the surface, a surface
adsorption isotherm has to be determined. Many models for adsorption isotherms have been defined
(Temkin, Freundlich, Langmuir and Frumkin) and each explains a different relationship between
concentration and inhibitor surface coverage on a metal or alloy surface [3, 4]. By measuring the
corrosion current density of the non-inhibited solution (Blank) and inhibited solution (or by measuring
polarization resistance), the surface coverage, , can be calculated from the following formula:

Icorr ( B )  Icorr ( I ) Rp ( I )  Rp( B )


= or =
Icorr ( B ) Rp ( I )

Where Icorr (B) and Rp (B) are the corrosion current density and polarization resistance of the Blank
solution, respectively, while Icorr (I) and Rp (I) are the corrosion current density and polarization
resistance of the inhibited solution. Based on the adsorption isotherm, the adsorption equilibrium
T
constant, Kad, can be calculated; for the Langmuir isotherm: KadC= ( ). This can then be used to
1T
calculate the free standard energy of adsorption, Gad = -RT Ln (Kad). By repeating the experiment at
different temperatures, the enthalpy of adsorption, Had, can be calculated from Ln C = (Had0/RT) +
constant. Chemisorption (chemical adsorption) makes strong covalent bonding between the chemical
and the surface, so the Gad is usually much higher than for physisorption (physical adsorption) that
involves van der Waals interaction. The criterion for chemisorption varies, it can require as little as -40
kJ/mol energy or as much as -100 kJ/mol energy [4-5]; physisorption requires energy between -5 to -25
kJ/mol [4]. The activation energy ('Ha) of corrosion is calculated using an Arrhenius type relationship
where [5],

351
 '+a
Icorr v exp( )
RT
The slope of this graph will represent -'Ha /R where R is the gas constant.

EXPERIMENTAL PROCEDURES

The ASTM G 109-92 test structure provides a less aggressive corrosion environment compared
with protocols for samples that were partially immersed in a 3.5% NaCl solution for the entire
experiment. In the test method described in G 109, Plexiglas dams hold the 3.0% NaCl solution in
contact with the surface of the concrete for two week periods and are then set to dry for 2 weeks with
this cycle repeating for the duration of the experiment. As seen in Figure 1, three steel rebar were cast in
concrete (density of 142 lbs/cu ft) with 1 inch coverage from the top and bottom rebar; concrete
dimensions were 3 inches width x 6 inches height, Plexiglas dams were 3 inches x 3 inches. Two
concrete samples were coated with Cortecs MCI 2020M inhibitor (inhibitor 1) and MCI 2022 sealer;
roughly 15 mL of inhibitor was absorbed into the concrete for 2 coats. Two concrete samples were
coated with MCI 2022 inhibitor (inhibitor 2) and sealer. All inhibitor and sealer were painted on with a
brush. The remaining 2 samples were untreated (references). Several days after the inhibitor and sealer
were applied, the Plexiglas dams were fixed to the top of the concrete beams with silicone.

The rebar potential, polarization resistance and current density data can provide information as to
whether the rebar is in the active or passive corrosion state. Estimates made from these parameters for
Tafel constants can be input into LPR analysis or can be used for corrosion rate measurement and
cathodic protection criteria. Evaluation of the effectiveness of corrosion inhibitors and the effects of
concrete composition is often based on these variables. For a more comprehensive approach to the
corrosion process, several tests methods were implemented in this investigation. These studies were
conducted using an EG&G Potentiostat/Galvanostat (Model 273A with a 5210 Lock-in amplifier),
EG&G M398 Electrochemical Impedance Software and a Gamry PC4/750
Potentiostat/Galvanostat/ZRA using electrochemical impedance spectroscopy EIS300 systems. The
steel rebar/concrete combination can be treated as a porous solution and was modeled by a modified
Randles electrical circuit. EIS tests performed on a circuit containing a capacitor and two resistors
indicate that this model is an accurate representation of an actual corroding specimen. EIS testing was
done by applying a small amplitude-alternating potential signal of varying frequency to the
concrete/rebar system, providing fundamental electrochemical parameters. A standard CuCuSO4
reference electrode was used with a steel rebar counter electrode in a 3-electrode configuration with a
steel working electrode.

In previous investigations using XPS depth profiling, it was determined that a 90-100 nm amine
rich layer and chloride ions were present at the surface of the steel rebar. The XPS results demonstrated
that both inhibitor and corrosive species had migrated in through the concrete capillary system, but the
inhibitor had managed to coat the surface and neutralize the corrosive species (chloride ions and carbon
dioxide) to protect the steel rebar [2]. This information led to investigating the mechanism by which
adsorption occurs. To collect data for adsorption isotherms, flat samples were polished (600 grit
sandpaper), placed in a flat cell and tested in solutions containing tap water and 3.5% NaCl with varying
inhibitor concentration. The Rp value (determined from the EIS Bode plots) was used to fit the data into
an adsorption isotherm model. To correlate the corrosion rate with the inhibitor concentration, a series of

352
linear polarization resistance (LPR) tests were conducted using Gamrys DC105 software and a blank
solution (no inhibitor) with 0.5% NaCl; inhibitor concentration was increased by 200 ppm for each
subsequent test. To explore the activation energy and adsorption thermodynamics for the inhibitor,
cyclic polarization was conducted in temperatures ranging from 23C to 63C.

RESULTS & DISCUSSION

Previous experiments (conducted on commercially available corrosion inhibitors) have shown


noticeable differences in the treated and untreated samples around 250 days of constant immersion [2, 6-
8]. In Figure 2, corrosion potentials vs time are graphed for comparison; this was a constant immersion
test. Inhibitor 1 was applied to the surface, mixed in the mortar and directly applied to the rebar before
casting (concrete density: 140 lbs/ft3). The graph also shows untreated concrete samples and samples
surface treated with other inhibitors (concrete density for L=130 lbs/ft3) [2]. Corrosion potentials for an
untreated low density concrete sample measured 150 mV more negative than the other samples. The
concrete sample was cracked open to physically verify that the rebar was corroding. Figure 3 shows a
comparison of the corrosion potential versus time with little variation over the course of a year. The steel
rebar appears to have formed a passive layer around day 150 and remained stable in the range of -40mV
to 135 mV. Figure 4 shows Rp values versus time obtained by curve fitting the bode plots (Figure 5).
The Rp values measured approximately 10000 ohms at the beginning of testing and increased to a range
between 50000 to 60000 ohms by day 400. EIS bode plots for treated and untreated concrete are from
initial tests and plots from data collected between day 371 and 400.

The potentiostatic tests (Figure 6) contrast the dramatic reduction in current density with
increasing inhibitor concentration. The corrosion current density for the blank solution was 10.5 A and
decreased to 0.45 A with 2000 ppm inhibitor; at saturation level (about 2000 ppm), the corrosion rate
remained steady. From the corrosion current for the given concentrations, different adsorption isotherms
were constructed to find the best fit for the data. Models were constructed based on surface adsorption
which is a function of the corrosion current and the concentration of the solution. Table 1 contains the
data obtained from linear polarization resistance. The EIS results showed that adsorption of inhibitor 1
on to the steel surface fits with the Langmuir adsorption isotherm [3, 4] since Ln C and Ln -Ln (1-)
have a linear relation as is shown in (Figure 7). The extent of surface coverage is expressed as the
fractional coverage, , or the ratio of adsorption sites occupied over the number of adsorption sites
available. The changes in enthalpy of adsorption (Had) and free standard energy of adsorption (Gad)
were obtained with adsorption isotherms and elevated temperature tests [3]. Based on results from cyclic
polarization, Ln Icorr vs. 1000/T oK was plotted (Figure 8); the slope of each line represents (-Had /R).
Figure 8 contains the data that was used to calculate the activation energy required to corrode the steel
with inhibitor (-46 kj/mol) and without (-30 kj/mol). The value calculated for the inhibitor would
indicate that the adsorption mechanism is achieved by chemically bonding to the surface.

CONCLUSIONS

Surface treated concrete samples with migrating corrosion inhibitors have been subjected to the
ASTM G 109 corrosion test for more than 400 days to confirm effectiveness. Corrosion potentials

353
ranged between -64 and -103 mV(Cu/CuSO4); polarization resistance values measured between 50 kohm
and 60 kohm. Potentiostatic tests showed a significantly reduced corrosion rate for steel rebar in the
presence of inhibitor. From the LPR and EIS analysis and adsorption isotherms, it was determined that
adsorption of inhibitor molecules to the steel surface most closely fit with Langmuir adsorption and was
controlled by a chemisorption mechanism.

ACKNOWLEDGEMENT

Thanks go to the National Aeronautics and Space Administration (NASA-IRA NCC 5-513
program) for their sponsorship of this grant.

REFERENCES

[1] D. Bjegovic and B. Miksic, Migrating Corrosion Inhibitor Protection of Concrete, MP, NACE International,
Nov. 1999.
[2] B. Bavarian, L. Reiner & C. Y. Kim, Corrosion Protection of Steel Rebar in Concrete by Migrating
Corrosion Inhibitors, NACE Corrosion/2003 paper #03364 (San Diego, CA).
[3] W. Durine, R. D Marco, A. Jefferson and B. Kinsella, Journal of the Electrochemical Society, 146 (5) 1751-
1756 (1999)
[4] M. L. Free, A new corrosion inhibition model for surfactants that more closely accounts for actual adsorption
than traditional models that assume physical coverage is proportional to inhibition, Corrosion Science,
Volume 46, Issue 12 , December 2004, Pages 3101-3113
[5] M. Lagrene, B. Mernari, M. Bouanis, M. Traisnel and F. Bentiss, Study of the mechanism and inhibiting
efficiency of 3,5-bis(4-methylthiophenyl)-4H-1,2,4-triazole on mild steel corrosion in acidic media,
Corrosion Science, Vol 44, Issue 3 , March 2002.
[6] B. Bavarian & L. Reiner, Improving Durability of Reinforced Concrete Structures using Migrating Corrosion
Inhibitors, NACE CORROSION/2004 Paper #04323 (New Orleans, LA).
[7] B. Bavarian & L. Reiner, Corrosion Protection of Steel Rebar in Concrete using Migrating Corrosion
Inhibitors, BAM, Germany, 2001.
[8] B. Bavarian & L. Reiner, Corrosion Inhibition of Steel Rebar in Concrete using MCI Inhibitors, EUROCORR
2000, London UK, September 2000.

354
Figure 1: ASTM G 109-92 standard concrete/rebar specimens.

100
MS1-surface treated L2022
50 MR1-rebar treated L2021
MM1-mortar coated surface L untreated
0 RF1-untreated

-50
Potential, (mV)

-100

-150

-200

-250

-300

-350

-400
0 50 100 150 200 250 300 350 400 450

Time of Submersion (Days)

Figure 2: Corrosion Potential vs Time for inhibitors that were applied to the surface, mixed in the mortar and
directly applied to the rebar before casting (Concrete density: 140 lbs/ft3); the graph also compares untreated
samples with untreated concrete (L =130 lbs/ft3) [2].

355
0

-50

-100
Potential, (mV)

-150

-200

-250 reference-1
inhibitor 2-1
-300 reference-2
inhibitor 1-1
-350 inhibitor 2-2
inhibitor 1-2
-400
0 50 100 150 200 250 300 350 400 450

Time of Submersion (Days)

Figure 3: Comparison of corrosion potentials for inhibitor treated and untreated concrete samples per ASTM
standard G 109.

60000

50000

40000
Rp (Ohms)

30000

20000
inhibitor 2-2
inhibitor 1-1
inhibitor 1-2
10000 reference-1
reference-2
inhibitor 2-1
0
0 50 100 150 200 250 300 350 400 450

Time of Submerged (Days)

Figure 4: Comparison of polarization resistance (Rp) for treated concrete with untreated concrete per ASTM G
109.

356
1.00E+05
inhibitor 1-1
inhibitor 1-1
inhibitor 2-1
inhibitor 2-1
reference-1
reference-1
1.00E+04
inhibitor 1-371
inhibitor 1-371
inhibitor 2-400
inhibitor 2-400
reference-371
reference-397
|Z| ohms

1.00E+03

1.00E+02

1.00E+01
0.0001 0.001 0.01 0.1 1 10 100 1000 10000 100000
Frequency, Hz

Figure 5: EIS bode plots for treated and untreated concrete from initial tests and plots from data collected between
day 371 and 400.

5.00E-04

4.50E-04

4.00E-04

3.50E-04
blank
Current Desnity (A/cm^2)

500 ppm
3.00E-04
1000 ppm
1500 ppm
2.50E-04
2000 ppm

2.00E-04

1.50E-04

1.00E-04

5.00E-05

0.00E+00
0 500 1000 1500 2000 2500 3000 3500 4000
Time (Sec.)

Figure 6: Potentiostatic tests demonstrate a dramatic decrease in current density with higher concentration of
inhibitor. Samples were polarized to +20 mV over the open circuit potential.

357
Figure 7: Langmuir adsorption isotherm for different migrating corrosion inhibitor concentrations.

-9.5
MCI
Blank
Linear (MCI)
y = -5.255x + 6.2183 Linear (Blank)
2
-10 R = 0.997

-10.5
Ln (Icorr)

-11

y = -4.051x + 2.006
R2 = 0.9862
-11.5

-12
2.95 3 3.05 3.1 3.15 3.2 3.25 3.3 3.35 3.4
o
1000/T (1/ K)

Figure 8: Activation energy calculations for corrosion reactions of steel with and without inhibitor at various
temperatures.

358
Concentration (ppm) Icorr (A) 1- Ln Ln (1-) Ln -Ln (1-)
0 10.5 0 1
200 6.32 0.398 0.602 -0.921 -0.508 -0.413
400 4.5 0.571 0.429 -0.560 -0.847 0.288
600 3.7 0.648 0.352 -0.434 -1.043 0.609
800 2.6 0.752 0.248 -0.285 -1.396 1.111
1000 1.7 0.838 0.162 -0.177 -1.821 1.644
2000 0.45 0.957 0.043 -0.044 -3.150 3.106
Table 1: LPR test results for given concentrations of inhibitor 1.

359
Presented at EUROCORR 2003, Budapest, Hungary

Improving Durability of Reinforced Concrete Structures using Migrating Corrosion


Inhibitors

Behzad Bavarian and Lisa Reiner

Dept. of Manufacturing Systems Engineering & Management


College of Engineering and Computer Science
California State University, Northridge, USA 91330

Abstract
Corrosion creates long term reliability issues for reinforced concrete structures. Billions of
dollars have been spent on corrosion protection of concrete and steel bridges, highways, and
reinforced concrete buildings. Among the commercial technologies available today, migrating
corrosion inhibitors (MCIs) show versatility as admixtures, surface treatments, and in
rehabilitation programs. The effectiveness of the MCIs (mixture of amine carboxylates and
amino alcohols) on reinforced concrete was evaluated throughout this project. Corrosion test
results conducted over 1500 days, 200 cycles per ASTM G109) using immersion and ponding in
3.5% NaCl solution indicated that polarization resistance (Rp) for the MCI coated concrete
was higher (60-80 kohms-cm2 with increasing trends) than non-coated concrete. The untreated
not only had lower Rp values, but also decreasing trends. Examination of the embedded steel
rebar after corrosion tests showed no corrosion attack for the MCI treated concrete samples,
while non-treated concrete showed corrosion. X-ray photoelectron spectroscopy (XPS) and depth
profiling confirmed that the inhibitor had reached the rebar surface in less than 150 days. Depth
profiling showed an amine-rich compound on the rebar surface that corresponded with the
increase in Rp and improved corrosion protection for the MCI treated steel rebar even in the
presence of chloride ions. Based on measured corrosion rate the life expectancy of a concrete
reinforced structure can be improved by more than 40 years.

1. Introduction
Corrosion is one of the main concerns in the durability of materials and structures. Much
work has been done to develop a corrosion inhibition process to prolong the life of existing
structures and minimize corrosion damages in new structures. Carbon steel is one of the most
widely used engineering materials despite its relatively limited corrosion resistance. Iron in the
presence of oxygen and water is thermodynamically unstable, causing its oxide layers to break
down. Corrosion undermines the physical integrity of structures, endangers people and the
environment, and is very costly. Because carbon steel represents the largest single class of alloys
used [1], corrosion is a huge concern. The billions of dollars committed to providing protective
systems for iron and steel have provided new ways of combating corrosion. Migrating corrosion

360
inhibitors (MCIs) are one means of protection for reinforced concrete structures. Previous studies
have established the benefits of using migrating corrosion inhibitors, the importance of good
concrete, and the significance of the ingredients used to make the concrete [2-6]. Reinforcing
steel embedded in concrete shows a high amount of resistance to corrosion. The cement paste in
the concrete provides an alkaline environment that protects the steel from corrosion by forming a
protective ferric oxide film. The corrosion rate of steel in this state is negligible. Factors
influencing the ability of the rebar to remain passivated are the water to cement ratio,
permeability and electrical resistance of concrete. These factors determine whether corrosive
species can penetrate through the concrete pores to the rebar oxide layer. In highly corrosive
environments (coastal beaches and areas where deicing salts are common), the passive layer will
deteriorate, leaving the rebar vulnerable to chloride attack, thereby requiring a corrosion
prevention system.
Migrating Corrosion Inhibitor (MCI) technology was developed to protect the embedded
steel rebar/concrete structure. Recent MCIs are based on amino carboxylate chemistry and the
most effective types of inhibitor interact at the anode and cathode simultaneously [2]. Organic
inhibitors use compounds that work by forming a monomolecular film between the metal and the
water. In the case of film forming amines, one end of the molecule is hydrophilic and the other
hydrophobic. These molecules will arrange themselves parallel to one another and perpendicular
to the reinforcement forming a barrier [3, 7, 14]. Migrating corrosion inhibitors are able to
penetrate into existing concrete to protect steel from chloride attack. The inhibitor migrates
through the concrete capillary structure, first by liquid diffusion via the moisture that is normally
present in concrete, then by its high vapor pressure and finally by following hairlines and
microcracks. The diffusion process requires time to reach the rebars surface and to form a
protective layer. MCIs can be incorporated as an admixture or can be surface impregnated on
existing concrete structures. With surface impregnation, diffusion transports the MCIs into the
deeper concrete layers, where they will inhibit the onset of steel rebar corrosion. Laboratory tests
have proven that MCI corrosion inhibitors migrate through the concrete pores to protect the rebar
against corrosion even in the presence of chlorides [4, 5].

