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Durability enhancement for

cementitious materials
through waterproofing by
organosilicon chemistry
Dr. Wei Cai, Construction Silicones, Wacker Chemie AG, Munich/Germany

CREATING TOMORROW’S SOLUTIONS

 MATERIALS

Damage associated with water inside the mass are a key threat to a more durable
cementitious product. With the help of organosilicon waterproofing agents, such damage
can be very effectively suppressed or fully prevented. In addition to the well-established
surface treatment approach, integral waterproofing by organosilicon agents further
enables more thorough, multi-faceted protection for cementitious systems in the long run.

TEXT Dr. Wei Cai, Construction Silicones, Wacker Chemie AG, Munich/Germany

WACKER CHEMIE AG

Durability enhancement for cementitious

materials through waterproofing by
organosilicon chemistry
1 Introduction For decades, organosilicon-based chemicals
Cementitious materials like concrete are main- have been used in the construction industry for the
ly composed of aggregates of various sizes such protection of various building materials including
as sand and rock, which are bonded together by cementitious types against moisture and conse-
fresh cement paste and become a rigid mass over quential deteriorations [2, 3, 4, 5]. For instance,
time. Although mostly hard and dense, cement- silanes carrying reactive and inert groups have
based systems are by their very nature still porous the capability to create a pronounced hydrophobic
and thus susceptible to damage and deterioration effect on finished mineral-based substrates after
caused by deleterious substances. Typical examples treatment [6]. When they are applied to the sub-
of such deterioration processes are alkali-silica re- strate material, the reactive groups such as alkoxy
action, sulphate attack, carbonation, frost damage silyl groups can react with hydroxyl groups exist-
etc. A common feature generally behind all these ing on the surface to form stable covalent bonds.
processes is the presence of water, in its liquid, sol- The silanes themselves can also react with each
id or gas state. Water can either act as a transport other through hydrolysis and condensation pro-
medium for the deleterious substances or be direct- cesses between the remaining alkoxy silyl groups
ly involved in the chemical or physical processes and can form a very thin but permanent layer of
[1]. As a result, most construction projects require polymer network covering the substrate surface. In
a certain type of proofing system to make cemen- contrast, the non-polar groups as the inert part of
titious products impervious to external water, as the silane molecules, e.g. alkyl groups, render the
well as other substances. substrate surface hydrophobic. As a result, water

1 Schematic illustration of silane molecules forming a polysiloxane network and exhibiting hydrophobic effects on mineral substrate

Hydrophobic effect

R R
All illustrations: Wacker Chemie AG

Si Si
OR’ OR’
OR’ OR’
OR’ OR’

Strong bonding

ure 1 Schematic illustration of silane molecules forming polysiloxane network and exhibiting hydrophobic effect on mineral substr

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 MATERIALS

R R R R R R R R

C O C O C O C O Si O Si O Si O Si

-
O O-
-
O O- O O O O
Ca++ Ca++

Si O Si O Si O Si Si O Si O Si O Si

Concrete Capillary Wall Concrete Capillary Wall

a) b)

