CONSEC 2016

Politecnico di Milano
Lecco, Italy
Date: July 02, 2015
Contact Author: Pascal COLLET, pascal.collet@total.com

Title: Concrete porosity reduction by Colloidal Silica Nano

technology
Authors: Pascal COLLET1, A. Brent Rollins2, Valery ANDRES3

1 TOTAL SA, Paris, FRANCE

2 Protecht Consulting, Chattanooga, Tennessee, USA

3 SCP France, Limours, FRANCE

Keywords: Colloidal silica, Nano technology, Porosity, Reliability, Durability

Abstract. TOTAL E&P are facing several different concerns regarding the durability of
marine structures and concrete infrastructure exposed to H2S. LNG Concrete outer tanks,
marine facilities such as quays, jetties, and water intakes and outfalls have shown
deterioration of reinforced concrete due to chloride or sulfate ingress leading to corrosion. As
TOTAL assets are all over the world, concrete quality is very dependent on local conditions
and available materials close to our site. To mitigate this risk to our operation, TOTAL has
begun testing several solutions to reduce the porosity and permeability of concrete.

This paper begins with an overview of the concrete degradation process in Oil&Gas context,
followed by an in-depth study of protection against chemical ingress by hydrophobic
impregnation with a state-of-the-art Nano technology. Cases study on concrete slab
application in 2014 and 2015 is included.

Concrete structure for Oil&Gas industry

TOTAL E&P assets for any kind of production - oil, gas or solar - is mainly composed of
process plant, storage tanks and export facilities (Fig 1).
Figure 1: typical plant layout with process, storage and offloading facilities

From Latin America to West Africa, from the Atlantic to the North Sea, we discover and
develop the oil and gas resources (1). As export is done usually by boat, oil tanker or LNG
carrier, assets are closer to the sea. Infrastructures are facing several different concerns
regarding the durability of marine structures such as severe storm, long term chloride ingress,
ice pressure and abrasion. Marine facilities such as quays, jetties, and water intakes and outfalls
have shown deterioration of reinforced concrete due to chloride or sulfate ingress leading to
corrosion.
As TOTAL assets are all over the world, concrete quality is very dependent on local
conditions and available materials close to site. Hydrocarbon products may content H2S and
TOTAL have to address this issue with a high porosity concrete level. On other target for LNG
storage tank will be to improve the secondary containment of LNG tank made in concrete.

.
Figure 2: Typical LNG full containment tank with concrete outer tank.

In accordance with all standard for full containment, the first liner in welded steel plates is
quite difficult to check at 100% for gas tight. That why, TOTAL try to improve the concrete as
a secondary gas tight barrier.
To mitigate this risk to our operation, TOTAL has begun testing several solutions to reduce
the porosity and permeability of concrete.
Colloidal Nano-Silica as Chemical Ingress Protection