2. EXPERIMENTAL PROCEDURES
This study focused on the usefulness of inhibitors and their means of application. Concrete
samples were cast (dimensions 280 mm x 110 mm x 150 mm per ASTM G109 and 100 mm x
100 mm x 250mm for immersion tests) using commercial grade silica, Portland cement, fly ash,
and limestone (concrete mixture ratio: 1 cement/2 fine aggregate/4 coarse aggregate). Five
samples (low density concrete at 2.08 g/cm3) were prepared with a 0.65 water/cement ratio and
five samples (high density concrete at 2.40 g/cm3) were prepared using a 0.35 water/cement
ratio. All samples had three class 60 steel rebar (with dimensions of 381 mm length, 12.5 mm
diameter) and were referenced to a Cu/CuSO4 electrode (Figure 1a). The rebar coverage layer
was maintained at 25.4 mm of concrete. Concrete compressive strengths ranged about 21 MPa
after 28 days of curing for the low density samples and 26 MPa for the high density. Migrating
corrosion inhibitors, MCI 2020, MCI 2020M, and MCI 2022 (sealer) were applied to the
concrete surface. The objective was to study the corrosion inhibiting properties and to determine
whether these inhibitors protect the steel rebar. Due to the low conductivity of concrete, the
corrosion behavior of steel rebar was monitored using electrochemical impedance spectroscopy

361
(EIS) was applied while samples were immersed in 3.5% NaCl at ambient temperatures.
Effectiveness of this MCI product was based on changes in the polarization resistance and the
corrosion potential of the rebar, measurements that can be performed without destroying the
sample. This data can provide early warning of structural distress and evaluate the effectiveness
of corrosion control strategies that have been implemented. Once rebar corrosion has proceeded
to an advanced state, where its effects are visually apparent on the concrete surface, it is too late
for minor patchwork. The key to fighting corrosion is in preventative measures.

a) b)
Figure 1: a) Concrete samples prepared per ASTM G109; b) concrete samples modified for
continuous immersion [8].

The experiments were conducted using Gamry EIS300 software and Echem Analyst. Bode
and Nyquist plots were created from the data obtained using the single sine technique. Potential
values were recorded and plotted with respect to time. By comparing the bode plots, changes in
the slopes of the curves were monitored as a means of establishing a trend in the Rp value over
time. To verify this analysis, the Rp values were also estimated by using a curve fit algorithm on
the Nyquist plots (available in the software). In these plots, the Rp and R: combined values are
displayed in the low frequency range of the bode plot and the R: value can be seen in the high
frequency range of the bode plot. The diameter of the Nyquist plot is a measure of the Rp value.
In this investigation, the steel rebar/concrete combination is treated as a porous solution and
modeled by a Randles electrical circuit [9]. EIS tests performed on a circuit containing a
capacitor and two resistors indicate that this model provides an accurate representation of a
corroding specimen. Electrochemical impedance technique has been widely used as a corrosion
measurement tool. A number of publications have reviewed both the theory and many areas of
application [10-12]. EIS tests, by means of a small amplitude signal of varying frequency, give
fundamental parameters relating to the electrochemical kinetics of the corroding system. The
values of concern in this study are Rp and R:. The Rp value is a measure of the polarization
resistance or the resistance of the surface of the material to corrosion. R: is a measure of the
solution resistance to the flow of the corrosion current. By monitoring the Rp value over time, the
relative effectiveness of the sample against corrosion can be determined. If the specimen
maintains a high Rp value in the presence of chloride, it is considered to be passivated or immune

362
to the effects of corrosion. If the specimen displays a decreasing Rp value over time, it is
corroding and the inhibitor is not providing corrosion resistance.
During this investigation, changes in the polarization resistance (Rp) and the corrosion
potential of the rebar were monitored to ascertain the degree of effectiveness for these MCI
products. The samples were tested on a weekly basis and the data was collected for analysis for
the first 500 days of exposures tests followed by monthly data collection. After 1,500 days of
testing, four concrete samples (One reference sample and three MCI treated concrete samples)
were cut open to remove the rebar for examination. A large area surface analysis was performed
on several MCI treated concrete samples using a Kratos Axis Ultra XPS in electrostatic lens
mode with resolution pass energy of 160 and an aluminum monochromator anode. The depth
profiles were conducted using Argon ions at 4 kV.
There were ten concrete samples in total, eight were surface impregnated with several coats
of MCI 2020 and MCI 2020M. The remaining two samples were left untreated and used as
control for comparison. Clear silicon was applied to the concrete/metal interface to prevent easy
access for ions. The testing environment was a solution of 3.5% NaCl and water with roughly
175 mm (7 inches) (Figure 1b) of each sample continuously immersed during testing, while the
ASTM G109 [8] was subjected to 3.5% NaCl salt solution ponding for every other two weeks for
roughly 210 cycles.

RESULTS
Many procedures have been developed for monitoring the corrosion of rebar in concrete,
each method attempts to improve a shortcoming of an existing technique. Measuring the open
circuit potential is very easy and inexpensive, but is not considered very reliable since the
potential provides no information about the kinetics of the corrosion process. Linear polarization
resistance (LPR) measurements are influenced by IR effects from the concrete. A significant
potential drop in the concrete makes an accurate determination of the potential of the rebar
surface very difficult. Electrochemical impedance spectroscopy (EIS) is able to overcome the
difficulties of the concrete resistance, yet requires more testing time. The different analytical
methods of electrochemical impedance spectroscopy are capable of giving more detailed
information than LPR. The rebar potential, polarization resistance and current density data can
provide information as to whether the rebar is in the active or passive corrosion state. Estimates
made from these parameters for Tafel constants can be input into LPR analysis or can be used for
corrosion rate measurement and cathodic protection criteria. Evaluation of the effectiveness of
corrosion inhibitors and the effects of concrete composition is often based on these variables. For
a more comprehensive approach to the corrosion process, several tests methods have been
implemented in this investigation.

Corrosion Potentials
The corrosion inhibition for the inhibitor identified as MCI 2020 has been investigated over
a period of 1500 days using EIS techniques. Throughout this investigation, changes in the
corrosion potential of the rebar were monitored to determine the effects of this commercially
available inhibitor. According to the ASTM (C876) standard [13], if the open circuit potential
(corrosion potential) is -200 mV or higher, this indicates a 90% probability that no reinforcing
steel has corroded. Corrosion potentials more negative than -350 mV are assumed to have a

363
greater than 90% likelihood of corrosion. Figure 2 shows the corrosion potentials for the high
and low density samples. The MCI treated samples showed a potential of roughly -100 mV after
1500 days of immersion in a salt solution. Given an open circuit potential of -570 mV for the
untreated (low density) sample, it is highly probable that corrosion initiation has occurred. Figure
3a confirmed these findings. The untreated high density concrete maintained a potential of -240
mV, but had a high resistance polarization and did not suffer any corrosion.

Figure 2: Comparison of Corrosion Potentials for MCI Treated Concrete with Untreated Samples
per ASTM G109 [8].

a) b)
Figure 3: a) Non-treated concrete, rebar showed localized corrosion attacks. b) MCI-treated
concrete, rebar did not show any corrosion attacks.

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Polarization Resistance
This electrochemical technique enables the measurement of the instantaneous corrosion rate.
This Rp value is related to the corrosion current Icorr by the following Stern-Geary equation [9]:

Icorr = B/( RpA) (1)

where A is the area of the metal surface evenly polarized and B is a constant that may vary from
13 to 52 mV for the case of steel embedded in concrete. Figure 4 shows EIS data for polarization
resistance that demonstrated an increasing trend for the MCI coated samples with polarization
UHVLVWDQFHYDOXHVEHWZHHQN-cm2 DQGN-cm2. The Rp value for the untreated low density
sample showed a declining trend of  N-cm2 at 350 days of partial immersion in the
aggressive solution. The calculated corrosion rate of the steel rebar in concrete based on the
measured polarization resistance values indicated a 1.6-2.2 mpy for the non-treated samples
while MCI treated samples were in the range of 0.18-0.22 mpy. This can result in an additional
30-40 years of service life for protected concrete structures compared with non-protected
concrete structures.

Figure 4: Polarization Resistance (Rp) Versus Time; Comparison of treated (MCI 2020 & MCI
2020M) low & high density concrete with untreated concrete.

X-ray photoelectron spectroscopy (XPS)


The XPS analysis of the rebar surface verified the inhibitors ability to penetrate through the
concrete pores by vapor phase diffusion and capillary effects. The data analyzed was consistent
with an organic compound carboxylate chemistry similar to the migrating corrosion inhibitor

365
compound (nitrogen, carbon and oxygen presence was attributed to MCI compound). Depth
profiling (using 4 kV Argon ions) measured an approximate 120 nm layer of amine compounds
on the rebar surface, confirming surface adherence after migration. Chloride was also found on
the surface of the rebar. The XPS results demonstrated that both the MCI and corrosive species
had migrated in through the concrete capillary system. Table 1, however, shows that MCI
managed to coat the surface and neutralize the corrosive species (chloride ions and carbon
dioxide) to protect the steel rebar.

Table 1: XPS analysis and spectrum of the rebar surface, untreated and MCI 2020M treated
concrete after 1500 days in 3.5% NaCl.

Atomic Conc% Mass Conc% Atomic Conc% Mass Conc%


Peak
Untreated Untreated MCI MCI
Fe 2p 0.87 3.32 0.08 0.3
O 1s 30.19 33.06 31.4 35.91
C 1s 62.48 51.37 59.43 48.12
Ca 2p 0.15 0.42 1.08 3.01
Si 2p 4.72 9.08 1.26 4.14
Cl 2p 0.84 2.04 1.11 2.81

N 1s 0.74 0.71 5.64 5.71

CONCLUSIONS
Migrating corrosion inhibitors effectiveness were studied in continuous long duration
corrosion tests, all samples but one (low density-untreated) have maintained a stable protective
layer that has improved the steel reinforcement performance in the corrosive environment. The
MCI products have successfully inhibited corrosion of the rebar in a 3.5% NaCl solution for the
duration of testing. MCI protected samples showed an average corrosion rate of 0.4 A/cm2 (less
than 0.17 mpy) compared to untreated samples that were 5.10 A/cm2 (2.2 mpy). This will
increase the life expectancy of a concrete reinforced structure by more than 40 years. XPS
analysis demonstrated the presence of inhibitor on the steel rebar surface indicating MCI
migration through the concrete. XPS depth profiling showed a layer of amine-rich compounds
and chloride ions on the rebar surface; however the neutralizing effects and film forming ability
of the inhibitor assured satisfactory corrosion resistance.

366
REFERENCES
1. http://www.corrosioncost.com/home.html
2. D. Bjegovic and B. Miksic, Migrating Corrosion Inhibitor Protection of Concrete, MP,
NACE International, Nov. 1999.
3. D. Stark, Influence of Design and Materials on Corrosion Resistance of Steel in Concrete, R
& D Bulletin, RD098.01T. Skokie, Illinois: Portland Cement Association, 1989.
4. B. Bavarian and L. Reiner, Migrating Corrosion Inhibitor Protection of Steel Rebar in
Concrete, Materials Performance, 2003.
5. B. Bavarian and L. Reiner, Corrosion Protection of Steel Rebar in Concrete using Migrating
Corrosion Inhibitors, BAM 2001.
6. J. P. Broomfield et al, Corrosion of Metals in Concrete, ACI 222R-96.
7. R. Dagani, Chemists Explore Potential of Dendritic Macromolecules as Functional Materials,
Chemical & Engineering News, American Chemical Society, June 3, 1996.
8. ASTM G109 Standard Test Method for Determining Effects of Chemical Admixtures on
Corrosion of Embedded Steel Reinforcement in Concrete Exposed to Chloride
Environments, Annual Book of ASTM Standards, Vol. 03.02, 1992.
9. D. Jones, Principles and Prevention of Corrosion, 2nd Edition, Prentice Hall, NJ, 1996.
10. G. Qiao and J. Ou, Corrosion Monitoring of Reinforcing Steel in Cement Mortar by EIS and
ENA, Electrochimica Acta, Vol. 52, 2007.
11. D. A. Koleva, K. van Breuge, J. H. W. de Wit, E. van Westing, N. Boshkov, and A. L. A.
Fraaij, Electrochemical Behavior, Microstructural Analysis, and Morphological
Observations in Reinforced Mortar Subjected to Chloride Ingress, Journal of the
Electrochemical Society, Vol. 154, 2007, pp. E45E56.
12. H. Saricimen, M. Mohammad, A. Quddus, M. Shameem, and M. S. Barry, Effectiveness of
Concrete Inhibitors in Retarding Rebar Corrosion, Cement and Concrete Composites, Vol.
24, 2002, pp. 89100.
13. ASTM C876 Standard Test Method for Half Cell Potentials of Reinforcing Steel in Concrete,
Annual Book of ASTM Standards, Vol. 04.02, 1983.
14. S. Sawada 1, J. Kubo, C.L. Page *, M.M. Page, Electrochemical injection of organic corrosion
inhibitors into carbonated cementitious Materials, Corrosion Science 49 (2007) 11861204

367
Corrosion Protection of Steel Rebar in Concrete with Optimal
Application of Migrating Corrosion Inhibitors, MCI 2022

Prepared for:
The Cortec Corporation
4119 White Bear Parkway
St Paul, MN 55110
(Report #1137)

Prepared by:
Behzad Bavarian, PhD
Professor of Materials Engineering

Lisa Reiner
Dept. of Manufacturing Systems Engineering & Management
College of Engineering and Computer Science
California State University, Northridge
March 2003

368
Steel corrosion is a major concern for any society with reinforced concrete structures. More
specifically, the United States, with its vast infrastructure of concrete and steel bridges,
superhighways, and reinforced concrete buildings has spent billions of dollars for corrosion
protection. Among the commercial technologies available today, migrating corrosion inhibitors
(MCIs) show versatility in that they can be incorporated as admixtures, surface treatment, or
used in rehabilitation programs. The effectiveness of Cortecs MCI 2022, a mixture of amine
carboxylates, amino alcohols and siloxane, on reinforced concrete using various application
methods was evaluated. Bode and Nyquist plots showed high polarization resistance values for
inhibitor treated concrete. XPS analysis verified the presence of inhibitor chemistry and chloride
molecules on the steel rebar surfaces. Depth profiling revealed a 100 nm amine-rich layer of
inhibitor along with chloride ions on the rebar, confirming that MCI had migrated through the
concrete coverage to suppress chloride ion corrosiveness. Eight concrete specimens were
prepared with reinforcement placed at 1 inch (2.5 cm) concrete coverage and tested for a period
of 400 days. MCI 2022 was applied directly to the rebar, by surface impregnation and combined
in a mortar coating. Electrochemical monitoring techniques were applied to samples immersed in
3.5% NaCl at ambient temperatures. The corrosion behavior of the steel rebar was monitored
using AC electrochemical impedance spectroscopy (EIS). The changes in the polarization
resistance and the corrosion potential of the rebar were compared with previous investigations
conducted on several admixtures and stainless steel rebar.

Introduction
Corrosion is one of the main concerns in the durability of materials and structures. Much effort
has been made to develop a corrosion inhibition process to prolong the life of existing structures
and minimize corrosion damages in new structures. Carbon steel is one of the most widely used
engineering materials despite its relatively limited corrosion resistance. Iron in the presence of
oxygen and water is thermodynamically unstable, causing its oxide layers to break down.
Corrosion undermines the physical integrity of structures, endangers people and the
environment, and is very costly. Because carbon steel represents the largest single class of alloys
used,1 corrosion is a huge concern. The billions of dollars committed to providing protective
systems for iron and steel have provided new ways of combating corrosion. Migrating corrosion
inhibitors (MCIs) are one means of protection for reinforced concrete structures. Previous studies
have established the benefits of using migrating corrosion inhibitors, the importance of good
concrete, and the significance of the ingredients used to make the concrete.2-7 Reinforcing steel
embedded in concrete shows a high amount of resistance to corrosion. The cement paste in the
concrete provides an alkaline environment that protects the steel from corrosion by forming a
protective ferric oxide film. The corrosion rate of steel in this state is negligible. Factors
influencing the ability of the rebar to remain passivated are the water to cement ratio,
permeability and electrical resistance of concrete. These factors determine whether corrosive
species like carbonation and chloride ions can penetrate through the concrete pores to the rebar
oxide layer. In highly corrosive environments (coastal beaches and areas where deicing salts are
common), the passive layer will deteriorate, leaving the rebar vulnerable to chloride attack,
thereby requiring additional help to prevent corrosion damage.