Figure 2 Schematic illustration of the inner surface of concrete capillary pore after treatment by a) oil-based hydrophobic
admixture and b) organosilicon-based hydrophobic admixture.
or moisture is repelled and cannot penetrate into be dry so that the penetrating and hydrophobizing 2 Schematic illustration
the substrate structure. With this, water-associated processes can take place. This means that materials of the inner surface of a
concrete capillary pore
processes such as blistering, fungi growth, salt at- with wet surfaces are not suitable for direct surface after treatment by
tack etc., which may easily cause health issues and treatment. In the case of freshly-mixed concrete, a) an oil-based
safety damage to the materials and structures in a sufficient drying time of several days or weeks hydrophobic admix-
use, can be significantly suppressed. needs to be ensured before hydrophobic agents can ture (left) and
b) an organosilicon-
Wacker has been a technology leader in the field be applied. based hydrophobic
of organosilicon-based construction chemicals for In order to provide longstanding comprehen- admixture (right)
post concrete surface treatment for more than six sive protection, it is also necessary to hydropho-
decades. The product series which is commercially bize the interior of the target object and convert the
available under the trade name SILRES® BS has whole of it into a water repellent mass. This is espe-
been very effectively applied to treat and protect a cially critical for cement-based materials, as water
wide range of buildings and public works [5, 6, 8]. is always present inside the cementitious matrix
By means of surface impregnation, coating, etc., – either as a chemical constituent of the hydration
these products help achieve excellent hydrophobic process or from external sources. Moreover, the po-
effects on treated substrates against water-induced rous and hydrophilic nature of the matrix renders
damage. Besides hydrophobicity, silane and silox- it susceptible to the deteriorations resulting from
ane chemistry also offers additional benefits such transport processes of water, thus impairing the
as anti-stain effects or brilliant wall colors, con- durability of the material significantly.
tributing to the overall aesthetics of construction In this article, the waterproof treatment of a
works. cementitious mass by using organosilicon chemi-
The application of organosiloxane agents can cals will be elaborated. We will be able to show
generate pronounced hydrophobicity within the that integral hydrophobation is key to the effec-
top layer of the surfaces of walls, floors or other tive and economical protection against any water-
building products. This provides exterior protection associated deterioration process. It is therefore the
against water-associated damage to a very high ideal approach to enhance the internal durability
level. However, there are several occasions where and reliability of a cementitious system.
the surface protection alone is insufficient or in-
appropriate. For instance, if the protective surface 2 Integral waterproofing of cementitious materials
layer gets damaged during service, the unprotected 2.1 Overview of current approaches
inner part will be subject to possible deleterious Integral waterproofing is a highly efficient solution
effects from the surrounding environment. Even to make cementitious materials such as concrete
with a tiny failed spot on the surface, the subse- water-repellent. It also has noticeable advantages.
quent capillary effect can draw moisture from the For instance, in construction works such as deep
surrounding environment into the dry mass, lead- underground or tunnelling projects, the dosing of
ing to water-induced internal deteriorations. Be- a hydrophobic additive can be easily incorporated
sides, the surfaces of the treated objects need to into the concrete batching process, just as conveni-

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MATERIALS

Water
WaterRepellence Test
Repellence Results
Test Results
Water Absorption (%) Depth of Water Penetration under
2,8
(* 30 min. immersion under water)
2 Pressure [5 bar / 72 hrs] (mm)
2,8 2
40 40 2 2

Water penetration under pressure (mm)

Water penetration under pressure [mm]

2,4 2,4
1,6 1,6

Admixture dosage (wt.% cement)

Admixture dosage [wt. % cement]

Admixture dosage [wt. % cement]

Admixture dosage (wt.% cement)

2 1,6 1,6
2 30
Water Absorption [%]

Water Absorption (%)

30
1,2 1,2
1,6 1,6 1,2 1,2
1 1
1 20 20
1,2 1,2 11 1
0,8 0,8
0,8 0,8
0,8 0,8
10 10
0,4 0,4 0,4 0,4
0,4 0,4 0,2
0,4 0,2 0,2 0,2
0,4 0,4 0,4

0 0 0 0 0 0 0 0
control control
SILRES®SILRES®
SILRES®SILRES®
Organic Organic Crystalline
Crystalline control control
SILRES®SILRES® BS SILRES®
BS SILRES® Crystalline
Crystalline
BS 1803 BS 1803 EPowder E
Powder 1803 1803PowderPowder
E E

