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Construction and Building Materials 132 (2017) 578–590

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Construction and Building Materials


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Review

A review on concrete surface treatment Part I: Types and mechanisms


Xiaoying Pan a, Zhenguo Shi b, Caijun Shi a,⇑, Tung-Chai Ling a, Ning Li a
a
College of Civil Engineering, Hunan University, Changsha 410082, China
b
Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark

a r t i c l e i n f o a b s t r a c t

Article history: The application of surface treatments in concrete has been widely investigated over the past decades.
Received 22 May 2016 Surface treatment technology has become more important in concrete structures especially in preventing
Received in revised form 26 November 2016 deterioration and damage when exposed to extremely aggressive environments, and in further extending
Accepted 3 December 2016
service life. This paper presents comprehensive details of four types of concrete treatments, including
surface coating, hydrophobic impregnation, pore blocking surface treatment and multifunctional surface
treatment. Additionally, the knowledge of their interaction mechanisms with cementitious substrate is
Keywords:
presented and discussed. The advantages and drawbacks of each treatment as well as the influencing fac-
Concrete
Surface treatment
tors on the protective effects of surface treatments on concrete, such as air permeability, bonding
Coating strength and cracking resistance, are also discussed. Despite decades of study, the mechanisms of many
Air permeability newly developed surface treatments remain poorly understood. A deeper understanding of the chemical
Bonding strength and physical reaction mechanisms is therefore essential, especially at micro-scale levels.
Ó 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
2. Types and mechanisms of surface treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
2.1. Surface coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
2.1.1. Traditional polymer coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
2.1.2. Polymer nanocomposite coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
2.1.3. Cementitious coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
2.2. Hydrophobic impregnation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
2.3. Pore-blocking surface treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
2.4. Multifunctional surface treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
3. Factors influencing the performance of surface treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
3.1. Air permeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
3.2. Bonding strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
3.3. Penetration depth / coating thickness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
3.4. Cracking resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
3.5. Substrate properties and application method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
4. Summary and perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587

⇑ Corresponding author.
E-mail address: cshi@hnu.edu.cn (C. Shi).

http://dx.doi.org/10.1016/j.conbuildmat.2016.12.025
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
X. Pan et al. / Construction and Building Materials 132 (2017) 578–590 579

1. Introduction knowledge of the interaction between surface treatment agents


and cementitious substrate. The second part reviews and compares
Durability problems of concrete structures usually begin with the effects of surface treatments and their durability performance
the deterioration of materials. Although the deterioration of mate- [11]. This paper provides a comprehensive review of the research
rials does not cause immediate safety problems at the beginning, it and development of surface treatments over the past 30 years. In
gradually creates a potential danger for the whole structure. addition, some insights and suggestions for further research are
Extensive research has been conducted over the last four dec- presented.
ades due to the economic impact caused by the durability problem.
Several methods to provide better and durable concrete or rein-
forced concrete structures have been proposed. The most common 2. Types and mechanisms of surface treatment
strategy adopted is to delay the degradation process of reinforced
concrete by decreasing the porosity by reducing the water-to- According to the chemical composition of surface treatment
cement ratio and adding nanoparticles. However, this method agents, they can be classified into two categories: inorganic and
has two main drawbacks: firstly, the protection might be sufficient organic treatments. Organic surface treatments are the most
in highly aggressive environments, such as marine, saline and alka- commonly-used treatments because of their good protective effect.
line land, and frigid area; and secondly this method has generally However, there are concerns over their poor fire resistance, ease to
led to overdesigning the whole structure [1–4]. Thus, several crack and detach, limited service life, and difficulty to be removed
approaches which are more economical are applied to provide after losing their protective effects [12,13]. The most common inor-
additional protection for materials against degradation [5–8]. They ganic surface treatment is sodium silicate solution (also known as
are (1) metal, epoxy resin and polymer coatings for steel rebar; (2) ‘‘waterglass”). To a much smaller extent, potassium silicates,
corrosion inhibitor; (3) electrochemical method which is usually lithium silicate, and fluosilicates have also been reported to be
used in concrete re-alkalization; and (4) concrete surface treat- used for inorganic surface treatments [3,14]. Although inorganic
ment. Among these methods, (1) and (2) cannot be used in old surface treatments have better durability performance, less
structures, and the effect of coatings for reinforced steel is a con- research has focused on this area, especially their penetration
troversial issue, because the corrosion rate increases rapidly in bro- depth and interactions with cementitious substrate.
ken areas of coatings. So far, the effect of corrosion inhibitors in In term of functions, the surface treatments are grouped into
prolonging the service life of steel bar is still unclear. Meanwhile, three types according to the EN 1504-2:2004 [15–17]: hydropho-
(3) can be used in existing structures but is relatively expensive. bic impregnation, impregnation, and coatings. However, this clas-
On the other hand, (4) concrete surface treatment has received sification does not include some newly developed surface
wider acceptance due to its effectiveness in preventing the ingress treatments. Thus, all the surface treatments discussed in this paper
of aggressive substances. are divided into four major groups: surface coating, hydrophobic
Since 1986, a hydrophobic agent named isobutiltrimetoxisilane impregnation, pore blocking surface treatment, and multifunc-
(100% pure) has been used on bridges in the United Kingdom to tional surface treatment. The following sections describe these four
prevent chloride penetration. Agencies in America and the Depart- types of treatment in detail.
ment of Transportation in Germany use hydrophobic agents on
bridges subjected to chloride penetration [9]. A detailed review
2.1. Surface coating
of the performances of surface treatment was presented by Bash-
eer et al. [10]. However, a lot of progress has been made in under-
Surface coating forms a continuous polymer film which acts as a
standing the mechanisms of surface treatment agents which have
physical barrier to prevent corrosive substances from penetrating
been commercially available for a long time. Moreover, a new gen-
into cementitious substrate [5,16,18]. There are several types of
eration of surface treatment agents has emerged over the last
surface coatings, including traditional polymer coatings, polymer/-
20 years.
clay nanocomposite coatings and cementitious coatings. Tradi-
This review includes two parts. This first part explores the clas-
tional polymer coating and polymer/clay nanocomposite coatings
sification, mechanisms and factors influencing the surface treat-
form a dense polymeric film with a thickness of about 0.1–1 mm
ment performances by summarizing the current state of
on the concrete surface, whereas, cementitious coating acts by