Migrating Corrosion Inhibitor (MCI) technology was developed to protect the embedded steel
rebar/concrete structure. Recent MCIs are based on amino carboxylate chemistry and the most
effective types of inhibitor interact at the anode and cathode simultaneously.2,3 Organic inhibitors

369
utilize compounds that work by forming a monomolecular film between the metal and the water.
In the case of film forming amines, one end of the molecule is hydrophilic and the other
hydrophobic. These molecules will arrange themselves parallel to one another and perpendicular
to the reinforcement forming a barrier.5 Migrating corrosion inhibitors are able to penetrate into
existing concrete to protect steel from chloride attack. The inhibitor migrates through the
concrete capillary structure, first by liquid diffusion via the moisture that is normally present in
concrete, then by its high vapor pressure and finally by following hairlines and microcracks. The
diffusion process requires time to reach the rebars surface and to form a protective layer.

MCIs can be incorporated as an admixture or can be surface impregnated on existing concrete


structures. With surface impregnation, diffusion transports the MCIs into the deeper concrete
layers, where they will inhibit the onset of steel rebar corrosion. Bjegovic and Miksic recently
demonstrated the effectiveness of MCIs over five years of continuous testing.2,3 They also
showed that the migrating amine-based corrosion-inhibiting admixture can be effective when
incorporated in the repair process of concrete structures.2 Furthermore, laboratory tests have
proven that MCI corrosion inhibitors migrate through the concrete pores to protect the rebar
against corrosion even in the presence of chlorides.6,7

Purpose
The objective of this investigation was to further study migrating corrosion inhibitors, focusing
on their usefulness and means of application. In many cases, there is thought to be an induction
period, where time is required for the inhibitor to migrate through the concrete pores. A high
density concrete may impede corrosive species from reaching the surface of the rebar and could
also prevent inhibitor from reaching the surface of the concrete. Direct application of the
inhibitor to the rebar surface would eliminate this concern. Also, a thicker coating of inhibitor
and mortar was investigated; this combination may be necessary to protect steel rebar in
extremely aggressive environments. Electrochemical monitoring techniques were applied while
samples were immersed in 3.5% NaCl at ambient temperatures. Due to the low conductivity of
concrete, the corrosion behavior of steel rebar had to be monitored using AC electrochemical
impedance spectroscopy (EIS). Effectiveness of this MCI product was based on changes in the
polarization resistance and the corrosion potential of the rebar, measurements that can be
performed without destruction to the reinforcing steel. This data can provide early warning of
structural distress and evaluate the effectiveness of corrosion control strategies that have been
implemented. Once rebar corrosion has proceeded to an advanced state, where its effects are
visually apparent on the concrete surface, it is too late for minor patchwork. The key to fighting
corrosion is to introduce preventative measures.

Experimental Procedures
For purposes of this study, the steel rebar/concrete combination is treated as a porous solution
and modeled by a Randles electrical circuit. EIS tests performed on a circuit containing a
capacitor and two resistors indicate that this model provides an accurate representation of a
corroding specimen. EIS tests, by means of a small amplitude signal of varying frequency, give
fundamental parameters relating to the electrochemical kinetics of the corroding system. The
values of concern in this study are Rp and R:. The Rp value is a measure of the polarization
resistance or the resistance of the surface of the material to corrosion. R: is a measure of the
solution resistance to the flow of the corrosion current. By monitoring the Rp value over time, the

370
relative effectiveness of the sample against corrosion can be determined. If the specimen
maintains a high Rp value in the presence of chloride, it is considered to be passivated or immune
to the effects of corrosion. If the specimen displays a decreasing Rp value over time, it is
corroding and the inhibitor is not providing corrosion resistance.

The experiments were conducted using an EG&G Potentiostat/Galvanostat (Model 273A with a
5210 Lock-in amplifier), EG&G M398 and Power Suite Electrochemical Impedance Software
and a Gamry PC4-750 Potentiostat with EIS300 software and Echem Analyst. Bode and Nyquist
plots were created from the data obtained using the single sine technique. Potential values were
recorded and plotted with respect to time. By comparing the bode plots, changes in the slopes of
the curves were monitored as a means of establishing a trend in the Rp value over time. To verify
this analysis, the Rp values were also estimated by using a curve fit algorithm on the Nyquist
plots (available in the software). In these plots, the Rp and R: combined values are displayed in
the low frequency range of the bode plot and the R: value can be seen in the high frequency
range of the bode plot. The diameter of the Nyquist plot is a measure of the Rp value.

Number of samples Application method


2 No treatment-control samples
2 MCI 2022 coated rebar
2 MCI 2022 treated concrete surface
2 2/8 to 3/8 inch mortar/MCI 2022 coating
Table 1. Shows the application method used for each sample.

As seen in Table 1, several methods were used to treat the concrete samples. The objective was
to determine whether the location of the inhibitor had any impact on its ability to protect the steel
rebar. Prior to the concrete batching, two rebars were immersed for 20 minutes in MCI 2022 to
ensure thorough coverage, then set to dry for several days. Concrete samples with dimensions 8
x 4 x 4 were prepared using an 8 inch steel rebar (class 60, 1/2 diameter) and one 8-inch
Inconel 800 metal strip (for the counter electrode). A concrete mixture containing commercial
grade-silica, Portland cement, fly ash, and limestone (concrete mixture ratio: 1 cement/2 fine
aggregate/4 coarse aggregate) were combined with one-half gallon water per 60-lb (27.22 Kg)
bag in a mechanical mixer. The mix resulted in a 0.5 cement to water ratio and the coverage
layer was maintained at one inch concrete for all samples. Compressive strengths were roughly
3750 psi for this medium density concrete cured for 28 days per ASTM C387. After curing,
samples were set to dry, then sandblasted to remove loose particles and provide surface
uniformity.

Two of the concrete blocks were surface impregnated with several coats of MCI 2022 and set to
dry. The inhibitor was applied to the surface of the concrete with a paint brush while partially
immersed in a shallow container of inhibitor. Mortar samples were prepared using a 10 lb (4.5
kg) bag of Quikrete mortar mix, 100 ml MCI 2022 and 800 ml water. The remaining two
samples were left untreated and used as standards for comparison. Clear silicon was applied to
the concrete/metal interface to prevent easy access for ions. Figure 1 shows the samples partially
immersed in a solution of 3.5% NaCl and water; roughly 7 inches of each sample was

371
continuously immersed in the solution for the entire testing period. A Cu/CuS04 electrode was
used as the reference and each sample was tested approximately every two weeks. The results
were compared with previous investigations conducted on several admixtures and stainless steel
rebar.

Figure 1. This photo shows four of the concrete samples partially immersed in a 3.5% NaCl solution.

Results & Discussion

Many procedures have been developed for monitoring the corrosion of rebar in concrete, each
method attempts to improve a shortcoming of an alternate technique. Measuring the open circuit
potential is very easy and inexpensive, but is not considered very reliable since the potential
provides no information about the kinetics of the corrosion process. Linear polarization
resistance (LPR) measurements are influenced by IR effects from the concrete. A significant
potential drop in the concrete makes an accurate determination of the potential of the rebar
surface very difficult. Electrochemical impedance spectroscopy (EIS) is able to overcome the
difficulties of the concrete resistance, yet requires more testing time. The different analytical
methods of electrochemical impedance spectroscopy are capable of giving more detailed
information than LPR. The rebar potential, polarization resistance and current density data can
provide information as to whether the rebar is in the active or passive corrosion state. Estimates
made from these parameters for Tafel constants can be input into LPR analysis or can be used for
corrosion rate measurement and cathodic protection criteria. Evaluation of the effectiveness of
corrosion inhibitors and the effects of concrete composition is often based on these variables. For
a more comprehensive approach to the corrosion process, several tests methods have been
implemented in this investigation.

Corrosion Potentials
The corrosion inhibition for Cortec MCI 2022 was investigated over a period of 400 days using
AC electrochemical impedance spectroscopy (EIS). Throughout this investigation, changes in the
corrosion potential of the rebar were monitored to determine the effects of this commercially
available inhibitor. According to the ASTM (C876) standard, if the open circuit potential
(corrosion potential) is -200 mV or higher, this indicates a 90% probability that no reinforcing
steel has corroded. Corrosion potentials more negative than -350 mV are assumed to have a
greater than 90% likelihood of corrosion. Figure 2 shows that the corrosion potentials for all the
samples were between the range of -25 mV to -150 mV after 100 days of immersion in NaCl.

372
0

-50

-100
P o t e n t ia l, (m V )

-150

-200

RF1-untreated MR1-rebar treated


-250
MS1-surface treated MM1-mortar coated surface

-300
0 50 100 150 200 250 300 350 400

Time of Submersion (Days)

Figure 2. Comparison of corrosion potential vs time for MCI treated and untreated samples.

Polarization Resistance
This electrochemical technique enables the measurement of the instantaneous corrosion rate. It
quantifies the amount of metal per unit of area being corroded in a particular instant. The method
is based on the observation of the linearity of the polarization curves near the potential Ecorr. The
slope expresses the value of the polarization resistance (Rp) if the increment diminishes to zero.
This Rp value is related to the corrosion current Icorr by means of the expression:
'E B
Rp 'E o 0 Icorr
'I Rp A
Where A is the area of the metal surface evenly polarized and B is a constant that may vary from
13 to 52 mV. For the case of steel embedded in concrete, the best fit with parallel gravimetric
losses, results in B= 26 mV for actively corroding steel, and B= 52 mV for passivated steel.
Figures 3 & 4 show that MCI treated concrete samples have higher Rp values compared with the
control sample. Figure 3 shows a declining trend for the untreated concrete sample and stable
polarization resistance values after 400 days of testing for the treated concrete. Figure 4 shows
Rp values obtained during linear polarization consistent with Figure 3. The inhibitor treated rebar
had the highest polarization resistance, the next highest Rp values were for the concrete with
mortar treatment, then surface treated concrete and finally the untreated concrete with somewhat
lower values around 27000 (ohm) (cm2). The corrosion rate in PA/cm2 is shown in Figure 5 and
the relative value is specified in Table 2. For example, at the present rate of corrosion, it is
estimated that the untreated sample will suffer corrosion damage in 10-15 years.

373
p
35000
RF1-untreated MR1-rebar treated
MS1-surface treated MM1-mortar coated surface
30000

25000
R p (O h m s )

20000

15000

10000

5000

0
0 50 100 150 200 250 300 350 400 450
Time submerged, Days

Figure 3. Comparison of polarization resistance (RP) for MCI treated & untreated concrete samples.

55000
P o la r iz a tio n R e s is ta n c e , R p , o h m .c m ^ 2

50000

45000

40000

35000

30000

25000
MCI on Rebar
20000 MCI in mortar
MCI on Concrete
15000 Non MCI Treated

10000
0 2000 4000 6000 8000 10000 12000 14000 16000
Time, Second

Figure 4. Linear polarization resistance tests on concrete samples partially immersed in 3.5% NaCl solution,
day 365.

374
Non-treated
2
MCI on Concrete

MCI in Mortar

Corrosion Rate, PA/cm^2


MCI on Rebar
1.5

0.5

0
1 2 3 4
Sample

Figure 5. Bar chart obtained from LPR data quantifying the corrosion rate (PA/cm2) for concrete samples on
day 365.

Corrosion rate (uA/cm2) Severity of Damage


< 0.5 no corrosion damage expected
0.5-2.7 corrosion damage possible in 10 to 15 years
2.7-27 corrosion damage expected in 2 to 10 years
> 27 corrosion damage expected in 2 years or less

Table 2. Proposed relationship between corrosion rate and remaining service life.

Bode Plots
Bode plots are not dependent on modeling the corroding system as are polarization resistance
values. The electrochemical impedance spectroscopy data are obtained by applying a single sine
wave over a range of frequencies while measuring the corresponding impedance. Since the
results are independent of an assumed model, the technique is highly reliable. Figure 6 shows a
comparison of the bode plots for the first day of testing. The similar results for day 1 are a good
indication that the concrete samples were consistently cast. Figure 7, the bode plot results from
day 400, shows an obvious decline in the impedance values measured for the control sample.
The passivating layer for this sample appears to have been breached, indicating a high likelihood
of corrosion. The MCI treated samples still have corrosion protection after 400 days in an
aggressive environment.

1.00E+04

Mortar MCI-Day 1
Concrete+MCI-Day 1
1.00E+03 Rebar+MCI-Day 1
l Z l (Ohms)

Control-Day 1

1.00E+02

1.00E+01
1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00 1.00E+01 1.00E+02 1.00E+03 1.00E+04
FREQUENCY (Hz)

Figure 6. EIS Bode plot for MCI 2022 treated & untreated concrete on day 1 of testing.

375
1.00E+05
Mortar MCI-Day 400
Concrete+MCI-Day 400
Rebar+MCI-Day 400
Control-Day 400

1.00E+04
l Z l (Ohms)

1.00E+03

1.00E+02
0.0001 0.001 0.01 0.1 1 10 100 1000 10000 100000
FREQUENCY (Hz)

Figure 7. EIS Bode plot for MCI 2022 treated & untreated concrete after 400 days of testing.

XPS Analysis
After 415 days of immersion in a NaCl solution, several samples were removed from testing for
XPS analysis and depth profiling. The rebar was removed from the concrete (Figures 8 & 9) and
its surface chemistry was assessed. Figure 10 shows the XPS spectrum from untreated rebar
sample after 450 days. It is similar to the spectrum shown in Figure 11 for the rebar removed
from an MCI treated sample after 415 days.

Figure 8. This photo shows the treated rebar still embedded in the concrete and the portion of the rebar that
was exposed to the corrosive environment.

376
Figure 9. Untreated rebar sample used for XPS analysis. Sample shows obvious indications of corrosion.

The major difference in the spectrums is the N 1s peak for nitrogen not seen on the untreated
rebar. The amine-rich compounds found on the rebar surface are associated with the MCI 2022
chemistry (75% water, 20 % silane/siloxane based sealer, 1-2% amino alcohols, 3-4% amine
carboxylate), derivatives of nitrogen. Figure 12 shows a narrow spectrum for the N 1s energy
band region verifying the presence of nitrogen. XPS chemical quantification results (Figure 11)
revealed organic compounds with carboxylate chemistry. Chloride was also detected at depths up
to 50 nm from the analysis surface on the rebar and at a concentration of approximately 0.52
atomic %. The XPS results demonstrate that both MCI and corrosive species had migrated in
through the concrete pores, but MCI had formed a protective film on the steel rebar surface.
These results are promising for the MCI product in its ability to protect steel rebar in concrete in
aggressive environments. Figure 13 shows several SEM micrographs of the rebar surface and the
EDAX analysis.

Figure 10. XPS spectrum of steel rebar removed from untreated concrete after 450 days of immersion.
Large area (1000 x 800 mm). Lens mode electrostatic; Resolution pass energy 160; anode: Mg (150 W).

377
peak position FWHM raw height RSF atomic mass atomic conc % mass conc %
BE (eV) (eV) (CPS)
C 1s 282.585 2.866 56290.7 0.318 12.011 53.88 41.91
O 1s 529.185 2.966 77068.9 0.736 15.999 32.79 33.98
N 1s 397.785 2.398 6550.4 0.505 14.007 3.99 3.62
Cl 2p 190.185 2.214 1641.7 0.964 35.460 0.52 1.18
Ca 2p 345.585 2.905 10461.1 1.950 40.078 1.64 4.25
Si 2p 100.185 2.587 7512.9 0.371 28.086 6.09 11.07
Fe 2p 742.785 5.120 9701.2 2.947 55.846 1.10 3.99

Figure 11. XPS spectrum analysis of steel rebar removed from MCI 2022 treated concrete after 400 days
immersion and chemical quantification.

Figure 12. High resolution XPS spectrum for nitrogen peak (N 1s region) on surface of steel rebar removed
from MCI 2022 treated concrete after 400 days immersion.

378
Elt XRay Int Kratio W% A%
N Ka 4.8 0.00310 1.00 3.47
O Ka 50.6 0.01715 3.73 11.31
Si Ka 87.1 0.00969 1.87 3.23
S Ka 5.2 0.00070 0.09 0.14
Cl Ka 3.0 0.00048 0.35 0.27
K Ka 8.6 0.00149 0.14 0.18
Ca Ka 107.3 0.01837 1.77 2.14
Fe Ka 2720.8 0.89617 91.06 79.26
0.94657 100.00 100.00

Figure 13. SEM photos (magnification: 100, 50 Pm) showing the surface of an MCI treated rebar after 400
days in a 3.5% NaCl solution and the EDAX analysis.

379
Conclusion
The MCI products have successfully inhibited corrosion of the rebar in a 3.5% NaCl solution for
415 days. Steel rebar corrosion potentials were maintained at approximately -150 mV, and rebar
polarization resistance showed a gradual increase reaching as high as 27,000 ohms. MCI coated
rebar and MCI added to mortar showed significant reduction in the corrosion rate. XPS analysis
demonstrated the presence of inhibitor on the steel rebar surface indicating MCI migration
through the concrete. Depth profiling showed a layer of amine-rich compounds and chloride ions
on the rebar surface; neutralizing effects of the inhibitor assured satisfactory corrosion resistance
in the presence of corrosive chloride ions.