Figure
Figure 3 Water3absorption
Water absorption measurement
measurement (30
(30 min. immer- FigureFigure
min. immer- 4 Water
4 Water penetration
penetration depth depth measurement
measurement underunder
5 5
3 Water absorption measurement resultsgroups
sion) of
sion) results results of different
different groups ofofconcrete
different groups ofspecimens,
of concrete concrete
specimens, bar4 for
Water
72penetration
bar depth
for 72 hours,
hours, acc. measurement
acc.
BS ENBS under 5 bar for 72 hours,
EN 12390-8:2009.
12390-8:2009.
specimens (30 min.
acc. BSimmersion),
1881 Partacc. BS 1881 Part 122:2011
122:2011. acc. BS EN 12390-8:2009
acc. BS 1881 Part 122:2011.
ent as any other conventional admixtures. No ex- facing molecules form a loose bonding with the
tra effort is thus needed for achieving the intended minerals of the inner pores. However, the bonding
waterproofing effect. It can also be very conveni- is not permanent and is subject to break down over
ent for waterproofing concrete parts of complex time, as physical or chemical deteriorations occur.
structures or blind side work where traditional Organosilicon-based chemicals can also be used
constructing methods would be difficult to imple- as hydrophobic admixtures for concrete. Similar to
ment and where lots of auxiliary set-ups need to be carbon-based chemicals, the molecules of silane
in place. Furthermore, long-lasting waterproofing or siloxane can also line the capillary pore walls
will reduce maintenance costs for the whole lifecy- via siloxane linkages, as illustrated in Figure 1.
cle of the concrete work dramatically. The alkyl groups of the molecules then render the
Integral waterproofing can be achieved by us- cementitious matrix hydrophobic. But unlike fatty
ing chemicals as hydrophobic admixtures mixed acid salts’ loose bonding with the inner surfaces of
with other constituents [9]. Carbon-based organics concrete pores, the hydroxyl groups of silanes and
such as fatty acid salts have been broadly used to siloxanes can chemically react with the hydroxyl
make concrete hydrophobic for many years [10]. groups on the concrete pore walls. Through a con-
The molecules of these chemicals, deposited in the densation process, strong -Si-O- bonds are formed
pores and voids within the concrete, form a thin and thus silanes and siloxanes are firmly attached
layer covering the inner pore surfaces. Subsequent- to the pore walls. Such condensation reaction can
ly, such layers can prevent water from penetrating also take place between neighboring silanes and si-
into the pore walls since the alkyl or alkenyl groups loxanes to form a polysiloxane network, if residual
of the molecules facing outward are non-polar and hydroxyl groups exist. Consequently, the polysi-
hydrophobic by nature. The groups of the inward- loxane coverage becomes an integral part of the
concrete pore system, leading to greatly enhanced
Table 1 Mix design of different groups of concrete specimens subject to waterproof-
durability performance (see Figure 2, right) in con-
ing testing. SRB denotes SILRES® BS 1803, SRP denotes SILRES® Powder E. “Organic”
denotes an oil-based hydrophobic agent, “Crystalline” denotes a crystalline water- trast to that of an oil-based admixture which is
proofing agent only deposited within the capillaries (see Figure 2,
left).
Content [kg/m³]
Constituent Apart from hydrophobic admixtures, there is
Control SRB SRP Organic Crystalline another type typically known as crystalline tech-
Cement 350 350 350 350 350 nology. These admixtures are essentially composed
Fine aggregate 798 798 798 798 798 of very fine powder-like ‘reactive’ particles which
Coarse aggregate 975 975 975 975 975 can function as pore-fillers by hydrating with free-
Water 168 168 168 168 168 ly available water inside the pores of the concrete
Superplasticizer 3.50 2.80 3.50 2.80 3.85 mass [11]. Such reactivity originates from their la-
Waterproofing agent 1.4 0.7 3.5 3.5 tent hydraulicity or pozzolanic activity, which can
-
(bwoc) (0.4%) (0.2%) (1%) (1%) also help to enhance the calcium-silicate-hydrate