Table 1
Properties of traditional polymer coating used for concrete surface treatment.

Curing mechanism Advantages Disadvantages


Epoxy resins Low shrinkage; Low fracture energy;
[19–27] Easy to cure; Low impact on strength;
Good chemical resistance; Poor hydrophobicity
Good adhesive strength; Low thermal stability;
Easy to weathering;
Poor resistance to the initiation and
propagation of cracks
Acrylic [28–33] Physically drying High resistance to hydrolysis Low bond strength;
and ultraviolet radiation; Poor ductility;
good alkali resistance Generally not applied for constant immersion in
water or soil
Polyur-ethane Excellent resistance to Poor resistance towards mechanical strains and
[34–41] weathering; self-healing; no deformation and/or degradation at high temperatures
shrinkage
580 X. Pan et al. / Construction and Building Materials 132 (2017) 578–590

forming a low permeability layer with a thickness of about 2– compared with virgin polymer [52]. However, research on the
10 mm. applications of polymer nanocomposite coatings in concrete struc-
tures is very limited [60,62–64]. Only a few researchers have inves-
tigated the properties of polymer/clay nanocomposite coatings on
2.1.1. Traditional polymer coatings
cementitious materials [51,65–67]. Though polymer/SiO2 and
Epoxy resins, acrylic and polyurethane are traditional protective
polymer/Al2O3 also show potential advantages in providing a bar-
coatings which have been used in the construction industry for
rier effect, their performances have not been evaluated. Natural
many years. The properties of these polymer coatings are listed
polymers like starch can be used for the preparation of nanocom-
in Table 1. Acrylic acid has good resistance to alkali, oxidation
posite materials because of their low price [56]. Their potential
and weathering, but its bonding strength and ductility are rela-
application in the concrete industry is worth investigating.
tively poor compared to epoxy resin [19]. Polyurethane coating
has better performance in protecting concrete with no shrinkage,
with high resistance to acid attack. However, it is not stable in a 2.1.3. Cementitious coatings
high alkaline environment. In addition, isocyanates which are the Polymer modified cementitious coatings are the most common
main raw materials that make up polyurethane are harmful to cementitious coatings used for concrete protection. Polymer mod-
human health. ified cementitious coatings are made with polymer (mainly acry-
The water resistance of the coated concrete is mainly related to late, polyurethane or epoxy) along with cement and aggregates
the barrier effect of the polymer coating. The kinetics of moisture (generally very fine aggregate). The addition of polymer greatly
transport in polymer coatings are usually described by Fick’s law improves the properties of strength, resilience, adhesion, chemical
[42–44]. However, the water diffusion in polymer coatings is com- resistance and impermeability of cement paste. There are four
plicated. The experimental results of Maggana et al. [45] showed main reasons why polymer modified cementitious coatings can
that water diffusion in epoxy coatings deviates from Fick’s law, provide additional protection for concrete [22]. First, the polymer
especially when the temperature is lower than 20 °C. Hence, it is forms a net structure in the hardened cement paste, which
necessary to evaluate the diffusion property of polymer coatings increases the toughness of the paste, and thus, surface micro-
at different temperatures before being applied to concrete. Accord- cracking can be reduced. In addition, the pore structure in polymer
ing to Vanlandingham et al. [46], water diffusion of polymer coat- cementitious coatings is different from ordinary cement mortar.
ings is related to two main factors. The first one is the availability Studies show that pores larger than 100 nm decrease while pores
of molecular-sized holes in the polymer, which depends on the smaller than 100 nm increase in polymer modified mortar. Third,
polymer microstructure, crosslink density, and morphology. These shrinkage can be mitigated when applying polymer-modified
three properties are functions of the degree of cure, molecular cement-based coatings. Modified cementitious coatings show good
chain stiffness, stoichiometry, and cohesive energy density of the ‘‘breathability” and considerable ‘‘crack-bridging” ability due to
coating. The second factor is the polymer-water affinity which is their low elastic modulus [18,68,69]. Furthermore, polymer modi-
related to the presence of hydrogen bonding sites along the poly- fied mortars have higher ultraviolet light (UV) resistance compared
mer chains. Due to the effect of polymer-water affinity, Fick’s law with polymer coatings [70–72]. Thus, they are strongly recom-
can only describe the beginning stage of water diffusion, but it is mended for use on cracked concrete since they can close existing
not applicable during the whole process [45,47]. cracks and maintain their protective effect for a long time
Failure patterns observed on polymer coatings/concrete sys- [18,73]. It is worth to mention that the effects of polymer modifie
tems include four types: blistering, cracking, holes and peeling cementitous are affected by the curing regimes [146].
[35,39,48–50]. Blistering indicates partial loss of adhesion result- Geopolymer can also be used as a protective coating for marine
ing from osmotic pressure. Cracking may be caused by shrinkage concrete [74–77]. There have been several attempts to use gopoly-
of coatings due to temperature change or cracking of cementitious mer as a protective coating in transportation infrastructure [78,79].
substrate. Uneven painting and osmotic pressure may cause holes It has been reported that geopolymeric coating is still in a good
and pores which greatly increase the permeability of the coating. state after 9 years of exposure in Rhode Island [80]. Geopolymer
Peeling is attributed to loss of adhesion caused by penetration of coatings show good durability even in highly aggressive environ-
aggressive substances into the substrate. In modern construction, ments. Zhang et al. [75–77] demonstrated that the use of geopoly-
coatings are usually built up of several layers to obtain a better mer coatings is more effective than the use of organic polymers,
protective effect. Furthermore, many efforts have been made by especially in salt water environments. In addition, geopolymer
researchers to improve their properties by adding various nano- has a glassy texture, and thus is graffiti resistant [78,79]. Salwa
fillers, which will be discussed in following Section 2.1.2 [19–21]. et al. [81] stated that geopolymer has a potential in fire resistant
and protective coatings for different surfaces including metal and
concrete due to their superior mechanical, chemical and thermal
2.1.2. Polymer nanocomposite coatings resistance properties. However, the shrinkage problem of geopoly-
Recently, polymer nanocomposite coatings have attracted great mer should be carefully considered, which may lead to failure of
interest in both academic research and engineering application due the coating.
to their remarkable properties over the virgin polymers. Polymer
nanocomposite coatings generally have higher strength, tensile
modulus, abrasion resistance, heat resistance, and thermal stabil-
ity. The addition of nanoparticles could reduce gas permeability
and flammability, etc. [51–57]. The incorporation of an inorganic
nanocomposite can improve the barrier properties and slow down
the degradation of polymers by increasing the diffusion path [58].
The lengthening of the diffusion path increases with tortuosity
which increases with concentration of nanocomposites and their
properties, such as aspect ratio and volume fraction [59–61]. Even
with a small dosage of nanocomposites, the gas permeability of a
polymer nanocomposite coating can be reduced by 50–500 times Fig. 1. Molecular structure of silane (a) and of siloxane (b) [144].
X. Pan et al. / Construction and Building Materials 132 (2017) 578–590 581