References
1. http://www.corrosioncost.com/home.html
2. D. Bjegovic and B. Miksic, Migrating Corrosion Inhibitor Protection of Concrete, MP, NACE
International, Nov. 1999.
3. D. Rosignoli, L.Gelner, & D. Bjegovic, Anticorrosion Systems in the Maintenance, Repair &
Restoration of Structures in Reinforced Concrete, International Conf. Corrosion in Natural &
Industrial Environments: Problems and Solutions, Italy, May 23-25, 1995.
4. D. Darling and R. Ram, "Green Chemistry Applied to Corrosion and Scale Inhibitors." Materials
Performance 37.12 (1998): 42-45.
5. D. Stark Influence of Design and Materials on Corrosion Resistance of Steel in Concrete." Research
and Development Bulletin RD098.01T. Skokie, Illinois: Portland Cement Association, 1989.
6. B. Bavarian and L. Reiner, Corrosion Inhibition of Steel Rebar in Concrete by Migrating Corrosion
Inhibitors, Eurocorr 2000.
7. B. Bavarian and L. Reiner, Corrosion Protection of Steel Rebar in Concrete using Migrating
Corrosion Inhibitors, BAM 2001.

380
MIGRATORY VCI INHIBITORS
FOR WET THERMAL INSULATION

By

B. A. Miksic
4119 White Bear Parkway
St. Paul, MN 55110

Published: April, 1989


Presented at the Symposium
Corrosion Under Wet Thermal Insulation,
at Corrosion/89, New Orleans.

381
GENERAL

The corrosion of metals under thermal insulation is an industry wide problem, specifically
during idle or cooling-down periods. The presence of condensed water, airborne
contaminants and corrosive agents that are generated through thermal decomposition and
aging of insulating materials further increases the rate of attack on underlying surfaces.
Due to failure of outer barrier wraps or jackets, the moisture content of the insulation can
often reach the point of saturation. This combined with elevated temperatures can cause
the corrosion rates to multiply to exceedingly high levels.

M I G R A T O R Y V C IS

The effectiveness of volatile corrosion inhibitors to inhibit corrosion of metals in recessed


and hard-to-reach areas is well documented (1). The idea has occurred to utilize the
unique transport mechanism of VCIs to stop the deterioration of metals under thermal
insulation and thus to extend the useful life of the structures. However, for VCIs to be
useful for this specific application, they must meet a specific set of requirements:

(1) VCI must be capable of migrating or penetrating to


relatively great distance form point of injection or application.

(2) They must be effective in arresting further corrosion under


existing corrosion or scale deposits.

(3) They must have balanced partial vapor pressure between VCI
compounds in the formulation in order to provide rapid saturation
of insulation jacket after application, and long term protection by
minimizing the length of time between the application.

EXPERIMENTAL

Based on the above requirements, a formulation has been developed which utilizes a
volatile, non-flammable liquid carrier (Cortec VCI-656x), to improve the migratory
capability of the inhibitors. Sections of carbon steel pipe covered with wet calcium silicate
thermal insulation were injected with the VCI at the metal/insulation interface. The entire
system was kept wet at an elevated temperature to provide high possible rates of
corrosion for the VCI to overcome. The rate of injection of the inhibitor was 1 gallon of
liquid per 23 cu. feet of insulation. The test pipes were prepared with blast-to-white metal
finish yielding maximum profile 1 to mils, insulated with calcium silicate insulation 1
thick and covered with 16 MIL aluminum jacketing prior to putting into test.

The test conditions were 200o F to 200o F surface temperature and 5 psig steam pressure
which was maintained by continuous water injection at 5 ml/hr. (2)

RESULTS AND CONCLUSIONS

382
After six months, the test was shut down and disassembled. The following visual
observations were made:

- Control pipe was approximately 80% covered with the major part
of the bottom half covered with a build-up of corrosion products.

- The pipe inhibited with liquid VCI was approximately 5% corroded


at the two of the water injection points.

Considering the severity of the test, and experience with anti-corrosion coatings under
similar conditions, it is believed that the VCI compounds show promise as an effective
method of corrosion protection under existing insulation. It should be further mentioned
that due to the unique transport mechanism, this method could result in significant material
and labor savings in extending the useful life of the insulated structures, as the cost of
reinsulating and repair could be considerable.

UNDERCOATING FOR INSULATED SURFACES

Another area of application is the new insulation work. Here the requirements for VCI
are somewhat different as compared to injecting into the existing (wet) insulation. A
typical case history involved a large Midwestern Utility that specified temporary coating
for their ESP precipitators that have been fabricated on the location near the Gulf Coast.

Those large units were partially insulated at the fabrication yard with the additional
requirement that the units had to withstand barge shipment to the Ohio location and up to
one year field storage without appreciable corrosion attack. The limiting factor for the
selection of temporary coatings were the start-up conditions, as the wall temperature of
the precipitators is 475oF with excursions up to 700oF anticipated. Wax like coatings were
ruled out due to high temperature conditions and concern for decomposition products that
would form under the insulation. The conventional zinc rich primers could not be used
because of Zn reversing the potential at elevated temperatures. Further obvious choice, the
polyester lining material was excluded due to the marginal surface preparation, dampness
in the yard and cost factor associated with the application of lining to large structures.

After careful review of the above requirements, a combination of contact and volatile
corrosion inhibitors has been developed to provide temporary protection for ESP
precipitators during fabrication, and in transit and storage before plant start-up. The
formulation was designated VCI-619 X and utilizes water as a carrier assuring safe
application from stand points of flammability and health hazard. The coating was designed
to withstand high start-up temperature conditions, thus eliminating concerns about
decomposition products that would be formed. The material is shop applied by spray or
brush to steel surfaces using commercial equipment and it does not require stringent
surface preparation as with the linings. It can be applied directly to the surfaces covered
with tight oxide film or scale. Treated surfaces are allowed to air dry from ten to sixty

383
minutes (depending upon ambient conditions) before further handling or covering with
insulation.

The temporary coating was submitted to laboratory and field tests to prove its
effectiveness in retarding corrosion attack. Under laboratory conditions described above, it
showed approximately 30% corrosion which, considering severity of the test was still
acceptable (control pipe was covered over 80% with heavy corrosion product). The field
experience showed even more promising results - a total of 20 ESP precipitators have
been coated and insulated together with the associated equipment. All units have been
transported by river to the Midwest location and stored on site for over 1 year. The
periodic inspection show no or minimum amount of corrosion under thermal insulation.

REFERENCES

(1) B. A. Miksic, Chemical Engineering, September 1977

(2) E. I. Dupont Co., Internal memorandum Jan 15, 1988 (Haldeman & Hughes)

384
Presented at the 2nd International Congress on Studies in Ancient Structures, 2001, Istanbul, Turkey

Effects of Migrating Corrosion Inhibitors on Reinforced


Lightweight and Common Mortars

G. Batis, E. Rakanta
Section of Materials Science and Engineering
Dept. of Chemical Engineering, National Technical University, Athens, Greece

ABSTRACT

In reinforced landmark, historical buildings, a series of mortars are commonly


used for rendering of horizontal elements or filling of vertical ones. Corrosion of
reinforcing steel represents the most important cause of concrete structure
deterioration. This paper studies the protective effect of the reinforcement
mortars, against rebars corrosion in mortar specimens containing corrosion
inhibitors as admixture or as impregnation agent.
The migrating corrosion effectiveness was assessed in lightweight concrete
with Greek pumice stone and in common mortar specimens. The inhibiting
behavior of organic aminobased migrating corrosion inhibitors against steel
corrosion was evaluated by specimens immersion into 3,5%w.t. sodium chloride
corrosive solution and by exposure to the atmosphere. The corrosion activity and
inhibiting efficiencies (IE) were tested by measuring the rebars weight loss, their
half - cell potential, carbonation depth and electrochemical measurements of
chronicles corrosion rate of rebars in concrete specimens.
The results of our experiments have shown that the presence of the inhibiting
protection increases in the mortars systems with the usage of migrating corrosion
inhibitor compared to the reference specimens without corrosion inhibitor.
Furthermore, common mortar specimens exhibited lower rebar corrosion rate than
the lightweight concrete specimens. Finally, specimens with corrosion inhibitor
exhibited the best corrosion protection results in corrosive conditions without
chloride ions.

385
1. INTRODUCTION

Corrosion of reinforcing steel embedded in concrete is becoming a significant


structural and financial problem. As it is known, in Greece, many historical
buildings and structures are located in coastal regions (islands) where the weather
is characterized by pollutants such as part particles Cl- and carbon dioxide, CO2.
This leads to an increased incidence of spalls, delimination and as a consequence
the deterioration of concrete in reinforced structures.
In restorations, a series of traditional construction materials such as mortars,
steel and grouts are commonly used for repairing and filling elements of
structures. They are generally composed of cement, sand, lime and water or
cement, sand, superplastisizer, and water [1]. Due to the fact, that the rest of the
construction and the repair mortar have high porosity, the durability of these
mortars is questionable as far as the corrosion of the reinforcement steel. This
results in an attack from probably all sides as the water can penetrate either from
the foundation and leakages in the roof or from porous walls [2]. As a result to a
all above mentioned, many times the use of chemical admixture is essential due to
blocking the ingress of chloride ions and oxygen, increasing the resistance of the
passive film on the steel to breakdown by chloride ions.[3-4]
The use of chemical admixtures, which acts as corrosion inhibitors, is a
method for preventing and delaying the onset of rebar corrosion. An ideal
corrosion inhibitor has been defined as a chemical compound, which, when
added in adequate amounts to concrete, can prevent corrosion of embedded steel
and has no adverse effect on the properties of concrete [5]. Nowadays chemical
corrosion inhibitors present an easily implemented solution to the growing
problem of corrosion of reinforcing steel in concrete. However, to be considered
viable, these additives should not only prevent or delay the onset of corrosion,
they must not have any detrimental effect on the properties of the concrete itself,
such as strength, setting time, workability and durability [6]. It must be clarified,
that corrosion inhibitors do not totally stop corrosion, but rather increase the time
to the onset of corrosion and reduce its eventual rate. Drawbacks of corrosion
inhibiting admixtures are that they may not remain in the repair area, potentially
reducing the concentration of the inhibitor bellowing necessary values and
secondly, when used in a limited area long a continuous reinforcing bar, there is
the potential for micro cell corrosion development [7].
The aim of this study is the examination of the performance, in chloride
environment of two different sets of steel reinforced mortar specimens
(lightweight and common mortar) together with corrosion inhibitor in an effort to
lower the corrosion rate of steel reinforcement. Corrosion parameters such as
corrosion rates, Icorr, Rp of reinforcing steel in mortar specimens from two
differences types of mortar have been evaluated by electrochemical measurements
and compared with that obtained from metal loss determination. Electrochemical
corrosion measurements gives a snapshot of how the system mortar steel
behaved under corrosive environments versus time. Linear polarization, as well as

386
Tafel technique are not destructive methods for assessing the instantaneous
corrosion current density. It has been widely used in monitoring corrosion of
laboratory measurements and allowed to compare the performance of inhibitors in
mortars specimens [8].

2. MATERIALS AND EVALUATION METHODS

2.1. Materials
Greek Portlant cement was used for whole mortar specimens in this study. The
chemical composition is given in Table 1.
Half of the test specimens were constructed with lightweight aggregate and the
rest of them were with Greek sand. The use of the porous lightweight aggregates
results in porosity increase, which could negatively affect the corrosion rate if
steel rebars.
The lightweight aggregate used was a Greek porous pumice of 0 to 8mm
diameter. The mean value of the sand grains diameter was 250_m < d < 4mm.
Round deform med reinforcing steel, nominally 12mm in diameter (_12) was used
for all test specimens. Fabrication of the steel for the test specimens simply
involved cutting to the consistent length of 100mm. Their chemical composition is
given in Table 1.
Drinking water from Athens water supply network and INHIB-M, corrosion
inhibitor alkanolamines based on, were used for the specimens construction. The
corrosion-inhibiting admixture was used according to the manufactures
instructions regarding dose rate and mixing into the concrete. INHIB-M protects
both the anodic and cathodic parts of the corrosion all. Its claimed to work by
depositing a physical barrier in the form of the surface film that inhibits corrosion
of the steel by preventing contact between moisture and oxygen. The inhibitor is
able to diffuse through the concrete through either a vapor or liquid phase.

Table1: chemical composition % of OPC cement.


SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3 CaO(f) LOI
20.67 4.99 3.18 63.60 2.73 0.37 0.29 2.414 2.41 2.52

Table2: chemical composition % of steel rebars.


C Mn S P Si Ni Cr Cu V Mo
0.18 0.99 0.047 0.023 0.15 0.09 0.09 0.21 0.002 0.021

2.2. Specimens Casting


The test specimens considered for the present study were 80mm long, 80mm wide
and 100mm high. They contained four identical steel rebars in the position shown
in figure 1. Copper wire cables were connected to each steel bar for
electrochemical measurements. Prior to the preparation, the surface of the steel
bars were washed with water, then immersed for 15 min in strong solution of HCl

387
with organic corrosion inhibitor washed thoroughly with distilled water to
eliminate traces of the corrosion inhibitor and chloride ions. Following that, they
were cleaned with alcohol and with acetone and then weighed to 0,1mg accuracy.
Thereafter, the bars were placed in moulds, as shown in figure 1, where the
mortars was cast and stored at ambient conditions in the laboratory for 24 hours.
After being demolded, were cured in tap water at 25 oC for 24 hours.
The specimens were stored for an additional 24h at ambient temperature and
thereafter the part shown in Figure 1 was insulated with epoxy resin.
Finally half of them were partially immersed in 3.5% w.t NaCl solution up to
20mm from the bottom of the mortar specimens and the rest of them were
exposed to the atmospheric conditions.

80

20
100
Epoxy resin 80

(_) (_)
Steel rebars
Figure 1: Schematic representation of reinforced mortar specimen (a) upper, (b)
latter view. Dimensions of specimens in mm

2.3. Evaluation Methods


The objective of these experiments was to investigate mortar with corrosion
inhibitor as corrosion protection system and evaluate its performance in reference
to specimens without any addition of admixtures.
The migrating corrosion effectiveness was assessed in lightweight concrete
with Greek pumice stone and in common mortar specimens. The inhibiting
behavior of organic alkanolamines based migrating corrosion inhibitors against
steel corrosion was evaluated by specimens immersion into 3,5%w.t NaCl
corrosive solution and by exposure to the atmosphere. The code numbers and the
composition for the different sets of specimens used in this study are shown in
Table 3. The experimental duration of this study was 1year. Whole experimental
procedure will be discontinued at the conclusion of two full years of testing.
Methods used to assess specimens performance included the corrosion
potential, carbonation depth, corrosion rate, and mass loss time dependence of the
rebars measurements.

388
Specimens with all categories were immersed in 3.5%w.t NaCl solution and
their electro chemicals values were examined in order to evaluate the
reinforcement corrosion in mortars. The test setup for both the Tafel plot as well
as the linear polarization resistance techniques included a potensiostat /
galvanostat, E.G & Model 263. Additionally, a computer program, Softcorr III
developed by E.G & G Princeton Research was used for applying the potential
scan, analyzing the parameters Icorr, Rp.
Half cell potential measurements for each of the test specimens were
recorded at regular intervals versus a saturated calomel reference electrode (SCE),
for the duration of this experiment. Initially, these measurements were taken every
day, until equilibrium conditions were established. Following, half cell
measurements were recorded every week. Twelve months after the start of this
experiment the specimens were removed from the corrosive environment and
broken in order to measure the carbonation depth and weight loss of steel rebars.

Table 3: Type and Composition of specimens


Specimens
Composition ratio
Corrosion
Code
Cement Pumice Sand Water inhibitor Remarks
name
(lt/m3)
K-I 1 3 - 1 - Category I:
KM-I 1 3 - 1 1.24 Immersed in
S-I 1 - 3 0.6 - 3,5%w.t
SM-I 1 - 3 0.6 1.24 NaCl
K-II 1 3 - 1 -
Category II:
KM-II 1 3 - 1 1.24
Exposed in
S-II 1 - 3 0.6 -
Atmosphere
SM-II 1 - 3 0.6 1.24

The steel rebars were cleaned from rust according to above mention procedure,
the metal loss was determined and the corrosion rates were calculated by the
following equation.

Corrosion rate (_m/y) = 8.76x107 W/ (A*T*D) (1)


W: metal loss in [g], A: area of steel in [cm2], T: time of exposure in [h], D:
density of steel in [g/cm3]
The carbonation of the specimens was determined by the method
recommended by RILEM CPC-18, on broken mortar pieces. The carbonation
depth of mortar was calculated in the interval section of the specimen using
phenolophalein and by measuring the area where the colour did not change to red.

389
3. MEASUREMENTS AND RESULTS

3.1. Category-I: Specimens immersed in 3.5%w.t NaCl


Half-cell potential measurements given in figure 2 came out from the first
category of specimens that were immersed in 3.5%w.t NaCl solution. According
to the standard test method ASTM C 876, Standard test method for Half Cell
Potentials of reinforcing Steel in Concrete, the more negative the voltometer
reading, the greater the probability of active corrosion. Values less than 350mV,
have as a result 90% probability of active corrosion. It is obvious that for all the
specimens there is a tendency for the reduction of their potential value from the
range of 300mV to 650mV.these measurements suggests a high probability of
an active stage of corrosion throughout the test period.