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 MATERIALS

(C-S-H) gel formation of cement hydration. Inside Table 2 Main fresh and hardened properties of different groups of concrete specimens.
hardened concrete, the hydration products of these SRB denotes SILRES® BS 1803, SRP denotes SILRES® Powder E. “Organic” denotes an
oil-based hydrophobic agent, “Crystalline” denotes a crystalline waterproofing agent
reactive substances can physically block the pores
or possible passages to the pores. Consequently, the Control SRB SRP Organic Crystalline
concrete matrix is converted into a water-resistant Slump [mm] 150 150 130 130 150
state, blocking its pores effectively against any Strength [MPa] 1d 33.9 27.3 31.8 - 26.1
flow of liquids, even under substantial hydrostatic 7d 50.3 44.7 49.6 40.6 52.2
pressure. 28d 58.5 52.8 57.2 58.2 58
Density [kg/m³] 2376.7 2338.3 2366.7 2393.3 2345
2.2 Concrete hydrophobization with
organosilicon admixtures
Experimental studies have been conducted by
Wacker to compare the waterproofing effect of
organosilicon-based agents with conventional
additives. The selected admixtures include a si-
lane/siloxane emulsion, a silane and an oil-based
powder, and a powder agent based on crystalline
technology. The mix designs of the respective test
groups are shown in Table 1. The mixing proce-
dures of the test groups were conducted in accord-
ance with BS EN 480-1:2014. As a prerequisite for
the sample preparation, the slump value of each
mixture was controlled to be within 130-150 mm,
by fine-tuning the respective dosage of the super-
plasticizer.
The basic fresh and hardened properties of the
concrete specimens are shown in Table 2. The re-
sistance to water penetration was measured with
the specimens completely immersed in water, as principles of the crystalline technology, as it aims 5 Image showing
shown in Figure 3. It is evident that all hydrophobic at forming, in the first place, pore blocking hy- water droplets on dry
cement powder treated
agents contribute to decreased capillary water ab- drates in the concrete matrix with the initial water
with an organosilicon
sorption, when compared to the untreated control ingress. hydrophobic agent on
specimen. The results thus clearly indicate that the In addition to testing the water absorption, the the left and untreated
tested organosilicon chemicals are effective as con- concrete specimens admixed with siloxane and crys- powder on the right.
The water droplet on
crete admixture in reducing the water absorption talline agents were also subject to a 72 hours water
the right-hand side
of the concrete specimens. Moreover, the water- penetration test under a hydraulic pressure of 5 bar. immediately seeps into
repelling performance of the mixture containing Although the crystalline agent specimen performs the lower layers of the
a 0.4% siloxane emulsion dosed by weight of ce- slightly better, the results in Figure 4 also show a untreated powder, while
the droplet on the left
ment (bwoc) and the 0.2% silane powder mix are noticeably lower penetration depth of the specimen
keeps afloat on the
on par with the 1% oil-based hydrophobic agent. treated with a 0.4% dose of Silres BS 1803 when hydrophobized base
In order to achieve a similar water-repellent ef- compared to the control specimen. However, it is without wetting the
fect, the dosage of the siloxane-based agents can important to note that siloxanes do not physically cement grains beneath
it. Yellow dashed line
be significantly lower than that of the convention- block any pores in the inner part of the capillary
denotes the boundary
al oil-based agent. This is a strong indication that system. These pores remain open and fully intact. between the treated and
organosilicon-based products are more efficient Waterproofing under hydraulic pressure is merely untreated cement
when it comes to hydrophobic performance. There achieved by modifying the wettability of the capil-
are basically two reasons for this: first, siloxane lary pore system.
molecules cover the capillary pores more effec- The sample treated with a 0.2% dose of Silres
tively than other agents, and second, the strong Powder E shows no significant change of penetration
bonding between the siloxanes and the minerals of depth as compared to the control group. This could
the concrete helps strongly maintain such an effect. be due to its rather low dosage level as compared to
The result also shows that the crystalline prod- the other specimens. Its hydrophobic modification of
uct absorbs higher amounts of water than the con- the capillary pores was not sufficient to markedly
trol specimen. This indicates that under the cor- resist water penetration under pressure, as compared
responding test scheme, the crystalline product to Silres BS 1803. Regarding the penetration depth,
produced a water-absorbing rather than a water- the crystalline group produced results better than the
repellent effect. This is in line with the working others. This is no surprise, since crystalline agents

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MATERIALS

0,6 0,6
a) Graywacke b) Rhyolite
0,5 Blank 0,5 Blank
SRB-a SRB-a
0,4 SRB-b 0,4 SRB-b

Strain [mm/m]
Strain [mm/m]

0,3 0,3

0,2 0,2

0,1 0,1

0 0

-0,1 -0,1
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
Number of Test Cycles Number of Test Cycles