2.2. Hydrophobic impregnation siloxane (1.5  106–7.5  106 mm diameter) allow them to pen-
etrate efficiently into a highly dense substrate, while also making
Hydrophobic impregnation operates through penetrating con- them very volatile. Typical molecular structures of silane and silox-
crete pores, enlarging the contact angle. The surface becomes ane are shown in Fig 1. Both silane and siloxane contain an alkyl
hydrophobic when the contact angle is larger than 90°. Thus, group and several alkoxy groups [82,83]. The alkyl group can
hydrophobic impregnation can inhibit penetration of water and reduce the surface tension of the concrete substrate, while the
water-born ions, but allows water vapor to enter or exit. structure of the alkoxy group is related to how silane/siloxane
Silane, siloxane and a mixture of these two components are the bonds to the concrete surface [84]. The characteristics of alkyl
most commonly-used hydrophobic impregnation. Small molecular groups significantly influence the hydrophobicity of silane and
structures of silane (1.0  106–1.5  106 mm diameter) and siloxane. The alkyl group with higher molecular weight (e.g. iso-
butyl and n-octyl) provides a higher degree of hydrophobicity than
the lower molecular weight alkyl group (e.g. methyl and ethyl). In
addition, the structure of the alkyl group is also related to the
degree of hydrophobicity, generally having the following order:
branched structure > straight chained > cyclic structure. Thus, the
structure and size of the alkyl group also play an important role
in the resistance of silane and siloxane to deterioration in alkaline
environments. On the other hand, the characteristics of the alkoxy
group (such as, ethoxy or methoxy) are associated with the pene-
tration depth of the silane or siloxane. An investigation showed
that silane treatment not only can provide a hydrophobic surface,
but also make the substrate surface tougher [85]. Thus, silane is
also as an effective agent to prevent cracking and heal cracks smal-
ler than 0.2 mm [85]. However, there are no adequate experimen-
tal results to explain this effect.
The chemical reaction between silane and cementitious sub-
strate is shown in Fig 2. In the first step, silane hydrolysis reacts
with water or water vapor in capillary pores, and the alkoxy group
will undergo hydrolysis and form silanol groups. Then, the unsta-
ble silanol molecules will lose water and condensate into silicone
resin. Consequently, the silanol groups in silicon resin react with
hydroxyl groups in the concrete substrate through hydrogen
bonds. Finally, the silicon resin bonds to substrate during drying,
and provides a water-repellent effect. The alkalinity of the concrete
acts as a catalyst in this reaction [62].

2.3. Pore-blocking surface treatment

Pore-blocking surface treatments have been used in buildings


and highway bridges for many years [15]. They can block the cap-
illary pores existing in concrete surface, so as to increase the hard-
ness and impermeability of the concrete’s surface layer.
Silicate-based solutions (e.g. lithium silicate, calcium silicate
and sodium silicate) and fluosilicate have been proved to be effec-
tive in blocking capillary pores in concrete surfaces [16]. Moon
et al. [86] studied the mechanism of calcium silicate as a surface
treatment. The SiO4- 4 ions contained in the treatment agent react
with the soluble Ca2+, Mg2+, Al3+ ions inside the mortar, and form
an insoluble colloid silicate. Eventually, the insoluble silicate acts
as a micro-filler, generating a compact microstructure and a dense
Fig. 2. The chemical reaction between silane and cementitious substrate [62]. surface, as shown in Fig 3. Sodium silicate is one of the most

Fig. 3. SEM photographs at the surface of mortar (3000): (a) control (b) calcium silicate treatment [86].
582 X. Pan et al. / Construction and Building Materials 132 (2017) 578–590

common pore blocking surface treatment agents. The interaction matrix, and the pozzolanic reaction with calcium hydroxide.
between sodium silicate and cement paste is shown as Eq. (1) Nano-SiO2 is generally produced by the sol-gel process or vaporiza-