K-I S-I SM-I KM-I


Potential (mV) vs saturated calomel

-100 0 2 4 6 8 10 12
reference electrode (SCE)

-200

-300

-400

-500

-600

-700
Time (months )
Figure 2: Half- cell potential measurements vs immersion time.

The results of mass loss measurements of reinforcing steel, after twelve


months of exposure in chlorides solution are given in figure 3. It is obvious that
mass loss differences are higher when lightweight mortars are compared to
common mortars that contain as aggregate sand. From these results, the
improvement of the mortars properties and consequently of the corrosion
performance of steel rebars when the aminobased corrosion inhibitor added is
evident. The INHIB-M, lowering the steel rebar mass loss after twelve months of
exposured by about 45% in lightweight mortar and 50% in common mortar
specimens.

390
250
192.475
Mass Loss (mgr)

200
152.82
150
104.225
100 77.725

50

0
K-I KM-I S-I SM-I
Specimens immersed in 3.5%w.t Na C
Figure 3: Mass loss measurements of lightweight and common mortars after 12
months of partially immerse to NaCl 3.5%w.t.

Carbonation of specimens versus time is shown in figure 4. Between mortars with


sand and mortars with Greek pumice as an aggregate, it is observed that the
specimens, which exhibit carbonation, were the latter mortars. Lightweight
specimens without corrosion inhibitor, exhibit 3.5 times higher carbonation depth
values than those with corrosion inhibitor. From these results, it seemed that the
corrosion inhibitor addition in the lightweight mortars protect steel by a
mechanism that seem to influence to carbon dioxide access.
14
12
Carbonation Depth (mm)

12
10
8
6
3.5
4
2
0 0
0
K-I KM-I S-I SM-I

Specimens immersed in 3.5%w.t Na C


Figure 4: Carbonation depth of lightweight and common mortars after 12 months
of exposure to NaCl 3.5%w.t.

In Tafel plot technique, a potential scan was applied to the specimens starting
from Ecorr and extending to 250mV either in the cathodic or anodic direction. The

391
current measurements in this case were the difference between anodic and
cathodic currents. Figure 5 gives the Tafel curves generated at chloride level of
3.5% w.t.in solution that specimens were been immerse. In linear polarization
technique, a controlled potential scan was applied to the specimens in a range
much smaller than that used in the Tafel plot. It was from Ecorr-25mV to
Ecorr+25mV. The Rp polarization resistance, which is the slope of the potential
current curve at Ecorr is related to Icorr. Table 4 is a comparison of the corrosion
rate values from electrochemical techniques with those from the mass loss
determination technique.
SUM.DAT -275

S-I.DAT
K-I.DAT -400
KM-I.DAT

-525

-650
E(mV)

-775

-900

-1025
-8 -7 -6 -5 -4 -3 -2

log(I)(log(A))

Figure 5: Tafel plots curves for reinforcing steel in common mortar and
lightweight specimens immersed in 3.5%w.t. NaCl

Table 4: Corrosion rates of reinforcing steel in mortars with and without


corrosion inhibitor, calculated by different techniques.
Linear polarization Weight loss
Tafel plot technique
Code technique determination
name Corrosion Corrosion Corrosio
Rp Icorr Rp Icorr Mass loss
rate rate n rate
(Ohms) (__) (Ohms) (__) (mg)
(mpy) (mpy) (mpy)
K-I 371.6 58.44 1.715 386.1 56.24 1.650 192.475 0.71193
KM-I 538.5 40.32 1.183 438.5 49.52 1.453 104.225 0.3855
S-I 460 47.20 1.384 480 45.15 1.325 152.82 0.5652
SM-I 1379 15.75 0.4617 1481 14.66 0.4298 77.725 0.2874

1.2. Category-II: Specimens exposed in atmosphere.


The results of mass loss measurements of reinforcing steel, after twelve
months of exposure in atmosphere are given in figure 6. The INHIB-M, lowering
the steel rebar mass loss after twelve months of exposured by about 44% in
lightweight mortar and 45% in common mortar specimens.

392
160
137.65
140
Mass Loss (mg)

120 111.675
100
77.15
80 61.05
60
40
20
0
K-II KM-II S-II SM-II
Specimens exposed in atmospher e

Figure 6: Mass loss measurements of lightweight and common mortars after 12


months of exposure to atmosphere.

Carbonation of specimens versus time is shown in figure 7. From these results, it


seemed that the corrosion inhibitor addition in mortars protect steel by a
mechanism that does not seem to influence to carbon dioxide access. The
carbonation depth in lightweight mortars is definitely higher than those in mortars
with sand as aggregates.

30
Carbonation Depth (mm)

25.5 24.4
25
19 19
20

15
10

0
K-II KM-II S-II SM-II
Specimens exposed in atmospher e

Figure 7: Carbonation depth of lightweight and common mortars after 12 months


of exposure to atmosphere.

393
4. CONCLUSIONS
The usage of corrosion inhibitors has decreased corrosion both in the specimens
that were partially immersed in 3.5%w.t NaCl as well as in those that were
exposed in atmospheric conditions exposed for about 45% and 50% respectively.
The results of the electrochemical measurements for calculating the corrosion
rate in order to have a first estimation of the corrosion of the mortar specimens
that were partially immersed in 3.5%w.t NaCl solution are certified and confirmed
by the results of the calculations of the reinforcements mass loss in the mortars for
a twelve month corrosion period.
The carbonisation with a high porosity aggregates is by far larger when
compared with the one in the specimens that were mortars made with common
sand. The corrosion in the lightweight mortars has reached the surface of the
reinforcements in a about a year's time and in that case the corrosion inhibitor has
decreased the reinforcements corrosion for about 45%. As a result the conclusions
of this study are in line with the confession that the usage of corrosion inhibitors
is doubling the lifetime of the constructions.

REFERENCES

1. Batis, G., Kouloumbi, N., Katsiamboulas A., 1996, Durability of reinforced


Lightweight Mortars with Corrosion inhibitors, Cement, Concrete and
Aggregates, CCAGDP, Vol. 18, No. 2, pp.118-125.
2. Batis, G., Chronopoulos, M., 1995, Durability of mortars for restoration,
Structural Studies of Historical Buildings IV, Vol. 1, Architectural Studies,
Materials and Analysis, International Coeference STREMA95, Chania, Kreta,
pp. 239-244
3. Kouloumbi, N., Batis, G., 1992, Chloride Corrosion of steel rebars in mortars
with fly ash admixtures, Cement and Concrete Composites, Vol. 14, pp.199-
207.
4. Batis, G., Pantazopoulou, P., 1999, Comperative Examination of the
Durability of Reinforced Concrete through Coatings and Corrosion Inhibitors,
International Conference on Infrastructure Regeneration and Rehabilitation
Improving the Quality of Life Through Better Construction, Sheffield, England,
pp. 683-692.
5. Hanson, C.M., Mammoliti, L., Hope, B.B, 1998, Corrosion Inhibitors in
Concrete Part I: The Principles, Cement and Concrete Research, Vol. 28,
No.12, pp. 1775-1781.
6. Mammoliti, L., Hanson, C.M., Hope, B.B., 1999, Part II, ibit Vol. 29, pp. 1583-
1589.
7. Miksic, B.A, Use of vapor phase inhibitors for corrosion protection of metal
products, International Conference Corrosion 83,No.308, pp.307-315.
8. Abdul- Hamid, J., Al-Tayyib, Mohammand Shamim Khan, 1988, Corrosion
Rate Measurements of Reinforcing Steel in Concrete by Electrochemical
Techniques, ACI Materials Journal, pp. 172-177.

394
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398



Evaluation of Migrating Corrosion Inhibitors Used in the Restoration and


Repair of Reinforced Concrete Structures

Matt Drew Jessi Jackson Meyer Joshua Hicks


Cortec Corporation Cortec Corporation Cortec Corporation
4119 White Bear Parkway 4119 White Bear Parkway 4119 White Bear Parkway
Saint Paul, MN 55110 Saint Paul, MN 55110 Saint Paul, MN 55110

ABSTRACT

Corrosion inhibitors used in reinforced concrete structures can greatly increase service life and reduce
long term maintenance costs. In this work, migrating corrosion inhibitors have been utilized in the
repairs of concrete structures that were deteriorating due to corrosion of embedded reinforcement.
These two projects show that migrating inhibitors have a direct and significant impact on the reduction
of corrosion.

The Randolph Avenue Bridge in Minnesota was repaired using an overlay incorporating a migrating
corrosion inhibitor in the westbound lanes. The repair of the eastbound lanes did not contain a
corrosion inhibitor. The rehabilitation was part of a Federal Highway Administration project and
measurements were also taken as part of a Virginia Tech study. Updated readings were performed in
2000, 2003, 2007, and 2011.

The Apple Street Parking Garage in Ohio contained precast double tees that had advanced corrosion
which led to full depth concrete repairs. Repairs were completed using concrete that included a
migrating corrosion inhibitor, and the application of a penetrating corrosion inhibitor to the rest of the
structure.

This paper will cover the corrosion rate data collection and present findings, which will include chloride
level analysis, half-cell potential readings, concrete resistivity readings, and linear polarization
resistance techniques.

Key words: Migrating corrosion inhibitor, concrete, reinforcement, half-cell potential, linear polarization
resistance, repair.

399

INTRODUCTION

Originally constructed in 1963, the Randolph Avenue Bridge spans Interstate 35E in Saint Paul,
Minnesota. Due to chloride induced corrosion, embedded reinforcement deteriorated to the point of
causing major cracking and spalling on the concrete bridge decks. In 1986, the top deck of the
Randolph Avenue Bridge was repaired in a project sponsored by the Minnesota Department of
Transportation. Both sides of the deck were repaired using a low slump, dense concrete overlay that
incorporated a migrating corrosion inhibiting admixture into one side while the other was left untreated
as the control. The treated westbound lanes have served as a real world comparison of corrosion
current reduction versus the untreated control eastbound lanes.

The rehabilitation of this bridge was part of a Federal Highway Administration project from 1986 to 1990
and a Virginia Tech Study in 1991 and 1992. Updated readings were performed by the Minnesota DOT
in 2003 and by Cortec Corporation(1) in 2000, 2007, and 2011.

The Apple Street Parking Garage in Dayton, OH is a pre-topped, precast, double tee garage. The lower
two levels were constructed in 1986 and the upper levels were added in 1989. During an inspection in
the early 2000s, the precast double tees were found to have advanced corrosion which led to
necessary full depth repairs of the concrete. In 2006, repairs were completed using ready mixed
concrete that included a migrating corrosion inhibiting admixture. Surface treatments were also made to
existing concrete outside of the patchwork using a penetrating corrosion inhibitor.

EXPERIMENTAL

Randolph Avenue Bridge

Background.

The rehabilitation process included the application of a low slump dense concrete that varied in depth
from 2.3 to 4.2 inches (58.4-106.7 mm). The mix design of the overlay can be seen in Table 1. An
aminoalcohol based migrating corrosion inhibiting admixture was added to the concrete overlay at 1
pint/yd3 (0.62 L/m3) for the two westbound traffic lanes. The eastbound lanes were repaired with the
same type of concrete which did not contain the corrosion inhibitor to act as the control. Prior to
application of the overlay, the deck was milled to a depth of 0.5 inches (13 mm) and the areas of
unsound concrete were removed. The cavities from the removal of the unsound concrete were filled
with the overlay concrete. The general slope of the bridge for water runoff appears to be towards the
northeast.

400

Table 1
Mix design parameters of the Randolph Avenue Bridge repair
Control Treated
Component
(lbs/yd) (lbs/yd)
Type I Cement 836 836
Water 270 270
w/c ratio 0.32 0.32
Coarse Aggregate 1385 1385
Fine Aggregate 1374 1374
Water Reducing Admixture 0.25 0.25
Air Entraining Agent 0.073 0.073
Corrosion Inhibitor - 0.95

Corrosion assessments were conducted on the eastbound (control) and westbound (aminoalcohol)
travel lanes of the structure by Virginia Tech researchers on two occasions, June 1991 and August
1992. The assessments included visual inspection, delamination survey, cover-depth survey, chloride
contents as a function of depth, corrosion potentials, and estimates of corrosion current densities (icorr)
using 3LP(2) Meter (Linear Polarization Device 1). Prior to the assessments completed by Virginia Tech,
the repair was part of a Federal Highway Administration Project until 1990.

In November 2000, technicians returned to the bridge and took new measurements. These included
linear polarization readings obtained by a Gecor 6(3) (Linear Polarization Device 2) instrument, and
copper/copper sulfate half-cell potentials. A new chloride analysis was also taken at various depths.

In June 2007 and July 2011, chloride analysis, alkalinity testing, and half-cell potential readings were
performed. Linear polarization readings using a Galvapulse(4) (Linear Polarization Device 3) instrument,
of corrosion current, corrosion rate, and concrete resistivity were also taken.

Apple Street Parking Garage

Background.

The concrete reinforcement is a steel mesh that is located 1.75-2 inches (44.5-50.8 mm) deep and is
0.19 inches (4.76 mm). The mesh was laid out in a 4 foot by 8 foot (1.22 m by 2.44 m) grid. In
November 2006, patchwork was completed using ready mixed concrete that incorporated an amine
carboxylate based migrating corrosion inhibiting admixture dosed at 1.5 pints/yd3 (1 L/m3).

Also in 2006, a water-based penetrating corrosion inhibitor was applied to both the deck and to the
underside at a coverage rate of 150 ft2/gal (3.68 m2/L). The substrate was allowed to dry for a week and
was then shot blasted prior to application of a 40% silane water repellant to the deck surfaces.

On July 1, 2009, linear polarization readings were obtained using Linear Polarization Device 3. Ten
corrosion current readings were taken at five different locations within the garage.

401

Chloride Contamination Levels.

At the Randolph Avenue Bridge, powdered concrete samples for chloride analysis were taken at mean
depths of 0-1, 1-2, and 2-3 inches (0-25, 25-51, and 51-76 mm) from six total locations, three on each
side of the bridge.

Samples were taken using a rotary impact type drill with a 0.5 inch (12.7 mm) sized bit. Three-gram
samples that passed through a #20 sieve were obtained from each depth. The powder was then mixed
with 20 ml of digestion solution for a total of 3 minutes and then 80 ml of stabilizing solution was added.
A calibrated electrode coupled to an Orion(5) Model 720-pH/ISE meter was then immersed in the
solution, and the chloride-ion concentration was recorded. This method was consistent with the
AASHTO: T260 Procedure C. The standard deviation for this chloride test was determined by testing
the six pulverized concrete Quality Assurance (QA) samples of known chloride content. Each QA
sample was tested five times.

Corrosion Current Measurements.

Corrosion current density (icorr) estimates were taken at the Randolph Avenue Bridge in June 1991 and
August 1992 using Linear Polarization Device 1. Readings were also performed in November 2000,
July 2007, and July 2011 using both Linear Polarization Device 2 and Linear Polarization Device 3.
Corrosion current density readings were also obtained at the Apple Street Parking Garage in July 2009
using Linear Polarization Device 3.

The icorr measurement is proportional to the corrosion rate through Faradays Law. The instruments
used measure the corrosion rate of steel in concrete by polarization resistance or linear polarization
techniques. This is a non-destructive technique that works by applying a small current to the rebar and
measuring the change in the potential. Then the polarization resistance, Rp, (the change in potential
measured), is divided by the applied current. The corrosion rate, icorr, is obtained from the polarization
resistance, Rp, by means of the Stearn and Geary relationship:

icorr = B/Rp, where B = 26 mV (1)

Each device used has different criteria for evaluating the corrosion rates which are described in Table
2, Table 3, and Table 4.1

Table 2
Corrosion intensity versus corrosion current and rate of corrosion found by Linear Polarization Device 1
Corrosion Current Corrosion Rate
Intensity of Corrosion
(A/cm2) (m/year)
<0.5 <5.8 Passive Condition
0.5-2.7 5.8-31.3 Low corrosion (damage possible in 1-15 years)
2.7-27 31.3-313.2 Moderate corrosion (damage possible in 2-10 years)
>27 >313.2 High corrosion (damage expected in 2 years or less)

402

Table 3
Corrosion intensity versus corrosion current and rate of corrosion found by Linear Polarization Device 2
Corrosion Current Corrosion Rate
Intensity of Corrosion
(A/cm2) (m/year)
<0.5 <1.2 Negligible corrosion
0.5-2.7 1.2-5.8 Low corrosion
2.7-27 5.8-11.6 Moderate corrosion
>27 >11.6 High corrosion

Table 4
Corrosion intensity versus corrosion current and rate of corrosion found by Linear polarization Device 3
Corrosion Current Corrosion Rate
Intensity of Corrosion
(A/cm2) (m/year)
<0.5 <5.8 Passive condition
0.5-5 5.8 to 58 Low corrosion
5-15 58 to 174 Moderate corrosion
>15 >174 High corrosion

Concrete Resistivity Measurements.