Figure 6 ASR-induced expansion results for specimens subject to cyclic exposure to 3% NaCl solution. SRB-A corresponds to a
silane product, SRB-B corresponds
6 ASR-induced to a silane/siloxane
have a different emulsion
working principle. Theyproduct. Dotted line
physically in redan
taining denotes the expansion
adequate limit
quantity of according
alkali to
and reactive
the VDZ
expansion method.
results for block the pores in the substrate, making them less silica are used to produce a concrete. The effective
specimens subject to
cyclic exposure to 3%
susceptible to water penetration under pressure. alkali and reactive silica are able to react with each
NaCl solution. SRB-A other in the pore solution environment in the con-
corresponds to a silane 2.3 Cement hydrophobization with crete to form an alkali-silica gel. The gel product
product, SRB-B cor- organosilicon additives swells if free moisture is available and creates a
responds to a silane/
siloxane emulsion prod-
Beyond the treatment of concrete, it is possible to volume increase that builds up stress inside the
uct. Dotted line in red hydrophobize the cement itself. Organosilicon addi- rigid mass. This can cause significant weakening of
denotes the expansion tives are able to make cement hydrophobic by cover- the cementitious matrix and lead to gradual func-
limit according to the ing cement grains with thin layers of hydrophobic tional failure of the concrete.
VDZ method
left: Graywacke
organosilicons. An example is shown in Figure 5. Improper raw materials (mainly aggregates)
right: Rhyolite Water droplets were placed on treated cement pow- due to resource scarcity or simply operational re-
der (left) and on an untreated sample (right). The strictions are additional reasons why ASR issues
water droplet on the untreated cement immediately occur nowadays. If left unattended or not properly
seeped in through open channels and wetted most of dealt with, the mechanical and durability damage
the powder on its way downwards. The water droplet can be substantial. Although rarely with immedi-
on the left remained on the surface of the hydro- ate failure, damaged concrete structures or units
phobized cement and was unable to penetrate the do need to be repaired or replaced eventually to
powder beneath. Cement treated with organosilicon restore full functionality. Preventive measures to
hydrophobic additives can even repel water while help deal with the potential ASR risk do exist. For
being static and is not susceptible to any surrounding instance, sourcing raw materials with low effective
moisture. Organosilicon-based hydrophobic agents alkali and reactive silica contents is one option. Us-
are therefore able to: ing ASR-inhibiting admixtures such as compounds
»» help stabilize cement against prehydration under based on lithium is another [12]. However, these
humid and warm conditions, especially when the measures are not always feasible. Suitable raw
cement is stored in bags. materials can be scarce and therefore too expen-
»» improve the anti-caking property of cement, as sive to source in the affected regions. Moreover,
the moisture-reliant agglomeration tendency of transporting large amounts of aggregates over long
cement particles is suppressed by the introduced distance imposes high environmental impact and is
hydrophobicity. not ecological in the long run, either.
»» manufacture hydrophobic cement which can
potentially function as a carrier for incorporat- 3.2 ASR mitigation with organosilicon admixtures
ing hydrophobic properties to cementitious mix- As shown in the previous section, organosilicon
tures, e.g. concrete, mortar etc. hydrophobic admixtures are able to effectively
hydrophobize a cementitious mass. Since the dam-
3 Mitigation of alkali-silica-reaction in concrete aging processes of ASR need water to be present,
3.1 Overview of current approaches hydrophobic treatment should be able to signifi-
Alkali-silica-reaction (ASR) is a well-known dura- cantly reduce or even completely inhibit the de-
bility issue threatening the long-term use of con- structive processes. Experimental investigations
crete. It can take place when raw materials con- have thus been carried out by Wacker to examine

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 MATERIALS

3 3
a) Graywacke b) Rhyolite
2,5 Blank 2,5 Blank
SRB-a SRB-a
2 SRB-b 2 SRB-b

Strain [mm/m]
Strain [mm/m]

1,5 1,5

1 1

0,5 0,5

0 0

-0,5 -0,5
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
Number of Test Cycles Number of Test Cycles