[87,88]. Some studies have also demonstrated that sodium silicate tion of silica. Its particle size ranges from 100 nm to 5 nm. As a
treatment can improve the durability of concrete, especially after siliceous material, nano-SiO2 has been intensively studied
post-treatment of cationic surfactant (alkyl quaternary ammonium [94,95]. Recently, Hou et al. [96,97] found that nano-SiO2 treat-
salts) [85,86,89]. Pan and Jia [87,90] demonstrated that sodium flu- ment can increase the impermeability of hardened cement pastes,
osilicate pretreatment can also enhance the performance of because it can reduce the volume of pores larger than 50 nm, and
sodium silicate. However, Ibrahim and Dai [15,91] showed that the threshold value of a pore network. The influence of nano-
sodium silicate treatment cannot significantly improve resistance SiO2 on the morphology of cement mortar is shown in Fig 5. It
to the penetration of water and chloride ions. It was reported that can be seen that pores with a size of about 10 lm are easy to
there is a lot of micro-cracking on concrete surface treated with observe in the untreated sample, while such pores become rare
sodium silicate as shown in Fig 4 [14]. In addition, the reaction in nano-SiO2-treated samples. Nano-MgO is another newly
of sodium silicate and calcium hydroxide will generate NaOH, explored chemical reactive nanocomponent in cement-based
which might increase the likelihood of alkali-silicate reaction [15]. materials though its application on surface treatment waits for fur-
ther investigation [147].
Na2 O  nSiO2 þ CaðOHÞ2  CaO  nSiO2  xH2 OðGelsÞ þ 2NaOH ð1Þ
Because of the good stability of calcium carbonate, many
During the last few decades, some researchers have attempted researchers have used calcium carbonate precipitation for concrete
to use nanoparticles for concrete surface treatment. A developed surface treatment. There are mainly two methods for generating
strategy to mitigate reinforcement corrosion in concrete is through calcium carbonate precipitation on concrete surface: bacterial
the use of electrokinetic nanoparticle (EN) treatment. Cardenas induced carbonate mineralization and dimethyl carbonate (DMC)
et al. [7,92] attempted to use EN treatment to improve the durabil- solution. Some bacteria, such as ureolytic bacteria, can produce a
ity of concrete. They found that an electrokinetic technique can urease enzyme which can catalyze the hydrolysis of urea, and pro-
enhance the effect of nanoparticle treatment on the quality of duce CO2 and ammonia [98–102]. The hydrolysis process increases
the concrete cover. Kupwade-Patil et al. [89] used EN treatment the pH, resulting in an increment of carbonate concentration, as
to drive pozzolanic nanoparticles into concrete. They reported that shown in Fig 6 [103]. Calcium carbonate crystals nucleate and pre-
the nanoparticles inhibit the ingress of chlorides, and increase ten- cipitate on bacterial cells, which increases the resistance of cemen-
sile strength by 25%. It was found that the treatment reduces the titious materials to aggressive substances. In terms of DMC, it is a
Ca(OH)2 content by approximately 8%, and forms additional cal- highly biodegradable and low toxicity solution. At room tempera-
cium silicate hydrate (C-S-H) and calcium aluminate hydrate (C- ture and pressure, DMC can hydrolyze slowly and form carbonate
A-H). Wu et al. [93] stated that the electrokinetic technique can and methanol (CH3OH) [104,105]. CH3OH has no side-effects in
cause nanoalumina particles to drift into concrete pores to refine relation to the treatment and environment, because it will oxidize
the porosity distribution and increase bond strength of rebar- into carbon dioxide and water in the air. On the other hand, car-
concrete interface. bonate can react with additive calcium ions, and thus forms car-
The prerequisite of effectiveness of nano-materials treatment bonate precipitation. Though both methods are eco-friendly, they
on cement-based materials is its penetration into the hardened still have some drawbacks. The culture of bacteria which induces