Colloidal Nano-Silica (CNS) has been in use since the 1970s and was originally developed
to reduce crude oil seepage from capped undersea wells. Since then, efforts have been made to
introduce CNS to conventional Portland cement concrete in various ways including both as an
integral admixture and as a post-initial set spray application. Recent academic research has
demonstrated the utility of CNS in Portland cement concrete, showing effects in reducing
chloride diffusion rates, decreasing drying shrinkage, increasing surface resistivity, and
increasing compressive strength. The study of the addition of CNS to concrete and cement
mortars is a fairly recent contribution of the research establishment. CNS consists of small
particles consisting of an amorphous SiO2 core with a hydroxylated surface and are insoluble
in water, (Bjornstrom & al.[2]).
The effectiveness of CNS begins with its particle size. The size of the particles is typically
between 1 and 500 nm, small enough to remain suspended in a fluid medium without settling
(Ltifi et. al. [9]). CNS is a stable dispersion of Nano-sized particles of amorphous silica. CNS
particles consist of a charged nucleus that is surrounded by an extended diffuse ionic
atmosphere. Colloids consist of particles with a size sufficiently small ( 1 m) not to be
affected by gravitational forces but sufficiently large ( 1 nm) to show marked deviations from
the properties of true solutions (Santos, et. al. [14]).
The main components of hydrated Portland cement pastes are Calcium Silicate Hydrate (C-
S-H) gel and Portlandite (calcium hydroxide). C-S-H gel occupies about 50-60% of the
hydrated paste by volume and is considered to be the major contributor to the behavior of the
paste. Calcium hydroxide makes up a significant amount of the hydrated cement paste (Nelson
& Young [11]). Pozzolanic additives contribute to strength enhancement by producing
additional C-S-H from calcium hydroxide. The reactions involved are complex, and are related
to a number of factors such as particle size and dispersion, chemical composition, minerology,
and morphology among other things (Du & Pang [4]).
CNS is an excellent source of Pozzolanic reaction, with its small particle size and surface
chemistry making it among the most reactive pozzolan sources known. CNS reacts with
calcium hydroxide in the pore space to form secondary C-S-H, reducing the size of capillary
voids and pores, which leads to a denser and more homogeneous structure, greatly improving
the mechanical properties of the concrete. Colloidal silica has much more surface area than
silica fume, making it able to achieve a higher level of reactivity when concrete is treated with
equal amounts of each (Hou, et. al. [6]). Multiple studies have shown that even a small addition
of colloidal silica can improve the mechanical properties of cementitious materials
(Kontoleontos, et. al. [|8]). Rashad's meta-analysis of CNS in 2014 is a comprehensive
overview of the research to date, demonstrating gains in compressive strength and reductions
in permeability and drying shrinkage. These gains in hardened properties may appear to be
hyperbole at first glance, but when it is considered that CNS is primarily reducing void space,
it follows naturally that nearly all hardened properties of concrete are affected in some way.

Reaction Details

There are two principal reactions that take place in colloidal silica treated concrete. First,
if the colloidal silica is added early enough, it can impact the primary C-S-H forming phase.
Second, the Pozzolanic reaction occurs in which calcium hydroxide is converted to C-S-H.
Calciumsilicatehydrate (CSH) is the primary hydration product and binding phase in
Portland cement concrete. The dashes indicate that no particular composition is assumed.
Instead it suggests a generic name for any amorphous or poorly crystalline calcium silicate
hydrate. A tremendous amount of research has been conducted into the nature of C-S-H,
including instrumentation such as X-ray diffraction, NMR spectroscopy, X-ray absorption
spectroscopy, TEM and SEM.
Colloidal silica affects the structural makeup of the silicate anion network. Colloidal silica's
ultrafine, high surface area particles are able to fill the microscopic voids between cement
particles. At early ages, the colloidal silica acts as nucleation sites or "seeds" for cement
hydrates, accelerating hydration. Nucleation is defined by Bullard et. al. [3] as "initiates the
precipitation of solids heterogeneously on solid surfaces or homogeneously in solution, when
the bulk free energy driving force for forming the solid outweighs the energetic penalty of
forming the new solidliquid interface." During the curing phase, the previously mentioned
Pozzolanic activity takes place, converting calcium hydroxide to C-S-H. However, the reaction
doesn't stop there. Colloidal silicas have been shown to improve the structure of existing C-
S- H by allowing it to precipitate as a small, dense, morphology. This change is due to the fact
that the colloidal silica modifies the internal structure of C-S-H by increasing the length of the
silicate chains, leading to a more dense paste structure (Kontoleontos, et. al. [8]).
Hydration of cement can be accelerated with the addition of colloidal silica. During the early-
age nucleation phase mentioned above, H2SiO2 forms and reacts with the available Ca2 to form
C-S-H particles that are distributed in the pore water, serving as seeds for the growth of the
more compact C-S-H phase. With the use of colloidal silica, the formation of C-S-H is no
longer limited to the cement grain surface alone, but also takes place in pore space (Hou, et. al.
[6]).

Laboratory Experimentation

For laboratory experimentation, a spray-applied CNS was chosen for study due to the lack
of information available in the literature regarding this method of utilization. The product used
is designed to be applied at either approximately the time of initial set of the concrete, or later
as a remediation aid to existing concrete. For laboratory experimentation, all samples were
treated at approximately the time of initial set while ensuring that all bleed water had evaporated
from the surface of samples. Samples were treated according to the manufacturer's
recommended practice, which is to spray to rejection. Rejection is defined by the manufacturer
as "product is still ponded on the surface at the end of fifteen minutes." Using this methodology,
some concretes must be treated multiple times to achieve the saturated effect. Spray-applied
CNS is theorized to be effective because of its small particle size, allowing it to penetrate deeply
into capillary voids.