Figure 7 ASR-induced expansion results for specimens subject to cyclic exposure to 10% NaCl solution. SRB-A corresponds to a
the corresponding influences.
silane product, SRB-B Two types
corresponds of ad-
to a silane/siloxane In theproduct.
emulsion secondDotted
test, line
rhyolite
in red aggregates were
denotes the expansion 7limit according to
ASR-induced
the VDZ
mixtures method.
were tested: one admixture was silane- exposed to the 3% NaCl solution up to 14 times, expansion results for
specimens subject to
based, the other was a silane/siloxane emulsion. as shown in Figure 6, right. Compared to the
cyclic exposure to 10%
Two types of ASR-prone aggregates were used to graywacke group, the average strain increase of NaCl solution. SRB-A
drastically increase the possibility of the ASR ef- the control specimen was much lower. The strain corresponds to a silane
fect in the concrete specimens. The mix designs of value amounted to 0.24 mm/m after 10 cycles and product, SRB-B cor-
responds to a silane/
respective test groups listed in Table 3 are all based did not exceed the 0.3 mm/m limit. This is un-
siloxane emulsion prod-
on the top-layer concrete composition suggested in derstandable, since rhyolite is less reactive than uct. Dotted line in red
the General Circular on Road Construction (ARS) graywacke with respect to ASR. However, the denotes the expansion
No. 04/2013, issued by the Federal Highway Re- specimens containing the silane and the silane/ limit according to the
VDZ method
search Institute of Germany (BASt) [13]. siloxane emulsion agents exhibited almost no vol-
left: graywacke
In order to evaluate the ASR resistance, a test- ume expansion at all. The average strain values right: rhyolite
ing method developed by the Association of Ger- detected after 10 cycles varied between 0.04 and
man Cement Manufacturers (VDZ) was adopted -0.04 mm/m, respectively.
[14]. According to this method, concrete prisms The results of the ASR tests using graywacke
with certain dimensions were subject to cyclic ex- aggregates exposed to a 10% NaCl solution are
posures to 3% and 10% NaCl solutions which act shown in Figure 7, left. The strain increase of the
as external alkali supply. To pass the ASR test, the control specimens was significant over the whole
volume expansion of the specimens is not allowed testing period. After 10 cycles of exposure to the
to exceed 0.30 mm/m with 3% NaCl solution and/ alkali source, the average strain value greatly
or 0.50 mm/m with 10% NaCl solution, after 10 exceeded the expansion limit of 0.5 mm/m, and
cycles. reached 1.97 mm/m. It is quite evident therefore
The results of the ASR tests with graywacke that graywacke aggregates can induce an ASR
aggregates, up to 14 exposure cycles with a 3% effect in ordinary concrete recipes if repeatedly
NaCl solution, are shown in Figure 6, left. The exposed to a concentrated external alkali supply.
average strain of the control specimen increased The specimens mixed with a silane agent showed
steadily over time, and after 10 exposure cycles
to the NaCl solution, it measured 0.39 mm/m, ex- Table 3 Mix design of different groups of concrete specimens subject to ASR testing.
ceeding the expansion limit of 0.3 mm/m. This is SRB-A corresponds to a plain silane product, SRB-B corresponds to a silane/siloxane
emulsion product
consistent with the fact that graywacke aggregates
are very ASR-sensitive and can greatly enhance Content [kg/m³]
ASR effects if they are used in ordinary concrete Constituent
recipes. However, the specimens containing the si- Control Graywacke-group Rhyolite-group
lane admix and silane/siloxane emulsion were not Cement 430 430 430 430 430 430
affected at all. The average strain values during Sand (0/2 mm) 525 525 525 525 525 525
the overall testing period varied between 0.04 and Aggregate Graywacke 1253 - 1253 1253 - -
0.05 mm/m, respectively. This clearly shows that (5/8 mm) Rhyolite 1211 - - 1211 1211
both the silane agent as well as the silane/siloxane Water 193.5 193.5 193.5 193.5 193.5 193.5
emulsion can significantly inhibit ASR-induced SRB-A - - 0.86 - 0.86 -
expansion with 3% NaCl solution as alkali supply. SRB-B - - - 2.15 - 2.15