Fig. 4. SEM photographs of surface concrete without treatment (a), and with sodium silicate treatment (b) [14].

Fig. 5. SEM images of nanoSiO2 /TEOS-treated mortar: (a) control, (b) nanoSiO2, (c) TEOS [96].
X. Pan et al. / Construction and Building Materials 132 (2017) 578–590 583

Fig. 6. The process of bacterial induced carbonate mineralization [103].

carbonate mineralization needs to be carefully controlled on con- concrete surfaces treated with silane–clay nanocomposite are
crete surface. In addition, the nutrient solution for the develop- shown in Fig. 7 [54]. It can be clearly seen that silane–clay
ment of these bacteria is expensive, and may result in nanocomposite coating blocks the micro pores presented on the
environmental eutrophication. The DMC solution is a green reagent untreated concrete. In addition, coverage of micro-voids could
compared with many surface treatment agents, but its treatment increase with clay content, which is directly attributed to the
process must follow specific introduction practices and does not impermeability of concrete to liquids or gases. Meanwhile, the
provide a good protection effect without multi-treatment. increase of clay content can reduce the surface roughness, and thus
decrease the surface area exposed to aggressive environments.
2.4. Multifunctional surface treatment According to Woo et al. [62], the lowest permeability was obtained
when the clay content was 5 wt%. But they also reported that the
The existing classification does not include some newly devel- chloride diffusion resistance of silane–clay nanocomposite treat-
oped surface treatments which have one or more of the three basic ment decreases compared with neat silane [59]. The possible rea-
functions mentioned above. Silane/clay nanocomposites, ethyl sil- son for this phenomenon is that the addition of clay particles
icate and super-hydrophobic paper sludge ash coating can be clas- leads to higher viscosity and a poorer wetting property which
sified into this group. reduces its penetration depth, though the barrier properties
Silane–clay nanocomposites are a new class of surface treat- increase. As there are no experimental data about the penetration
ment agent. They not only exhibit a hydrophobic effect, but also depth of silane–clay nanocomposites, this hypothesis needs further
change the microstructure in concrete cover. Woo et al. [62] investigation [59,62].
demonstrated that the effect of silane on reducing permeability Ethyl silicate (or tetraethylorthosilicate, TEOS) is an alkoxysi-
and chloride diffusion of concrete is substantially improved even lane compound. It can be produced through the reaction between
with the addition of clay particles. Typical SEM photographs of alcohol and tetrachlorosilane. TEOS has been widely used in stone

