50th ASEP Anniversary International Convention & Exposition, “Safer, Smarter & Greener”

Technical Proceedings ISSN 1656-7757, September 28-30, 2011 Makati City, Philippines

POSSIBILITY OF SEA WATER AS A GREENER MATERIAL IN

CONCRETE
Nobuaki Otsuki, Tokyo Institute of Technology, Japan
Daisuke Furuya, Tokyo Institute of Technology, Japan
Tsuyoshi Saito, Tokyo Institute of Technology, Japan
Yutaka Tadokoro, Nippon Steel ＆ Sumikin Stainless Steel Corporation, Japan

ABSTRACT: In the near future, fresh (tap) water will be very difficult to get and scarce. It is
said that in 2025 half of the mankind will live in the areas where fresh (tap) water is not
enough. Also, UN and WMO are predicting 5 billion people will be in short of even
drinking water. Also, in the present, there are some areas where sea water or chloride
contained water are used as mixing water with or without intension.

The authors believe that the possibilities of using sea water as mixing water in concrete
should be investigated seriously.

In this paper, the authors would like to show various possibilities of using sea water as
mixing water in RC members.
The possibilities are shown as follows;
1. Mixed with pozzolanic materials (Blast furnace slag powder, Fly ash, etc.) expecting to
fix the free chloride ion.
2. Mixed with corrosion inhibitor.
3. Reinforced with stainless steel or corrosion resistant reinforcement.
4. Others.

KEYWORDS: sea water; blast furnace slag; corrosion; stainless steel; hydration products;

1. INTRODUCTION

Besides shown in the introduction, the authors have investigated chloride attack in marine
environment. In these investigations, the authors compared durability of concrete with OPC
and BFS cement and mixed with fresh water and sea water. The results (the authors will
show the research in the later chapter) showed "the difference of durability between the
concrete mixed with fresh (tap) water and mixed with sea water is not so much, but the
difference between the concrete with OPC and BFS cement is very large. Also, the BFS
cement concrete mixed with sea water showed better durability than the OPC concrete mixed
with fresh (tap) water."

Inspired by the fact, the authors believe there are various possibilities of using sea water as
mixing water from the point of concrete technology.

In this paper, the following possibilities are introduced.

(1). Mixed with pozzolanic materials (Blast furnace slag powder, Fly ash, etc.) expecting to
fix the free chloride ion.
(2). Mixed with corrosion inhibitor.
(3). Reinforced with stainless steel or corrosion resistant reinforcement.
Also, the possibility of using sea water as curing water was investigated.

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 50th ASEP Anniversary International Convention & Exposition, “Safer, Smarter & Greener”
Technical Proceedings ISSN 1656-7757, September 28-30, 2011 Makati City, Philippines

2. MIXED WITH VARIOUS KIND OF CEMENT

In 1969, around 200 specimens were manufactured to examine the effect of sea water as
mixing water and exposed in tidal zone in Yokosuka, Japan. The followings show the
specimens, materials, test results and considerations [1].

2.1 Materials and manufacturing specimens

2.1.1 Materials

As cements, Ordinary Portland cement, High Early Strength cement, Moderate cement, Blast
Furnace Slag cement and Aluminate cement were used. Also, the amounts of SO3 were
changed. Some cements contained 2% more SO3 than the others.
As mixing water, fresh water and sea water were used. The chemical components of sea
water are shown in Table 1.
River gravel was used for coarse aggregate, and the maximum size was 25mm. Also, river
sand was used as fine aggregate.
The used steel bars were 9mm diameter round bars which were conformed to the Japan
Industrial Standard. The steel bars were treated by 2% ammonium citrate to be no rust and
shiny surface.

2.1.2 Manufacturing specimens

The mix proportions of concrete are shown in Table 2.

The size of the specimen was 15cm diameter and 30cm height. There were specimens for
strength, potential measurement and steel corrosion. Also 3 steel bars were embedded in the
specimens for potential and corrosion, whose covers were 3, 5 and 7cm as shown in Fig. 1.

2.1.3 Curing

The specimens were de-molded one day after casting, except specimens with aluminate
cement in that case they were de-molded 4 days after casting. After de-molding, the
specimens were cured in under water (21 degree) until 7 days old after casting. Then the
specimens were exposed in tidal condition.

2.2 Test items

2.2.1 Compressive strength

Compressive strengths were measured at the ages of 7days (only for high early strength
cement concrete), 28days, 1 year, 5 years, 10 years and 20 years. The tests were performed
according to Japan Industrial standards. In a same condition, 3 specimens were tested and the
test data were averaged.

2.2.2 Corroded areas of steel bars

Corroded areas of steel bars were measured using a planimeter and percentages against steel
bars’ surfaces were calculated. For each conditions 3 to 5 steel bars were tested and the
values were averaged.