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 MATERIALS

a) untreated b) treated

8 Optical microscope images under UV-light of concrete specimens: left: untreated blank sample right: treated with silane/siloxane emulsion
infiltrated by fluorescent resin. The specimens shown contain graywacke aggregates and were cyclically exposed to a 3% NaCl solution.
Blue arrows denote cracks through hardened cement paste. Red arrows denote cracks through coarse aggregates
al microscope images under UV-light for concrete specimens (a. untreated blank sample; b. treated by silane/siloxane emulsion) i
n. The specimens shown contain Graywacke aggregates and were cyclically exposed to 3% NaCl solution. Blue arrow denotes c
ent paste. Red arrow denotesa cracks through
moderate coarse
increase aggregates.
of strain Figure
over time, but at a 8 Optical microscope
3.3 Further discussionimages under UV-light for concrete
k sample; b. treated by silane/siloxane emulsion)
rate lower than infiltrated
that of the control by fluorescent
group. After 10 resin. The specimens
The above shown
results clearly contain
demonstrate Graywacke
that organo- aggreg
sed to 3% NaCl solution. Blueexposure
arrow denotes cracks
cycles, the average through hardened
strain value reachedcement paste.
silicon Red arrow
chemicals denotes inhibit
can effectively cracksthethrough
ASR- coarse a
0.94 mm/m, which is well above the expansion induced expansion in concrete, even if the concrete
limit. However, the specimens mixed with the si- contains highly alkali-sensitive aggregates and/or
lane/siloxane emulsion remained almost fully in- excessive alkali supplies are present. The reason for
tact. The strain increased very slowly, and the av- this beneficial effect results from the hydrophobic
erage value did not exceed 0.34 mm/m, which was properties of siloxane- and silane-based agents
the best performance among all groups. Therefore, which come into play. ASR issues occur as soon as
specimens admixed with silane/siloxane emul- alkali and reactive silica are present and form gel
sions had the most ASR-stable properties, even products inside the concrete. However, if there is no
if undergoing the very harsh cyclic exposures to or only limited access to moisture, the ASR gel will
NaCl solutions with concentrations up to 10%. not be subject to swelling which is the root cause for
The results for the rhyolite aggregates in Figure 7, detrimental stress build-up and cracking inside the
right, were also encouraging. The control speci- concrete mass.
mens again showed a steady increase of average As shown above, organosilicon admixtures such
strain which was significantly milder than that of as silanes or siloxanes can render the cementitious
the graywacke control group due to the lower reac- matrix highly hydrophobic. Consequently, any po-
tiveness of rhyolite with alkali. The average strain tential pathways to ASR gels inside the matrix can
value after 10 exposure cycles was 0.42 mm/m, be hydrophobized, preventing moisture from get-
without exceeding the 0.5 mm/m limit. The speci- ting into contact with the swellable gels. Even path-
mens admixed with a plain silane produced lower ways formed at later stage, e.g. microcracks related
expansion levels than the control specimen. Af- to ongoing thermal or mechanical stress, remain
ter 10 exposure cycles, the average strain value water repellent, owing to the integral nature of the
reached 0.29 mm/m. This shows that silanes can hydrophobic treatment. Hence, ASR-induced dam-
effectively prevent ASR-induced expansions in age can be avoided reliably.
cementitious systems containing rhyolite aggre- By this means, the use of organosilicon admix-
gates. Best among all, however, was the silane/si- tures is a preventive measure, which is especially
loxane emulsion specimen. It hardly produced any advantageous when ASR-unstable raw materials
volume increase during the entire test period. The are encountered in real life applications. More-
average strain value after 10 cycles reached 0.04 over, organosilicon admixtures create sufficiently
mm/m, which is more than ten times below the stable bonds with cementitious phases, even un-
official expansion limit and far below the control der harsh chemical or physical conditions. This
specimen values. This is very convincing evidence further enhances the long-term protection against
that the silane/siloxane emulsions can effectively ASR effects, as the hydrophobic performance can
help to inhibit ASR in specimens containing rhyo- be well preserved over an extended period of time.
lite aggregates even undergoing cyclic exposures A straightforward example is presented in Figure 8.
to 10% NaCl solutions. In the untreated specimen (Figure 8, left), major

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 MATERIALS

through cracks have developed in the grains of the coarse aggre-

gate, due to the ASR effect. While in the treated specimen (Figure
8, right), hardly any cracks have formed in the matrix.

4 Summary
Organosilicon hydrophobic agents are highly versatile and yet
unique chemicals which enable extraordinary waterproofing
performance in cementitious materials. Due to their exceptional
chemical and physical stability, they can achieve particularly
effective water repellency and can significantly enhance con-
crete durability even under very harsh conditions. In addition to
surface treatment applications, organosilicon agents can also be
used as integral waterproofing agents. In this case, their protec-
tion against undesired water penetration into the cementitious
mass is more distinct and more durable. Furthermore, the inte-
gral use of organosilicon agents can provide further beneficial
effects against water-associated deterioration processes such as
the Alkali Silica Reaction. Such products are able to enhance the
ASR stability of concrete, even if ASR-unstable raw materials
are present in the cementitious matrix.
www.wacker.com

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