Fig. 7. SEM photographs of untreated concrete surface (a), concrete treated with silane (b), silane-3 wt% clay nanocomposite (c), and silane-5 wt% clay nanocomposite (d)
[62].
584 X. Pan et al. / Construction and Building Materials 132 (2017) 578–590

treatment and the refractory industry [106]. Recently, Franzoni 3. Factors influencing the performance of surface treatment
et al. [2,107] found that TEOS can effectively enhance the quality
of concrete surfaces by either brushing or immersion. The protection provided by surface treatments varies with the
TEOS itself does not have binding ability, but it can form a silica condition of the concrete substrate and treatment process
gel and fill the pore network through the hydrolyzing process. As [13,115]. To ensure good surface treatment of concrete, it is neces-
an alkoxysilane, its hydrophobic effect can last for more than sary to obtain a comprehensive understanding of the factors which
6 months [108], and therefore before hydrolysis completes it can affect the performance of surface treatment [116,117].
also protect the substrate by preventing the entry of corrosive sub-
stances. A two-stage reaction takes place as TEOS penetrates into
3.1. Air permeability
the capillary pores on concrete surface, as shown in Fig 8. Firstly,
TEOS hydrolyzes, forming silanol and ethanol. The silanol dehy-
Air permeability primarily influences the performance of
drates and condensates in the second stage in which silica gel pre-
surface-treated concrete in two aspects. On one hand, the greater
cipitates inside the pore structures. On the other hand, ethanol
the air permeability, the faster the carbonation rate, and thus, rein-
evaporates quickly leaving no damage to either the treatment or
forced steel bars are more susceptible to corrosion. Vries et al.
the substrate [109]. In addition, Pigino et al. [2] showed that TEOS
[115] found that diffusion of water vapor of surface-treated con-
displays pozzolanic behavior. It reacts with calcium hydroxide in
crete should be 60% less than that of untreated concrete. On the
concrete substrate, forming calcium silicate hydrate as shown in
other hand, sufficient permeability to water vapor should be
Fig. 9.
allowed, because concrete needs a certain degree of breathability.
The following reasons mainly guarantee that TEOS has potential
Otherwise, accumulation of water beneath the surface can cause
to protect concrete structure effectively in an environmentally
great damage in freezing and thawing cycles [9]. Moreover, Liu
friendly way: (1) TEOS has low viscosity and small molecular size
et al. [118] demonstrated that breathability affects the adhesion
which allows it to penetrate deeply into concrete substrate [110].
between the concrete matrix and coatings. Also, when the emis-
(2) The by-products of TEOS are non-toxic (water and ethanol).
sion rate of water vapor was less than 283 lg/s, the adhesion
(3) The silica gel has excellent compatibility with cementitious
strength between the coating and the concrete matrix was found
materials and good stability in outdoor environments; (4) TEOS
to significantly decrease [119]. Therefore, the effect of concrete
will not block all open pores and only partially reduces permeabil-
surface treatment on air permeability must be carefully consid-
ity to air [111]. However, it has three drawbacks: (1) slow reactive
ered. The air permeability of many polymer coatings, such as epoxy
rate [106]; (2) easy to crack during shrinkage and drying; and (3) a
and polyurethane, is almost zero [116], which is one of the main
limited effect on carbonated concrete since its effect is not signifi-
disadvantages of polymer coatings. Studies have shown that silane
cant in lime stone. These drawbacks might be improved by the
and siloxane do not have a significant effect on air permeability,
addition of a catalyst, nanoparticles, and additives, but these addi-
and thus they cannot resist the ingress of carbon dioxide [10].
tions require further investigation [112–114].
There are several methods for measuring the air permeability of

Fig. 8. Reaction of TEOS in concrete surface: (a) hydrolysis reaction, and (b) condensation reaction [107].

Fig. 9. The products of reaction between TEOS and Ca(OH)2 (left), and the chemical profile (right) [2].
X. Pan et al. / Construction and Building Materials 132 (2017) 578–590 585