Linear Polarization Device 2 calculates the concrete resistivity by means of the formula,

Resistivity = 2 R D (2)

where R = resistance by the iR drop from a pulse between the sensor counter-electrode and the rebar
network and D = counter-electrode diameter of the sensor

The value of the concretes resistance is used as an additional parameter for the interpretation of the
rate of corrosion. Table 5 shows the interpretation of the results.2

Table 5
Correlation of resistivity measurements to corrosion rate using Linear Polarization Device 2
Resistivity Corrosion Rate
>100-200 k cm Very low, even with high chloride and carbonation
50-100 k cm Low
10-50 k cm Moderate to high where steel is active
<10 k cm Resistivity is not the parameter controlling corrosion rate

Half-Cell Potentials.

ASTM C 876 corrosion half-cell potentials were measured on the Randolph Avenue Bridge for both the
eastbound and westbound travel lanes with Linear Polarization Device 2 in November 2000, June
2007, and July 2011. The Minnesota Department of Transportation also conducted half-cell potential
readings in 2003. According to ASTM C 876, the results can be interpreted in Table 6.

403

Table 6
Corrosion potential using half-cell potential readings from Linear Polarization Device 2
Potential Probability of Corrosion
>-200 mV Less than 10%
-200 mV to -350 mV 50%
<-350 mV Greater than 90%

Carbonation.

Carbonation of concrete is a process by which carbon dioxide from the air penetrates the concrete and
reacts with the hydroxides, such as calcium hydroxide, to form carbonates. This process increases
shrinkage on drying (promoting crack development) and reduces the alkalinity of the concrete. High
alkalinity is needed to protect embedded rebar from corrosion; consequently, concrete should be
resistant to carbonation to prevent steel corrosion.3 The carbonation of powdered concrete samples
taken from the Randolph Avenue Bridge was determined by using phenolphthalein (alkalinity)
measurements.

RESULTS AND DISCUSSION

Randolph Avenue Bridge

Chloride Threshold.

Chloride threshold refers to the concentration of chlorides at which corrosion in the steel is initiated.
Based on the service life prediction model, Life 365, the chloride threshold of the concrete used in the
Randolph Avenue Bridge is 0.05 percent of the concrete.4 This converts to 0.4% by weight of the
cement and 3.35 lbs/yd (1.98 kg/m3).

Chloride content readings were taken at 0-1, 1-2, and 2-3 inches (0-25, 25-51, and 51-76 mm) from 3
different locations on each side of the bridge. These readings indicated that the overall chloride levels
in the control side were slightly higher than in the treated side. As can be seen in Table 7, the chloride
levels have continued to rise at the level of the steel.

Table 7
Average chloride levels of Randolph Avenue Bridge
Treated Side (lbs/yd3) Control Side (lbs/yd3)
Depth (0-1) (1-2) (2-3) (0-1) (1-2) (2-3)
1991 3.5 0 0.7 7.7 2.5 1.9
1992 6.5 1.1 1.9 9.5 3.5 2.5
2000 11.7 1.6 1.3 17.2 6.2 2.4
2007 11.7 1 2.6 20 7.4 2.3
2011 12.3 4.9 1.8 14.7 6.6 3.5

Corrosion Current Readings.

Corrosion currents of rebar have increased on both sides of the bridge since the year 2000, when the
treated side had very low corrosion currents, an average of 0.0081 A/cm2, approximately 42% below
readings taken on the control side (average of 0.014 A/cm2).

The corrosion current readings that were taken in July of 2011 are substantially higher at almost all
points on the bridge. As shown in Table 7 the control side has reached the chloride threshold at the
depth of the reinforcing steel. As seen in Table 8, the average corrosion rate of the treated side is 35%
of the level on the control side. The highest rate of corrosion was measured in the center section of the
control
2012 side
by NACE which was
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for permission compared
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any form in part or insection which
whole must is 0.4202
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404

a reduction of 67%. This reduction is confirmed by the half-cell potentials which show a high probability
of corrosion in the control South Central section seen in Table 10.

In Table 8, the average corrosion current data is presented comparing segments of the bridge using
Linear Polarization Device 2. In 2011 all readings taken on the treated areas of the bridge were much
lower than the readings taken on the control side. Additionally, all three control locations had average
corrosion rate readings that would be considered active, whereas the treated side readings were all in
the passive range. This indicates the corrosion inhibiting admixture is functioning as expected.

Table 8
Average corrosion rates for each bridge section of Randolph Avenue Bridge
Treated Lanes Control Lanes
Northwest North Central Northeast Southwest South Central Southeast
Year
(A/cm2) (A/cm2) (A/cm2) (A/cm2) (A/cm2) (A/cm2)
2000 0.0081 0.0006 0.0077 0.093 0.175 0.145
2007 0.1258 0.2522 0.4231 0.2982 0.1878 0.368
2011 0.2659 0.4202 0.3196 0.6254 1.2755 0.8607

Figure 1 shows the comparison of corrosion rate readings on the control side versus the treated side
using Linear Polarization Device 2. Prior to 2007, both sides of the bridge showed average corrosion
rates in the passive range, however the treated side exhibited 40% lower readings. Now that the control
side has entered active corrosion, the treated side is exhibiting corrosion rates that are approximately
85% less.

Figure 1: Average corrosion rates of the Randolph Avenue Bridge

Weather can be a factor that affects readings. Of particular importance is the humidity level as the
moisture in the concrete affects the conductivity and readings that are taken. To mitigate the effects of
the weather, the surface was prepared using ASTM C876. This method requires a specific pattern of
adding moisture to the concrete so a consistent environment is achieved across all areas.

405

Alkalinity Levels.

The core samples from 2011 were tested and exhibited average alkalinity levels between 1640 and
1840 mg/L. The samples that were taken from the treated side of the bridge show results of higher
alkalinity levels, which can signify the presence of corrosion inhibitor and resistance to carbonation. The
data is compiled in Table 9.

Table 9
Alkalinity results organized by the section of the Randolph Avenue Bridge
Treated Control
Alkalinity Average Alkalinity Average
Sample Sample
(mg/L) (mg/L) (mg/L) (mg/L)
NW 0-1" 1680 SW 0-1" 1800
NW 1-2" 1800 1800 SW 1-2" 1920 1800
NW 2-3" 1920 SW 2-3" 1680
NC 0-1" 1800 SC 0-1" 1920
NC 1-2" 1800 1840 SC 1-2" 1800 1800
NC 2-3" 1920 SC 2-3" 1680
NE 0-1" 1920 SE 0-1" 1560
NE 1-2" 1800 1760 SE 1-2" 1680 1640
NE 2-3" 1560 SE 2-3" 1680

Half-Cell Potentials.

The half-call potential readings taken in 2011 can be seen in Table 10. The average reading for each
side of the bridge shows that the potential for corrosion is higher on the control side than that of the
treated side according to Table 6.

Table 10
Half-cell potential values from each segment of the Randolph Avenue Bridge
Treated Control
Rebar NW (mV) NC (mV) NE (mV) SW (mV) SC (mV) SE (mV)
1 -378 -130 -130.3 -84 -332 -231
2 -331.3 -128.7 -93.3 -91.5 -397.5 -248.5
3 -294.3 -98.3 -59.7 -88.5 -381.5 -187
4 -239.7 -83.3 -68.3 -104 -400 -150
5 -227.3 -72.3 -82.7 -97.5 -392 -125.5
6 -183.7 -79 -37 -99 -400 -117.5
7 -185 -69.3 -36.7 -122 -404.5 -140
8 -170.3 -72 -46.3 -163.5 -381.5 -147
9 -156 -78 -79.3 -231 -397.5 -181
10 -172 -76.3 -167 - - -206.5
11 -190.7 -74.3 -192 - - -270.5
12 - -97.3 -189.7 - - -
13 - -96.3 -191.7 - - -
14 - - -218.7 - - -
Average -229.8 -88.9 -113.8 -120.1 -387.4 -182.2

406

The time versus average half-cell potential results, shown in Figure 2, shows that the potential for
corrosion within the bridge is higher on the control side and has been for 20 years. This data along with
the rest of the supporting information suggests that levels of corrosion in the treated side are lower than
in the control.

Figure 2: Average half-cell potentials of the Randolph Avenue Bridge

Apple Street Parking Garage

Corrosion Rate Readings.

All readings at the Apple Street Parking Garage were performed using Linear Polarization Device 3. All
locations had average readings in the passive to low levels according to Table 4. Fifty readings were
taken in total; 10 readings at 5 different locations throughout the garage. All readings can be seen in
Table 11.

Table 11
Corrosion current readings for treated areas of the Apple Street Parking Garage
Location 1 Location Location Location 4 Location 5
Reading
(A/cm2) 2 (A/cm2) 3 (A/cm2) (A/cm2) (A/cm2)
1 2.97 1.75 0.51 1.62 3.12
2 1.76 1.35 0.57 0.65 0.89
3 3.01 1.08 0.47 0.81 0.36
4 1.22 1.37 0.26 1.17 0.38
5 1.59 6.76 0.32 0.96 0.25
6 3.48 1.38 0.41 0.24 0.24
7 1.55 0.96 0.6 0.26 0.52
8 2.15 8.22 0.4 0.92 0.22

407

9 6.43 9.71 0.45 0.62 6.63
10 5.28 3.37 0.38 1.2 2.86
Average 2.94 3.6 0.43 0.84 1.55

CONCLUSIONS

Aminoalcohol and amine carboxylate based corrosion inhibitors have proven beneficial when used in
repair of concrete that has cracked and spalled due to chloride induced corrosion of the embedded
reinforcing steel. In the Randolph Avenue Bridge, corrosion was significantly decreased compared to
the control due to the presence of the aminoalcohol corrosion inhibiting admixture. The Apple Street
Parking Garage is showing very low corrosion currents due to the high affinity of the amine carboxylate
corrosion inhibiting admixture and the penetrating corrosion inhibitor. The lower corrosion currents are
due to the adsorption of the aminoalcohol and amine carboxylate molecules on the embedded
reinforcing steel, showing that these molecules can displace existing chloride and water molecules.
Thus, corrosion rates can be decreased significantly.

ACKNOWLEDGMENTS

Authors thank American Engineering and Testing, Inc for their assistance in obtaining readings on the
Randolph Avenue Bridge. They would also like to thank Chris Przywara, Structural Engineer with THP,
Ltd. and Rae Jean Nicholl of S.M.A.R.T. Distribution for their assistance with the Apple Street Parking
Garage readings.

REFERENCES

1) Germann Instruments, Inc., Galvapulse TM GP-5000 Instruction and Maintenance Manual, 2005.

2) Andrade, C., Fullea, J., Alonso, C., The Use of the Graph Corrosion Rate-Resistivity in the
Measurement of Corrosion Current, International Workshop MESINA, Instituto Eduardo Torroja,
Madrid, Spain, 1999.

3) Kosmatka, Steven and Panarese, William, Design and Control of Concrete Mixtures Thirteenth
Edition, Portland Cement Association, Skokie, Illinois, 1994 rev. pp. 72.

4) Thomas, M.D.A. and Bentz, E.C., Life-365 Computer Program for Predicting the Service Life and
Life-Cycle Costs of Reinforced Concrete Exposed to Chlorides. University of Toronto, Toronto, Canada,
April 21, 2000, pp. 9.

5) Alfred J Gardiner PE et al, Affects of a Migrating Corrosion Inhibitor on Bridge Decks in St. Paul,
Minnesota, August 27, 2003.

408
Corrosion Inhibition of Steel Rebar in Concrete
By Migrating Corrosion Inhibitors

Bezad Bavarian and Lisa Reiner


Dept. of Civil and Manufacturing Engineering
California State University, Northridge
18111 Nordhoff Street
Northridge, California 91330-8347

Corrosion of embedded steel is one of the major causes of concrete deterioration in reinforced concrete
structures. This type of corrosion results when a corrosive species, water and air, penetrate through the
concrete pores to the steels surface. The key to inhibiting rebar corrosion is to restrict the permeability of
concrete. Migrating corrosion inhibitors and concrete sealers can reduce the corrosive ion mobility and
permeability by decreasing concrete porosity.

The effectiveness of several commercially available migrating corrosion inhibitors and concrete sealers for
steel rebar (class 60) in concrete was investigated. Concrete specimens were prepared with reinforcement
at 1 and 2 inches of concrete coverage. Corrosion inhibitors and sealers were applied to the surfaces of the
concrete after they had been cured for 28 days. Specimens were immersed in a 3.5% sodium chloride
solution. Using Electrochemical Impedance Spectroscopy, the specimens were tested to determine changes
in their resistance polarization, Rp, over a 52-week period. The Rp values are significant because they are
inversely proportional to the rate of corrosion. The open circuit potential versus a Cu/CuSO4 reference
electrode (ASTM C876) was also monitored as a function of time to ascertain the probability of corrosion
activity.

MCI 2022 has successfully demonstrated corrosion inhibition of steel rebar in 3.5% NaCl solution. This
MCI product has exhibited promising corrosion inhibiting properties by maintaining a high resistance
polarization (low corrosion rate) for the rebar in concrete. The reference concrete samples (non-protected),
however, have shown a decline in their resistance polarization, indicative of corrosion.

INTRODUCTION

Corrosion of steel rebar is the major cause of concrete deterioration in reinforced and prestressed concrete
structures. Billions of dollars each year are spent to repair the damages resulting from this type of corrosion
that initiates when salts, water and air penetrate through the pores of concrete and reach the surface of the
steel. In general, embedded steel rebar in concrete is stable; the concrete provides a highly alkaline,
protective environment. Problems arise when the embedded concrete structure is exposed to the
aforementioned corrosive species.

Chemical admixtures have been combined with concrete as a possible means of preventing chloride ions
from reaching the steel's surface. Inhibitors have the effect of promoting a passive layer at the steels
surface, which makes it more difficult for the chloride ions to remove electrons. A reduction in the
corrosion rate can occur if the permeability of the concrete is restricted. Migrating corrosion inhibitors
(MCI) can reduce the corrosive ion mobility and neutralize these corrosive species.

Migrating Corrosion Inhibitor (MCI) technology was recently developed to protect the imbedded steel
rebar/concrete structure. MCIs are based on amino-carboxylate chemistry. They are very effective

409
mixed cathodic and anodic corrosion inhibitors. Under normal conditions these substances enhance the
vapor pressure. Increased pressure causes the inhibitor molecules to diffuse through the concrete. This
diffusion process requires a period of time to migrate through the concretes pores. Once the MCIs migrate
to the rebars surface, a protective layer is formed. This suggests that the migratory inhibitors are
physically adsorbed onto the metal surfaces1.

MCIs can be incorporated as an admixture or can be used by surface impregnation of existing concrete
structures. With surface impregnation, diffusion transports the MCIs into the deeper concrete layers. They
will delay and inhibit the onset of corrosion on steel rebar. Bjegovic and Miksic recently demonstrated the
effectiveness of MCIs over four years of continuous testing1. They also showed that the migrating amine-
based corrosion-inhibiting admixture can be effective when they are incorporated in the repair process of
concrete structures2. Furthermore, laboratory tests have proven that MCI corrosion inhibitors migrate
through the concrete pores and protect internal steel bars against corrosion even in the presence of
chlorides3-4.

The objective of this investigation was to study the corrosion inhibition of several commercially available
migrating corrosion inhibitors on steel rebar in concrete. Electrochemical monitoring techniques were
applied while samples were totally immersed in 3.5% NaCl at ambient temperatures. Due to the low
conductivity of concrete, the corrosion behavior of steel rebar had to be monitored using AC
electrochemical impedance spectroscopy (EIS). During this investigation, changes in the resistance
polarization and the corrosion potential of the rebar were monitored to ascertain the degree of effectiveness
for these MCI products. The results were compared with previous investigations conducted on several
admixtures and stainless steel rebars.

EXPERIMENTAL PROCEDURES

In theory, the steel rebar/concrete combination can be treated as a porous solution that can be modeled by a
Randles electrical circuit. EIS tests performed on a circuit containing a capacitor and two resistors indicate
that this model is an accurate representation of an actual corroding specimen. EIS testing allows for the
determination of fundamental parameters relating to the electrochemical kinetics of the corroding system.
This is attained through the application of a small amplitude-alternating potential signal of varying
frequency to the corroding system. Because processes at the surface absorb electrical energy at discrete
frequencies, the time lag and phase angle, theta, can be measured. The values of concern in this study are
Rp and R. The Rp value is a measure of the polarization resistance or the resistance of the surface of the
material to corrosion. R is a measure of the solution resistance to the flow of the corrosion current.

By monitoring the Rp value over time, the relative effectiveness of the sample against corrosion can be
determined. If the specimen maintains a high Rp value in the presence of chloride, it is considered to be
"passivated" or immune to the effects of corrosion. If the specimen displays a decreasing Rp value over
time, it is corroding and the inhibitor is not providing corrosion resistance.

The EG&G Instruments Potentiostat/Galvanostat Model 273A and EG&G M398 Electrochemical
Impedance Software were used to conduct these experiments and to record the results. Bode and Nyquist
plots were produced from the data obtained using the single sine technique. Potential values were recorded
and plotted with respect to time. By comparing the bode plots, changes in the slopes of the curves were
monitored as a means of establishing a trend in the Rp value over time. To verify this analysis, the Rp values
were also estimated by using a curve fit algorithm on the Nyquist plots (available in the software).
Results from EIS tests were organized into bode and Nyquist plots. Based on these plots, the Rp and R
combined values are displayed in the low frequency range of the bode plot and the R value can be seen in
the high frequency range of the bode plot. The diameter of the Nyquist plot is a measure of the Rp value.