Chloride Ponding

Chloride ponding tests were run in accordance with AASHTO [1]. The mix design utilized
a range of w/cm ratios with 25% class F fly ash by weight of cementitious materials. Specimens
were cast in 150 x 300 mm cylinder molds, with edges sealed with silicone. The chloride
solution was topped off every three days on average. From those tests, chloride diffusion rates
were calculated using second order Fickian diffusion. Each set of tests was compared to an
untreated control that did not receive a CNS spray treatment.

Duration of Ponding, Untreated Treated Improvement

3% NaCl Solution, Performance Performance (%)
days (Mean D, m2/s) (Mean D, m2/s) (untreated D -
 90 3.90E-12 1.10E-12 255%
90 3.00E-12 8.00E-13 275%
90 1.20E-11 3.40E-12 253%
90 8.10E-12 2.80E-12 189%
90 8.30E-12 2.70E-12 207%
90 6.20E-12 2.00E-12 210%
90 5.80E-12 1.90E-12 205%
Table 1

The results presented in table 1, above demonstrate a significant reduction in chloride

diffusion behavior of the CNS-treated concrete compared to the untreated controls.

Non-Steady State Chloride Migration Testing

During the course of experimentation, it was decided that a non-steady state testing regime
could lead to rapid determination of chloride migration in treated and untreated specimens. The
Nord Test Standard 492 utilizes NaCl and NaOH solutions in combination with an applied
voltage to electrochemically introduce chlorides to a concrete specimen. After the treatment
period (usually 24 hours), the specimen is split and silver nitrate solution is used to precipitate
chlorides, resulting in a measurable "reaction front" (Fig.3).

Figure 3: Precipitated chlorides after treatment with silver nitrate

Sample Depth of Chloride Avg. % Reduction from

Penetration Control
(mm) (Control-Exp)/Exp
Control 1 14.1
Control 2 13.5
Control 3 12.1
Average of 3 Samples 13.2 ---
Exp 1 9.2
Exp 2 9.7
Exp 3 9.1
Average of 3 Samples 9.3 41.9 %

Table 2
 Although NT-492 has been demonstrated to be a good indicator of chloride permeability,
the test method is not yet widely accepted in the United States as a replacement for chloride
ponding or rapid chloride permeability.

Life Cycle Corrosion Modeling

Several software models for predicting service life of concrete exposed to chlorides have
been developed. The approaches used by these models differed from each other considerably,
leading to the Strategic Development Council of the American Concrete Institute (ACI)
identifying the need to develop a standard model. A workshop sponsored by the National
Institute of Standards and Technology (NIST), ACI, and ASTM was held in 1998, "Models for
Predicting Service Life and Life-Cycle Cost of Steel-Reinforced Concrete." [9] At this
workshop the decision was made to develop a standard model under the jurisdiction of ACI
Committee 365 "Service Life Prediction". The model was developed utilizing normal ACI
protocol and consensus procedures for producing committee documents. Life 365 was born, a
collaborative effort between national standards bodies and industry.
The service life (in years) produced by the Life 365 software assumes that the primary mode
of degradation of concrete is by chloride ingress attacking the rebar. The calculations involved
are based on 1st and 2nd order Fickan diffusion models. An initial time period to rebar exposure
to chlorides is predicted based on the diffusion coefficient and the depth of cover. The
propagation time is then calculated to see how long the rebar will take to corrode enough to
affect the structural properties of the concrete. Using a stochastic approach, Life 365 estimates
the distribution of possible service life for a given concrete mix and corrosion protection
strategy (Ehlen, [7]).
For the example Life 365 results presented below in Table 3, the average of the chloride
diffusion coefficients were used for both the untreated and treated concretes. Rebar cover was
set at 75 mm, and the exposure conditions for the Port of New Orleans "marine spray zone"
were set. Total slab thickness was set at 250 mm, with a 25% fly ash mix at a 0.42 w/cm ratio.
Defaults were left in place for corrosion propagation period (6 years) and allowable chloride
concentration by weight of concrete (0.05%). See the software-generated report in Appendix
A, "Supplementary Materials".