surface-treated concrete, including water absorption-desorption, and the possible methods are summarized as follows: (1) The spec-
dry-cup/wet-cup method, and Autoclam air permeability [10]. imen treated with the impregnation product is split into two parts,
and water is sprayed over the fracture surfaces. The penetration
3.2. Bonding strength depth is taken as the thickness of the hydrophobic layer [15]. This
simple method can evaluate the penetration depth quickly. How-
Surface treatment should have good adhesion to concrete sub- ever, it is a destructive method, and cannot be used for impregna-
strate, which can ensure its long-term performance and protection tion treatments without hydrophobic effect. (2) The penetration
of concrete. Previous investigation showed that the bonding depth can be calculated though Eq. (2), proposed by Dhir et al.
strength of coatings should be not less than 1.4 to 1.75 MPa [131]. This method assumes the treatment agent is distributed
[120]. According to Berndt [121], the average bond strength of dif- equally at different depths, which is not the case in reality. (3)
ferent epoxy coatings ranges between 2.9 and 4.0 MPa, and the Inductive coupled plasma optical emission spectroscopy (ICP-
bond strength for cementitious mortar is about 2.2–3.3 MPa. These OES) was used to measure the penetration depth through detecting
adhesions are generally governed by several factors, such as prop- the chemical element profile in a concrete surface layer [4]. Though
erties of the coating and primer, the quality and condition of sub- this method can accurately measure the penetration depth, it is
strate, and the method of application of coatings time-consuming. (4) Red soluble pigment can be mixed with an
[18,74,114,118,122]. Researchers have found that the surface impregnation treatment agent, then the penetration depth is
roughness of substrate might influence the adhesion of coatings. determined by measuring the thickness of the red layer.
And the roughness depends on the compressive strength of sub- The penetration depth of surface treatment agents depends on
strate and the properties of aggregates [123–125]. It is known that the following factors [2,129,131]: (1) properties of the surface
organic coatings will degrade after aging, but less research has treatment agent, particularly the molecular size and viscosity; (2)
been focused on the bonding strength after aging of coating the type of solvent; (3) the properties of the concrete substrate,
systems. such as porosity and saturation degree; (4) the reaction time;
As shown in Fig 10, ASTM D4541 and ASTM C321-00 can be and (5) reaction rate, such as the water-repellent film formed by
modified for measuring the bonding strength of coatings. In ASTM silane impeding its own penetration. Silanes and siloxanes can
D4541, the coated concrete is drilled by a diamond driller to sepa- penetrate into concrete and form a hydrophobic layer due to their
rate the center part of the coating from the whole coating system. small molecular nature [85]. The penetration of alkyl triethoxysi-
Then, a metal sheet is fixed on the coating using rapid setting lane is deeper than for other silanes due to its lower reaction rate.
epoxy. The bonding strength equals the stress added to the metal According to Dai et al. [15], both silane-based gel and silane-based
sheet when the coating separates from the substrate. This method cream can achieve deeper penetration than liquid silane. This is
is widely used for in-situ testing, but is a time-consuming because both gel and cream contain highly active silane content,
approach [126]. Sometimes, the measurement is less accurate even though their viscosities are much higher than liquid-based
because the coating system is susceptible to damage during the silane. Meanwhile, the liquid silane evaporates fast during applica-
preparation for testing. Liu et al. [127] modified ASTM C321-00 tion, while silane gel and cream remain on the surface for a longer
to determine the bonding strength of coatings. As shown in time.
Fig 10(b), two concrete blocks are bonded together by a layer of For surface coatings, their penetration depths are often a few
coating, then loading is added to the blocks to separate them. millimeters or even less. Therefore, penetration depth has little
Recently, Czarnecki et al. [128] used an ultrasound approach to effect on their protection. However, the coating thickness signifi-
measure the bonding strength. This is a non-destructive test, and cantly affects their performance [10,15,132]. Generally, coating
much more convenient in comparison with the previous discussed thickness can be measured directly. The thicknesses of concrete
approach, but still requires further research and improvement. coating can also be measured by a mobile nuclear magnetic reso-
nance (NMR) instrument. This method is a non-destructive tech-
3.3. Penetration depth / coating thickness nique, and can be used on site [133,134]. Recently, Sondej et al.
[135] proposed using X-ray micro-computed tomography and con-
Impregnation surface treatment agents should penetrate into focal laser-scanning microscopy as non-destructive techniques to
the substrate as deeply as possible to ensure long-term durability evaluate the coating thickness. However, this technique is cur-
[129,130]. There is no direct measurement to determine the pene- rently only allowed to be used on circular concrete pipes now.
tration depth of impregnation. Researchers have tried different Table 2 summarizes several penetration depths of impregnation
methods to investigate the penetration depth of impregnation, treatment agents/thicknesses of concrete coatings.

Fig. 10. Testing for measuring coating bonding strength [118, 127, 128].
586 X. Pan et al. / Construction and Building Materials 132 (2017) 578–590