Ten concrete samples with dimensions 8 x 4 x 4 were prepared. Each sample consisted of one 8 inch
steel (class 60) rebar (3/8 diameter) and one 8-inch Inconel metal strip (counter electrode). The rebar
prior to being placed in concrete were exposed to 100% RH (relative humidity) to initiate corrosion.
Teflon tape was wrapped around the top 2-3 inches of inconel and rebar to prevent corrosion rust at the

410
concrete/metal interface. Concrete was mixed with one-half gallon water per 60-lb. bag (.4-.5 cement to
water ratio) in a mechanical mixer. Inconel and rebar were placed one inch apart and two inches from the
bottom of the wood container before concrete was poured. Five rebars were placed one inch from the side
of the box and five were placed two inches. The concrete was vibrated by machine after being poured into
the boxes. This was done to minimize bubbles and slurry. The concrete was air cured for 24 hours, then
removed from the wooden crates and placed in 8 inches of water to continue the curing process. The
concrete specimens were removed from water and set out to dry (approx. 28 days; the attained compressive
strength of concrete was about 2,8003,200 psi). The concrete blocks were sandblasted to remove loose
particles, debris, and rust deposited on the metal. This process left the concrete with a marginally smoother
surface. Red shrink-wrap was placed on each of the exposed rebars to prevent additional corrosion.

CORTEC MCI 2021 BASE SEALER was applied on two concrete samples. CORTEC MCI 2021
INHIBITOR & BASE SEALER were applied on two concrete samples. CORTEC MCI 2022 BASE
SEALER was applied on two concrete samples. CORTEC MCI 2022 INHIBITOR & BASE SEALER
were applied on two samples. The remaining two concrete blocks were used as control references.
These samples were immersed in 3.5 % NaCl solution (roughly 6-7 inches of each sample was immersed in
the solution continuously). EIS (Electrochemical AC Impedance Spectroscopy) testing was started after 24
hours of immersion using a Cu/CuS04 electrode.

MCI 2021, the thicker of the two inhibitors, did not adhere to the concrete and fell to the bottom of the
container after ten hours of immersion in solution. This resulted in a heavy white blanket of residue. Two
coats of base and/or inhibitor were applied to each sample. There was nothing notable about the MCI
2022. The 2022 inhibitor and base sealer resembled a dilute (thin) milky white fluid.

RESULTS and DISCUSSION

The corrosion inhibition of two commercially available migrating corrosion inhibitors (Cortec MCI 2022
and 2021) was investigated over a period of 400 days using AC electrochemical impedance spectroscopy
(EIS). Throughout this investigation, changes in the resistance polarization and the corrosion potential of
the rebar were monitored to determine the degree of effectiveness for the Cortec MCI 2021 & 2022
products. According to the ASTM (C876) standard, if the open circuit potential (corrosion potential) is
between 0 and -200 mV, this indicates a 90% probability that no reinforcing steel has corroded. Corrosion
potentials more negative than -350 mV are assumed to have a greater than 90% likelihood of corrosion.

Figure 1 shows corrosion potentials for the MCI 2021 and untreated control samples dropped from
200 mV to 600 mV, which indicates a 90% probability of corrosion attack on the reinforcing steel.
Figure 2 shows that the corrosion potentials for MCI 2022 without inhibitor were 200 mV; for samples
with inhibitor, the corrosion potentials were 120 mV. All of the MCI 2022 samples had corrosion
potentials in the non-corroding range per ASTM C876.

AC electrochemical impedance spectroscopy (EIS) showed that MCI 2021 and reference samples had a
gradual reduction in their resistance polarization, from about 10000 ohms to less than 600 ohms, which is
similar to the drop in their corrosion potentials and strongly indicative of steel rebar corrosion (Figures 3-
8). Figures 3-8 show that the resistance polarization for MCI 2022 without inhibitor (samples) gradually
increased from 10,000 to 100,000 ohms; for samples with inhibitor, the Rp was 10,000 at the beginning of
the experiment and ended at close to 200,000 ohms. An increase in the Rp value was observed after about
200 days, indicating that Migrating Corrosion Inhibitors (MCIs) require an induction period for diffusion
into the concrete to reach the metal rebar.

The samples coated with the MCI 2022 Inhibitor and Base Sealer showed the greatest amount of corrosion
resistance; the corrosion resistant behavior was similar to stainless steel rebar (investigated in a subsequent
project)5-6. These results are extremely promising for the MCI 2022 product in its ability to protect steel
rebar in concrete in aggressive environments.

411
CONCLUSION

Corrosion inhibition of two commercially available migrating corrosion inhibitors (Cortec MCI 2022 and
2021) on steel rebar in concrete was investigated while the concrete was totally immersed in 3.5% NaCl at
ambient temperatures using electrochemical monitoring techniques.

The MCI 2022 products have successfully inhibited corrosion of the rebar in a 3.5% NaCl solution for 400
days. Steel rebar corrosion potentials were maintained at approximately -120 mV, and rebar resistance
polarization reached as high as 200,000 ohms. Both results indicate excellent corrosion resistance
performance. The MCI 2021 and untreated samples have shown a decline in their resistance polarization
and corrosion potentials, indicative of corrosion. The lack of corrosion inhibition of MCI 2021 could be
due to the lack of its adhesion to the concrete surface, thereby leaving the concrete with no protection.

In summary, the experimental results demonstrate that the MCI 2022 products offer an excellent inhibiting
system for protecting reinforced concrete in an aggressive 3.5% NaCl solution. These results are extremely
promising for the protection of steel rebar in concrete in aggressive environments.

REFERENCE

1. D. Bjegovic and B. Miksic, Migrating Corrosion Inhibitor Protection of Concrete, MP,


NACE International, Nov. 1999.

2. D. Bjegovic and V. Ukrainczyk, Computability of Repair Mortar with Migrating


Corrosion Inhibiting Admixtures, CORROSION/97, paper no. 183 (Houston, TX:
NACE, 1997.

3. D. Rosignoli, L.Gelner, and D. Bjegovic, Anticorrosion Systems in the Maintenance,


Repair and Restoration of Structures in Reinforced Concrete, International Conference
Corrosion in Natural and Industrial Environments: Problems and Solutions, Grado, Italy,
May 23-25, 1995.

4. R. Martinez , A. Petrossian, , and B. Bavarian, Corrosion of Steel Rebar in Concrete,


presented at the 12th NCUR, April 1998.

5. R. Martinez , A. Petrossian, B. Bavarian, Investigation of the Corrosion Behavior of


Steel Rebar in Concrete in High Chloride Environments Through the Use of
Electrochemical Impedance Spectroscopy, June, 1998.

6. L. Reiner and B. Bavarian, Corrosion of Steel Rebar in Concrete,


presented at the 14th NCUR, Missoula, Montana, April 2000.

412
413
414
415
416
417
Testing of Randolph Street Bridge
Background:
In 1986, the deck of the bridge that carries Randolph Street over I-35E in St. Paul, Minnesota, was
rehabilitated. The rehabilitation process included the application of a Low Slump Dense Concrete
(LSDC) overlay that varied in depth from 2.28 to 4.2 inches. Cortec MCI-2000 was added to the
LSDC at 1 lb/yd3 (0.6 kg/m3) for the two westbound traffic lanes. Prior to overlay, the deck was
milled to a depth of 0.5 in (13 mm) and the areas of unsound concrete were removed. The cavities
from the removal of the unsound concrete were filled with the overlay concrete. The general slope
of the bridge for water runoff appears to be towards the northeast.

Corrosion assessments were conducted on the eastbound (control) and westbound (MCI) travel lanes
of the structure by Virginia Tech researchers on two occasions, June 1991 and August 1992. The
assessments included visual inspection, delamination survey, cover-depth survey, chloride contents
as a function of depth, corrosion potentials, and estimates of corrosion current densities (icorr).
SHRP-S-658 contains all information from the 1991 and 1992 study.

In November 2000, technicians from Cortec Corporation and American Engineering Testing
returned to the bridge and took new measurements. These included Gecor 6 readings and
copper/copper sulfate half-cell potentials. A new chloride analysis was also taken at various depths.
Cortec report number 01-019-1425 contains the data obtained in 2000.

This report, 07-151-1425, will contain data obtained during the June 2007 evaluation. A technician
from American Engineering Testing used a Profometer to locate rebars in concrete and did Chloride
testing. Technicians from Cortec Corporation did alkalinity testing and took GalvaPulse readings of
corrosion current and corrosion rate, and Gecor 6 readings of resistivity and half-cell potential.

Purpose:
The purpose of this study was to follow-up on the benefit of MCI-2000 in reducing reinforcing steel
corrosion.

Materials:
Geocisa Gecor 6
GalvaPulse
Proceq SA Profometer
Rotary Impact Type Drill with a bit
Alkalinity Test Kit
Tap water

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418
Methods:
AASHTO: T260 Procedure C, Sampling and Testing for Chloride-Ion in Concrete and Concrete Raw
Materials
Gecor 6 method for measuring concrete resistivity and half-cell potential
GalvaPulse method for measuring corrosion current and corrosion rate
Alkalinity

Procedures:
Chloride Contamination Levels
Powdered concrete samples for chloride analysis were taken at mean depths of 0-1, 1-2, and 2-3
in (0-25, 25-51, and 51-76 mm) from 3 different locations on each side of the bridge.

A diagram of these locations is included at the end of this report. Samples were taken using a rotary
impact type drill with a sized bit. Three-gram samples that passed through a #20 sieve were obtained
from each depth. The powder was then mixed with 20 ml of digestion solution for a total of 3 minutes
and then 80 ml of stabilizing solution was added. A calibrated electrode coupled to an Orion Model 720-
pH/ISE meter was then immersed in the solution, and the chloride-ion concentration was recorded. This
method was consistent with the AASHTO: T260 Procedure C. The standard deviation for this chloride
test was determined by testing the six pulverized concrete Quality Assurance (QA) samples of known
chloride content. Each QA sample was tested five times.

Corrosion Current Measurements


Corrosion current density (icorr) estimates were taken with the Gecor 6 instrument in November 2000
and a GalvaPulse instrument in July 2007. These same estimates were taken in June 1991 and August
1992 using a 3LP device. The icorr measurement using the 3LP device is proportional to the corrosion
rate through Faradays Law. The Gecor 6 and GalvaPulse measure the corrosion rate of steel in
concrete by polarization resistance or linear polarization techniques. This is a non-destructive
technique that works by applying a small current to the rebar and measuring the change in the half-cell
potential. Then the polarization resistance, Rp, (the change in potential measured), is divided by the
applied current. The corrosion rate, icorr, is obtained from the polarization resistance, Rp, by means of
the Stearn and Geary relationship:

icorr = B/Rp, where B = 26 mV.

The criteria for estimating the condition of the reinforcement in relation to the different devices
measured value of the rate of corrosion have been defined as1:

Table 1. Corrosion intensity versus corrosion current and rate of corrosion found by LP3 device
(K.Clear)
Corrosion Current Corrosion Rate
Intensity of Corrosion
(PA/cm2) (Pm/year)
<0.5 <5.8 Passive condition
0.5-2.7 5.8 to 31.3 Low corrosion (damage possible in 10-15 years)
2.7-27 31.3 to 313.2 Moderate corrosion (damage possible in 2-10 years
>27 >313.2 High corrosion (damage expected in 2 years or less)

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Corporation is strictly prohibited.

419
Table 2. Corrosion intensity versus corrosion current and rate of corrosion found by Gecor 6
Corrosion Current Corrosion Rate
Intensity of Corrosion
(PA/cm2) (Pm/year)
<0.5 <1.2 Negligible corrosion
0.5-2.7 1.2 to 5.8 Low corrosion
2.7-27 5.8 to 11.6 Moderate corrosion
>27 >11.6 High corrosion

Table 3. Corrosion intensity versus corrosion current and rate of corrosion found by GalvaPulse
Corrosion Current Corrosion Rate
Intensity of Corrosion
(PA/cm2) (Pm/year)
<0.5 <5.8 Passive condition
0.5-2 5.8 to 58 Low corrosion
2-5 58 to 174 Moderate corrosion
>27 >174 High corrosion

Concrete Resistivity Measurements


Gecor 6 calculates the concrete resistivity by means of the formula:

Resistivity = 2 * R * D, where

R = resistance by the iR drop from a pulse between the sensor counter-electrode and the rebar network
D = counter-electrode diameter of the sensor

The value of the concretes resistance is used as an additional parameter for the interpretation of the
rate of corrosion. According to Andrade2, the following interpretation of the results is possible:

Table 4. GeCor 6 correlation of resistivity measurements to corrosion rate.

Resistivity Corrosion Rate


>100 to 200 k: cm Very low, even with high chloride and carbonation
50 to 100 k: cm Low
10 to 50 k: cm Moderate to high where steel is active
<10 k: cm Resistivity is not the parameter controlling corrosion rate

Half-Cell Potentials
ASTM C 876 corrosion half-cell potentials were measured for both the eastbound and westbound
travel lanes with a Gecor 6 in November of 2000 and June 2007. According to ASTM C-876, the
results can be interpreted as follows:

Table 4b. Corrosion Potential


Potential Probability of Corrosion
>-200 mV Less than 10%
-200 mV to -350 mV 50%
<-350 mV Greater than 90%

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420
Carbonation
Carbonation of concrete is a process by which carbon dioxide from the air penetrates the concrete and
reacts with the hydroxides, such as calcium hydroxide, to form carbonates. This process increases
shrinkage on drying (promoting crack development) and reduces the alkalinity of the concrete. High
alkalinity is needed to protect embedded rebar from corrosion; consequently, concrete should be
resistant to carbonation to prevent steel corrosion3. The carbonation of powdered concrete samples
taken from the bridge was determined by using phenolphthalein (alkalinity) measurements.

Attached Figures/Tables:
East and Westbound Randolph St. Bridge Deck Test Locations (Figure 1)
East and Westbound Randolph St. Bridge Deck Average Half-Cell Potential, Resistivity and
Corrosion Rates by Location (Figure 2)
Average Half-Cell Potential versus Year (Figure 3)
Average Corrosion Rate versus Year (Figure 4)
Average Chloride Contamination levels (Table 5)
Average Corrosion Currents using GalvaPulse (Table 6)
Average Corrosion Rates using GalvaPulse (Table 7)
GalvaPulse Measurements for Control Side of Bridge (Table 8)
GalvaPulse Measurements for MCI-2000 Treated Side of Bridge (Table 9)
Alkalinity Results (Table 10)
Summary of Half-Cell Potentials (Table 11)
Summary of Resistivity Measurements (Table 12)

Summary of Results:
1. In 2001, it was predicted the chloride concentration in the control side of the bridge would reach of
0.4wt% (of cementious materials) at the rebar in 19.5 years from the application of the overlay, or in
the year 2005, if the chloride level continues to increase at its current rate. The MCI-2000 treated
side was estimated to reach 0.4wt% (of cementious materials) of chlorides in 36 years from the
application of the overlay, or in the year 2022. Revision of these predictions based on calculations
from 2007 show that the Control side is estimated extended to the year 2016 and the MCI-2000
treated side is now estimated to the year 2013. It is not surprising that these would occur about the
same rate, or even faster on the MCI side, where there is a tendency for water to pool at the bottom
of the northeast corner.

The decrease in rate of ingress of chloride could be due to less being used to de-ice roads as
winters have been milder the past few years. However, in 2000 and presently, the chloride
content in all areas was over 300-400ppm, which has known to cause problems with
corrosion and increase the freeze/thaw cycles. (See Table 5 for data and calculation.)

2. Corrosion currents of rebar have increased on both sides of the bridge since the year 2000,
when the MCI-2000 treated side had very low corrosion currents, an average of 0.013
PA/cm2, approximately 40% below readings taken on control side (average of 0.022
PA/cm2). These reading were taken in cold weather, but the 2007 readings were taken when
it was warmer. It hadnt been raining, but areas were wetted very well before measurements
were taken. The MCI-2000 treated side had an average of 0.21PA/cm2 and the control side
had as average of 0.34 PA/cm2; giving the MCI-2000 treated side corrosion currents still
approximately 40% lower. (Data is presented in Table 6.)

3. In two out of three locations on the MCI treated areas of bridge, the corrosion rate values
were much lower than the control, showing the effectiveness of the MCI inhibitor. Only the
SW (control) portion of the bridge had corrosion rate readings that would be considered an
Project #07-151-1425 Page 4 of 14 December 6, 2007
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421
active (although low level) versus the other 5 passive corrosion levels. Figures 1 and 2 show
the location of rebar and readings, as well as the average half-cell readings, corrosion rates
and concrete resistivities for both the control and MCI treated sides. Raw data from the
GalvaPulse measurements of the bridge is included in Tables 8 and 9.

4. The concrete on the 21 year old bridge deck overlay showed alkalinity measurements
between 1320 to 1680mg/L. The areas that had been treated with MCI show higher amounts,
which can indicate the presence of MCI and resistance to carbonation. (See Table 10 for raw
data.)

5. The resistivities measured by the Gecor 6 in 2000 ranged from 100 kohm.cm to 600 kohm.cm.
In 2007, the range was 36 kohm.cm to 80 kohm.cm. This shows in increase in possible
corrosion which is consistent in the rise of other parameters measured such as Cl-, Corrosion
current, and corrosion rates. (See Table 12.)