Mix Mean D (m2/s) Initial Corrosion Calculated Service

Untreated 0.42 w/cm 6.76E-12 32 years 38 years
Treated 0.42 w/cm 2.10E-12 107 years 113 years

Table 3

Field applications of the technology

As a new comer in the civil engineering works under its colloidal form the SCP technology
wants to show in various cases the pertinence of its use to protect concrete structures.
The technology show benefits not only for its inner performance but also mercy to its ease
of application, as shown below.

Concrete jetty protection application

Location: GUINEA GULF

Area: 1.000 sqm.
Situation: sea shore
 Structure highlights: 3.5x1.75m slabs poured on shore then placed on metallic beams
Technical requirements: underneath protection from ocean splash, on scaffoldings
and under influence of the ocean swell. Use of electrical supply was forbidden which
conducted to a low pressure application with back pack hand sprayer.

Figure 4: under and above slab of Warf

Details of intervention: two half days by two trained applicators. A survey is

programmed as parts of the structure have been left untreated to let a comparison
possible for the future.

No delay, no electricity, careless of the temperature from 0 to 40C (under very high
temperature, a wetting of surfaces to be treated avoids evaporation phenomena). As a non-toxic
product SCP can be used in any area or ambient.
Chloride ingress tests are plan on 2016.

Old concrete slab waterproofing

Location: France
Area: 100 sqm.
Situation: Land.
Structure highlights: 7x7m concrete armored slabs poured in 1968 strongly damaged
by aerial aggression.
Technical requirements: the concrete must be treated to pass a standard test to be
qualified under the Oil & Gas storage facility use.
Figure 5: concrete slab after treatment

Details of intervention: Applied in 90 with an airless gun. Test passed, concrete

waterproofed. One of the benefits for the customer is the FastTrack application and
other one is the capacity to walk and travel on the treated concrete afterwards.

Permeability tests (according to NF X30-420) were done before and after SCP treatment.
The area chosen showed major surface cracks and represented the worst quality of concrete
found. The results show a decrease of permeability by a factor of 50.
Note that the device used to proceed couldnt seal the sides regarding its genuine conception,
by getting 10 cm into the matrix of the concrete, the device was sealed onto it but showed
superficial water displacement on the top of the concrete, outside the area of the chamber.
Usually the DIN 1048, water permeability under pressure is the laboratory test method specified
to show permeability of protected concrete. The cylinders (drilled from the ground) are place
into a proven sealed chamber. Water is applied only on the surfaces treated to show real
waterproofing.SCP never failed this test, on new as very old concrete.

Old concrete walls remediation

Location: FRANCE
Area: 2 sqm to proceed to testing.
Situation: South of France.
Structure highlights: 1938 armored concrete underground cavern structure
contaminated by crude oil, decontaminated, very porous with structural degradation.
Walls thickness varies from 2 to 3 meters.
Technical requirements: the concrete must pass several test to comply with specific
needs of the customer, as EN 12390-8/ DIN 1048, specific gravity etc.
Details of intervention: Application with a handy airless gun and test passed. Work
still in its pre specification agenda. SCP is asked to offer a double skin protection to
the concrete as a backup technology. It is also valued as a primer to avoid pinholes
at time of application of a heated polymer membrane.

Conclusions
 Based on these trial tests on several assets and the feedback from drilling department
regarding the colloidal technology, TOTAL will continue to improve and test this solution to
reduce the overall porosity of the concrete.
One of interest of this technology is also on how is deployed and it looks like easy to treat
when its required. Total expect to avoid to destroy and rebuild where the main interest of the
concrete is to be watertight and durable.

References

[1] AASHTO (American Association of State Highway Transportation Officials, 2002)

"Standard Method of Test for Resistance of Concrete to Chloride Ion Penetration."
AASHTO T-259. Washington, DC.
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effects of colloidal nano-silica for beneficial calcium-silicate- hydrate formation in
cement. Chemical Physical Letters 392, 242-248.
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