Table 2 combination makes a positive contribution to concrete with a


The penetration depth of impregnation treatment agent / thickness of concrete crack width of about 0.08 mm. A few studies have been carried
coating.
out to study the cracking resistance of surface treatments. Tittarelli
Ref. Treatment Measuring methods Penetration depth et al. [8] reported that silane can be used as a restorative method in
methods / thickness the presence of 0.5-mm wide cracks. Godkowska [139] developed a
[131] Epoxy resin Micrometer 200  400 lm model to calculate the cracking resistance of protective polymer
[132] Methacrylate Micrometer 100  150 lm coatings and polymer cement subjected to short-term and long-
[132] Acrylic Micrometer 100  300 lm
[15,129,133], Silane Hydrophobic layer/ About 12 mm
term loading. Though this forecasting method has potential for
NMR sensor application in the design of protective coatings, the experimental
[4] Ethyl silicate ICP-OES P19 mm test results are generally found to be higher than that obtained
[15] Sodium Hydrophobic layer Almost 0 mm by calculation. The reason is that the forecasting method only cal-
silicate
culates the mean stress, which is usually lower than the maximum
stress, as indicated in Fig 11.
DryWeighðgÞ There are two testing methods to measure the crack-bridging
WetWeighðgÞ
 VolumeAppliedðcm3 Þ
Mean Penetration DepthðcmÞ ¼ ability of coatings. One of them measures the crack-bridging ability
Areaðcm2 Þ indirectly by measuring creep of coatings [126]. Strips of coatings
ð2Þ are fixed in two jaws and subjected to a constant stress of
0.5 MPa at room temperature. This method mainly considers the
3.4. Cracking resistance physical properties of coatings, but it is difficult to reflect the
actual situation. Another method is a direct crack-bridging test
With a relatively low tensile strength, concrete easily cracks [140–142]. A crack is cut by a saw on the center of a concrete slab.
[136,137]. Thus, barrier properties will be lost soon after the appli- Then, forces should be added to the concrete sample to control the
cation of any surface treatment system that does not have ade- development of the crack at about 0.5 mm/min. The stress is
quate crack healing ability or cracking resistance. Yoon [138] recorded in the displacement process, as shown in Fig 12. In the
found that polymer coatings and silane treatment can protect con- first stage, the crack develops with the increase of stress, and the
crete which has cracks with a maximum width of 0.06 mm. Their concrete slab finally breaks. After that, stress decreases rapidly

Fig. 11. Graph of the displacement (a) tensile strain (b) sharing strain in the coating-concrete (c) combining plane at relaxation zone length [139].
X. Pan et al. / Construction and Building Materials 132 (2017) 578–590 587

Table 3
Number of coatings required to follow water absorption limit guidelines established
in literature [145].

Water Information source Material


absorption
Silane/ Silane/
Limit
siloxane siloxane
dispersed in dispersed in
water solvent
50% German Committee for 3 2
Reinforced Concrete
75% The US NHRP Report 244: >4 3
‘‘National Cooperative
Highway Research Program’’
80% Vries et al. >4 4

4. Summary and perspective

Protection through surface treatment is a complex issue, which


includes various physical–chemical mechanisms. On the basis of
the literature review, some conclusions can be drawn: (1) Surface
treatments can prevent the ingress of aggressive substances to
improve the performance and service-life of concrete structures.
Fig. 12. Stress of the concrete and coating system during a crack-bridging ability
According to the mechanism, surface treatment agents can be clas-
testing [142].
sified into four types: surface coating, hydrophobic impregnation,
pore blocking surface treatments and multifunctional surface
and represents the crack-bridging ability of the coating. The
treatment agents. (2) Over the last three decades, there have been
response of coating under loading is shown in stage III. Finally,
many significant advances in surface treatment methods. New sur-
the abrupt change in the stress results from the failure of the coat-
face treatment agents are emerging. The main tendency is to
ing near the cracking. Although the test can characterize the
improve their protective effect and resistance to weathering. (3)
behaviors of coating under cracking, during the experiment it must
Surface treatment is mainly affected by air permeability, bonding
be ensured that the concrete and coating are tested under pure
strength, penetration depth/thickness, crack resistance, substrate
tensile stress which is difficult to obtain. Otherwise the accuracy
properties and application method. Therefore, the surface prepara-
of the experiment cannot be guaranteed.
tion of substrate before treatment is essential for its effectiveness
and failure patents.
3.5. Substrate properties and application method To get a full understanding of surface treatment methods, the
following aspects need to be considered in future research: (1)
The effect of surface treatment is affected by age and water con- Though the mechanism of organic coating and silane/siloxane are
tent of the concrete substrate, treatment methods (spraying, clarified, further experimental studies on polymer/clay nanocom-
brushing or immersion) and the amount of treatment agent [10]. posite coating and pore blocking treatment are needed. (2) The
Baltazar et al. [143] found that the effectiveness of surface treat- protection provided by surface treatment agents varies according
ment is more significant in concrete with higher porosity, because to the condition of the concrete substrate and treatment process;
treatment agents can penetrate more easily and deeply into that therefore, further studies are required to develop a selection
concrete. In addition, the capillary water might impede the pene- method. (3) The Ca(OH)2 content in hardened cement paste will
tration of some treatment agents. Siloxane cannot be applied on affect the reaction of silane, ethyl silicate, and silicate-based pore
wet surface, while the alkyl triethoxysilane which undergoes blocking treatments, but there is no research showing the effect
hydrolysis with water can be used on wet substrate. As for most of cement type on the selection of surface treatment. (4) There
treatment agents, the age of the substrate also affects the effective- are no definitive acceptance criteria for many of the properties dis-
ness of surface treatment. Hydrophobic treatment works for cussed in this article. (5) Specifications and guidelines for treat-
10 years when treated on 6-month old concrete, but this long- ment methods and preconditioning of concrete substrate are very
term effect cannot be achieved when treatment is applied on early important and necessary.
age concrete because the hydration of cement creates a new sur-
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