6. The Average Half-Cell Potential versus Year (shown in Figure 3) and the Average Corrosion
Rate versus Year (shown in Figure 4) show MCI treated side lower than control except for
the first reading taken after the repair. It is important to note that three different instruments
have been used for these measurements and that Tables 1 through 3 should be used to
interpret the values. (A summary of half-cell potentials can be found in Table 11 and a
summary of resistivity measurements can be found in Table 12.)

References:
1) Germann Instruments, Inc., GalvaPulse TM GP-5000 Instruction and Maintenance Manual,
2005

2) Andrade, C., Fullea, J., Alonso, C., The Use of the Graph Corrosion Rate-Resistivity in the
Measurement of Corrosion Current, International Workshop MESINA, Instituto Eduardo
Torroja, Madrid, Spain, 1999.

3) Kosmatka, Steven and Panarese, William, Design and Control of Concrete Mixtures
Thirteenth Edition, Portland Cement Association, Skokie, Illinois, 1994 rev. pp. 72.

4) Thomas, M.D.A. and Bentz, E.C., Life-365 Computer Program for Predicting the Service
Life and Life-Cycle Costs of Reinforced Concrete Exposed to Chlorides. University of
Toronto, Toronto, Canada, April 21, 2000, pp. 9.

Project: 07-151-1425
Est. Project Cost: 25 hours
For: Cortec Corporation
From: Andrea Hansen
Jessi Jackson
Sara Johnson
Brian Benduha

Date: November 30, 2007

cc: Boris Miksic


Anna Vignetti
Art Ahlbrecht
Rita Kharshan
Project #07-151-1425 Page 5 of 14 December 6, 2007
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Corporation is strictly prohibited.

422
Figure 1: Location of Rebar on Randolph Street Bridge
Eastbound Lane = Control; Westbound Lane = MCI Treated
(Note: this chart has been flipped from previous report so N is on top)

CURB
LOCATION 1 (MCI) LOCATION 2 (MCI) LOCATION 3 (MCI)
NORTH 35E

WEST BOUND TRAFFIC MCI-2000

SOUTH 35E
EAST BOUND TRAFFIC CONTROL

LOCATION 5 (Control) LOCATION 4 (Control)


LOCATION 6 (Control)

CURB

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423
Figure 2: Randolph Street Bridge Half-Cell Potential, Corrosion Rate, Resistivity, and Chloride Results
Eastbound Lane = Control; Westbound Lane = MCI Treated
(Note: this chart has been flipped from previous report so N is on top)

CURB
LOCATION 1 (MCI) LOCATION 2 (MCI) LOCATION 3 (MCI)

-104 mV (<10% probability of corrosion) -101 mV (<10% probability of corrosion) -302 mV (50% probability of corrosion)
2.42Pm/year (passive condition) 2.53 Pm/year (passive condition) 2.29 Pm/year (passive condition)
62 k:xcm (low corrosion rate) 65 k:xcm (low corrosion rate) 66 k:xcm (low corrosion rate)

SOUTH 35E
WEST BOUND TRAFFIC MCI-2000
NORTH 35E

EAST BOUND TRAFFIC CONTROL

LOCATION 6 (Control) LOCATION 5 (Control) LOCATION 4 (Control)


-85 mV (<10% probability of corrosion) -399 mV (>90% probability of corrosion) -112 mV (<10% probability of corrosion)
3.86Pm/year (passive to low corrosion) 1.83Pm/year (passive condition) 5.15 Pm/year (moderate corrosion)
70 k:xcm (low corrosion rate) 42 k:xcm (moderate to high corrosion rate) 36 k:xcm (moderate to high corrosion rate)

CURB

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424
Figure 3: Average Half-Cell Potential versus Year

MCI
CONTROL Average Half-Cell Potential (mV)
1980 1985 1990 1995 2000 2005 2010

-110
Ecorr (mV)

-160

-210

-260

-310
Year

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425
Figure 4: Average Corrosion Rate versus Year

25.000

MCI LP3
20.000 Control LP3
MCI GeCor 6
Control Gecor 6
MCI GalvaPulse
15.000
Control GalvaPulse

10.000

5.000

0.000
1990 1995 2000 2005 2010
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426
Table 5. Cl content in lbs/yd3
MCI Side (Average) Control Side (Average)
Depth (0-1) (1-2) (2-3) (0-1) (1-2) (2-3)
2007 11.7 1.0 2.6 20.0 7.4 2.3
2000 11.7 1.6 1.3 17.2 6.2 2.4
1992 6.5 1.1 1.9 9.5 3.5 2.5
1991 3.5 0.0 0.7 7.7 2.5 1.9

Calculation for Time until Chloride Threshold of 0.4wt% (of cementious materials) is Reached
Control
2.3 lbs/yd3 chlorides at 2 21 years after overlay was placed. 836 lbs/yd3 of cement in mix
2.3/836 *100 = 0.28% Cl- by weight of cement in 21 years
0.28%/21 = 0.013%Cl- per year *30 years =0.4% Cl-
1986+30=2016 (expected year chloride threshold will meet 0.4wt% in control concrete.)

MCI
2.6 lbs/yd3 chlorides at 2 21 years after overlay was placed. 836 lbs/yd3 of cement in mix
2.6/836 *100 = 0.3% Cl- by weight of cement in 21 years
0.3%/21 = 0.014% Cl- per year *27 years =0.4% Cl-
1986+27=2013 (expected year chloride threshold will meet 0.4wt% in MCI concrete.)

Table 6. Corrosion Current using GalvaPulse, PA/cm2


MCI-2000 CONTROL
NW NC NE SW SC SE
Rebar # Average Average Average Rebar # Average Average Average
1 0.164 0.196 0.127 1 0.345 0.129 0.419
2 0.235 0.235 0.109 2 0.778 0.151 0.268
3 0.180 0.177 0.205 3 1.008 0.156 0.292
4 0.210 0.204 0.241 4 0.371 0.156 0.341
5 0.193 0.260 0.261 5 0.294 0.180 0.345
6 0.202 0.237 0.284 6 0.314 0.172 0.346
7 0.200 0.232 7 0.321
Average 0.20 0.22 0.21 Average 0.52 0.16 0.33

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427
Table 7. Rate of Corrosion using GalvaPulse, Pm/year

MCI CONTROL
NW NC NE SW SC SE
Rebar # Average Average Average Rebar # Average Average Average
1 1.901 2.276 1.477 1 3.999 1.500 4.866
2 2.730 2.726 1.267 2 9.019 1.755 3.107
3 2.089 2.048 2.376 3 11.690 1.812 3.384
4 2.439 2.369 2.798 4 4.305 1.805 3.956
5 2.242 3.016 3.025 5 3.408 2.089 3.998
6 2.345 2.745 3.296 6 3.642 1.998 4.014
7 2.315 2.687 7 3.719
Average 2.29 2.53 2.42 Average 5.15 1.83 3.86

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428
Table 8. GalvaPulse Measurements for Control Treated Side of Bridge
SW rebar 19mm area 5659 current 19
point 17 27 37 47 57 67
ecorr -83.76 -127 -153.7 -120 -82.82 -68.32
Icorr 1.0982 0.3803 0.6393 0.3973 0.4059 0.3292
resistance 7.8 8 7.6 8.6 8.5 8.9
Corr Rate 12.73912 4.41148 7.41588 4.60868 4.70844 3.81872
point 18 28 38 48 58 68
ecorr -78.14 -90.07 -87.27 -83.76 -68.08 -69.95
Icorr 0.3527 0.3655 0.2171 0.2041 0.2198 0.2449
resistance 14 12 14 13 12 13
Corr Rate 4.09132 4.2398 2.51836 2.36756 2.54968 2.84084
point 19 29 39 49 59 69
ecorr -71.36 -58.49 61.53 -59.42 -44.92 -66.68
Icorr 0.1956 0.1359 0.1788 0.1915 0.3147 0.1991
resistance 16 16 15 16 13 13
Corr Rate 2.26896 1.57644 2.07408 2.2214 3.65052 2.30956
point 110 210 310 410 510 610
ecorr -74.16 -72.29 -75.1 -72.99 -68.55 -78.84
Icorr 0.1695 0.1488 0.2232 0.2288 0.1287 0.1872
resistance 14 17 15 14 12 15
Corr Rate 1.9662 1.72608 2.58912 2.65408 1.49292 2.17152
SC rebar 19mm area 5659 current 39
point 15 25 35 45 55 65 75
ecorr -246.3 -288 -318.4 -360.7 -288.4 -295 -282.8
Icorr 0.1848 0.2243 0.2236 0.1984 0.2067 0.1946 0.1988
resistance 8 8.9 7 5.1 6.6 8.3 10
Corr Rate 2.14368 2.60188 2.59376 2.30144 2.39772 2.25736 2.30608
point 16 26 36 46 56 66 76
ecorr -356.3 -362.4 -389.3 -396.8 -471.2 -442.4 -409.2
Icorr 0.1852 0.2099 0.1945 0.1768 0.2471 0.1952 0.2334
resistance 8.3 9.1 7.6 8.4 6 8.7 11
Corr Rate 2.14832 2.43484 2.2562 2.05088 2.86636 2.26432 2.70744
point 17 27 37 47 57 67 77
ecorr -348.3 -387.6 -427 -426.7 -405 -401.2 -392.8
Icorr 0.2132 0.1221 0.1413 0.2302 0.2129 0.2094 0.2166
resistance 10 12 11 6.2 8.1 8.9 10
Corr Rate 2.47312 1.41636 1.63908 2.67032 2.46964 2.42904 2.51256
point 18 28 38 48 58 68 78
ecorr -361.4 -387.6 -406.1 -382.3 -380.9 -359.3 -333.4
Icorr 0.1478 0.143 0.1678 0.1122 0.1471 0.1705 0.1521
resistance 12 10 6.3 12 12 12 17
Corr Rate 1.71448 1.6588 1.94648 1.30152 1.70636 1.9778 1.76436
SE rebar 19mm area 5659 current 39
point 14 24 34 44 54 64 74 84
ecorr -28.54 -43.75 -58.49 -72.99 -82.59 -35.09 -18.95 -5.147
Icorr 0.6206 0.5476 0.4054 0.5968 0.524 0.2966 0.4428 0.349
resistance 6.9 7.5 7.6 8.4 8.4 9.3 8.3 8.100
Corr Rate 7.19896 6.35216 4.70264 6.92288 6.0784 3.44056 5.13648 4.0426
point 15 25 35 45 55 65 75 85.000
ecorr -174.3 -193.2 -128.4 -91.71 -80.95 -88.2 -83.06 -91.950
Icorr 0.2649 0.5281 0.3879 0.2811 0.8402 0.3523 0.1732 0.263
resistance 9.4 7.6 10 12 11 11 12 11.000
Corr Rate 3.07284 6.12596 4.49964 3.26076 9.74632 4.08668 2.00912 3.05196
point 16 26 36 46 56 66 76 86.000
ecorr -190.6 -154.4 -125.4 -111.8 -110.9 -98.26 -97.33 -100.300
Icorr 0.2925 0.2117 0.3423 0.1697 0.2508 0.2541 0.1423 0.295
resistance 10 12 9.5 11 10 12 16 12.000
Corr Rate 3.393 2.45572 3.97068 1.96852 2.90928 2.94756 1.65068 3.42548

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429
Table 9. GalvaPulse Measurements for MCI-2000 Treated Side of Bridge
NW rebar 19mm area 5659 current 34
point 11 21 31 41 51 61 71
ecorr -21.75 -54.51 -137.8 -138.9 -109.4 -47.02 -19.18
Icorr 0.1085 0.1443 0.1256 0.1816 0.1 0.1355 0.1241
resistance 11 9.2 11 7.5 12 11 10
Corr Rate 1.2586 1.67388 1.45696 2.10656 1.16 1.5718 1.43956
point 12 22 32 42 52 62 72
ecorr -59.89 -35.56 -48.9 -65.04 -68.32 -62.47 -115.1
Icorr 0.0961 0.1708 0.1224 0.0977 0.0829 0.2162 0.0778
resistance 15 8.8 12 11 8.9 8.9 12
Corr Rate 1.11476 1.98128 1.41984 1.13332 0.96164 2.50792 0.90248
point 13 23 33 43 53 63 73
ecorr -112.3 -97.8 -68.78 -70.42 -81.89 -92.41 -102.7
Icorr 0.074 0.1302 0.0829 0.0828 0.1079 0.1304 0.1215
resistance 18 13 15 16 13 12 14
Corr Rate 0.8584 1.51032 0.96164 0.96048 1.25164 1.51264 1.4094
point 14 24 34 44 54 64 74
ecorr -183.2 -110.4 -69.95 -82.82 -74.16 -88.44
Icorr 0.1237 0.1006 0.1134 0.1677 0.1654 0.2121
resistance 11 10 10 10 9.6 7.7
Corr Rate 1.43492 1.16696 1.31544 1.94532 1.91864 2.46036 0
NC rebar 19mm area 5659 current 39
point 11 21 31 41 51 61
ecorr -82.82 -108 -207.7 -193.9 -143.6 -164.2
Icorr 0.2269 0.2042 0.2297 0.2772 0.2794 0.3849
resistance 11 11 10 8.9 10 9.2
Corr Rate 2.63204 2.36872 2.66452 3.21552 3.24104 4.46484 0
point 12 22 32 42 52 62
ecorr -65.27 -91.95 -102.9 -110.2 -140.3 -157.6
Icorr 0.2152 0.3079 0.1957 0.2112 0.3639 0.3314
resistance 12 7.9 12 12 10 8.9
Corr Rate 2.49632 3.57164 2.27012 2.44992 4.22124 3.84424 0
point 13 23 33 43 53 63
ecorr -73.93 -48.66 -50.53 -68.08 -68.32 -101.7
Icorr 0.1946 0.1805 0.2039 0.2226 0.1734 0.3362
resistance 16 16 16 11 15 13
Corr Rate 2.25736 2.0938 2.36524 2.58216 2.01144 3.89992 0
NE rebar 19mm area 5659 current 39
point 11 21 31 41 51 61 71
ecorr -193.7 -236 -302 -334.8 -354.9 -398.9 -429.8
Icorr 0.2078 0.1198 0.3638 0.5317 0.2463 0.5523 0.2574
resistance 11 12 9.3 7 9.4 7.6 8.5
Corr Rate 2.41048 1.38968 4.22008 6.16772 2.85708 6.40668 2.98584
point 12 22 32 42 52 62 72
ecorr -281.9 -288.9 -320.5 -341.8 -375 -401.9 -432.6
Icorr 0.1932 0.2854 0.7807 0.4434 0.9579 0.6074 0.4858
resistance 8.6 11 9.9 8.2 6.8 7.2 6.8
Corr Rate 2.24112 3.31064 9.05612 5.14344 11.11164 7.04584 5.63528
point 13 23 33 43 53 63 73
ecorr -105.9 -124.9 -184.3 235.1 -331.3 -361.2 -435.8
Icorr 0.1474 0.0858 0.1639 0.1352 0.8829 0.8293 0.6082
resistance 18 23 13 16 5.7 5.1 6.4
Corr Rate 1.70984 0.99528 1.90124 1.56832 10.24164 9.61988 7.05512

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430
Table 10. Alkalinity Results

MCI Treated Concrete Control Concrete


Alkalinity as Concrete Alkalinity as
Concrete # of Average, # of Average,
CaCO3 ppm (# Sample CaCO3 ppm (#
Sample ID drops ppm drops ppm
of drops x20x6) ID of drops x20)
N.C. 0-1" 12 1440 S.C. 0-1" 11 1320
N.E. 0-1" 13 1560 1480 S.E. 0-1" 11 1320 1280
S.W. 0-
N.W. 0-1" 12 1440 10 1200
1"
N.C. 1-2" 13 1560 S.C. 1-2" 12 1440
N.E. 1-2" 13 1560 1560 S.E. 1-2" 13 1560 1520
S.W. 1-
N.W. 1-2" 13 1560 13 1560
2"
N.C. 2-3" 14 1680 S.C. 2-3" 13 1560
N.E. 2-3" 14 1680 1680 S.E. 2-3" 14 1680 1640
S.W. 2-
N.W. 2-3" 14 1680 14 1680
3"
All samples tested @ a 1:6 dilution All samples tested @ a 1:6 dilution
Table 11. Summary of Half-Cell Potentials
MCI-2000 CONTROL
NW NC NE SW SC SE
X X X X X X
Average Average Average Average
Average Average
-99 -66 -191 -86
-355 -145
-93 -78 -211 -96
-395 -141
-107 -101 -258 -111
-423 -118
-125 -112 -298 -99
-427 -117
-111 -111 -342 -77
-411 -115
-101 -138 -385 -41
-402 -91
-94 -429 -381 -86
-78
Average of each horizontal bar
-104 -101 -302 -85 -399 -112
Overall Average
-169 -198

Table 12. Summary of Resistivity Measurements


MCI-2000 CONTROL
NW NC NE SW SC SE
X X X X X X
Average Average Average Average Average Average
67 65 90 51 70 55
66 83 79 64 62 38
59 70 68 74 50 33
49 53 62 56 50 30
64 68 50 63 36 37
63 47 47 41 44
70 67 36
62 65 66 70 42 36
Average Average
64 50

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