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 50th ASEP Anniversary International Convention & Exposition, “Safer, Smarter & Greener”
Technical Proceedings ISSN 1656-7757, September 28-30, 2011 Makati City, Philippines

2.2.3 Corrosion depths of steel bars

Corrosion depths of steel bars were measured at the ages of 20 years using a thickness gauge.

2.3 Test results and considerations

2.3.1 Compressive strengths

The compressive ratio was defined as the ratio between the compressive strength of concrete
mixed with sea water and that mixed with fresh water. The time dependent changes of the
compressive strength ratios were shown in Fig. 1. From this figure, the ratios were
somewhere between 0.9 to 1.1, and the influence of mixing water was not so much.

2.3.2 Corroded areas of steel bars

The time dependent changes of corroded areas were shown in Fig.3. As shown from this
figure, the influence of the kind of cement is much larger than those of mixing water. Also, it
is clearly recognized that the influence of mixing water is negligible.
The corrosion resistant ability of BFS cement can be recognized far better than those of OPC,
HSC and moderate cement even mixed with sea water.

2.3.3 Corrosion depths

The corrosion depths after 20 years’ exposure are shown in Fig.4. As shown from this figure,
the influence of the kind of cement is larger than that of mixing water. The corrosion depths
with BFS are less than the others’ no matter the kind of mixing water.

2.4 Conclusions

From this 20 years’ exposure test, the kind of mixing water has little influence on the strength
and corrosion. Especially about corrosion, the specimens with BFS is far better than with
OPC, HSC and moderate cement notwithstanding the kind of mixing water. So, in tidal zone,
there is possibility use sea water as mixing water, considering the kind of cement.

Table 1. Chemical compositions of sea water as mixing water

Density pH Chemical compositions (mg/l)
(20 °C) (20 °C) Na K Ca Mg Cl SO4 CO3

1.024 8.03 10125 387 376 1180 17136 2412 65

Table 2. Mix proportions of concrete

Cement Mixing G.max Slump Air W/C S/a Unit amount
type water (mm) (cm) (%) W C S G Ad(l) AE(c.c.)
OPC Freshwater 25 6.6 3.4 52.7 37.0 153 290 740 1261 2.9
Sea water 25 5.6 3.2 53.4 36.0 155 290 718 1277 2.9 -
OPC+SO3 Freshwater 25 6.4 4.0 54.5 37.0 158 290 734 1251 2.9 -
Sea water 25 5.1 3.4 55.2 36.0 160 290 713 1270 2.9 -
HPC Freshwater 25 3.7 3.9 53.1 37.0 154 290 738 1258 2.9 -
Sea water 25 5.7 3.1 55.2 36.0 160 290 711 1263 2.9 -

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 50th ASEP Anniversary International Convention & Exposition, “Safer, Smarter & Greener”
Technical Proceedings ISSN 1656-7757, September 28-30, 2011 Makati City, Philippines

Moderate Freshwater 25 6.5 4.8 52.4 37.0 152 290 7742 1264 2.9 -
Sea water 25 4.6 4.0 53.1 36.0 154 290 720 1280 2.9 -
BFS Freshwater 25 3.5 3.0 52.4 37.0 152 290 738 1258 2.9 -
Sea water 25 4.0 3.8 53.1 36.0 154 290 716 1274 2.9 -
BFS+SO3 Freshwater 25 4.2 3.8 54.8 37.0 159 290 729 1242 2.9 -
Sea water 25 4.7 4.1 55.5 36.0 161 290 708 1258 2.9 -
Aluminate Freshwater 25 6.3 3.1 52.1 37.0 151 290 737 1256 2.9 20
Sea water 25 5.1 3.5 52.8 36.0 153 290 716 1272 2.9 -

Figure 1. The outline of the specimen for corrosion test

Figure 2. Time dependent changes of compressive strength ratios (mixed with sea
water/mixed with fresh water)

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 50th ASEP Anniversary International Convention & Exposition, “Safer, Smarter & Greener”
Technical Proceedings ISSN 1656-7757, September 28-30, 2011 Makati City, Philippines

Fresh water as mixing water

Figure 3. The time dependent changes of corroded areas (%)

Fresh water as mixing water

Figure 4. Corrosion depths of steel bars after 20 years’ exposure

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 50th ASEP Anniversary International Convention & Exposition, “Safer, Smarter & Greener”
Technical Proceedings ISSN 1656-7757, September 28-30, 2011 Makati City, Philippines

3. MIXED WITH CORROSION INHIBITOR

It is reported that the NO2-/Cl- ratio is over 0.82, the steel bars can be protected from
corrosion, and the surface of the steel bars are passivated.
In the case of the mix proportions shown in Fig.2, the chloride contents are around 2.74
kg/m3 and 77.2mol/m3. This is calculated by the water content (160kg/m3) and chloride
concentration of the used sea water (17100ppm).
Also, same kind of corrosion inhibitor contains 35% Ca(NO2)2 in the solution. The
manufacturer showed the properties of concrete (strength, setting time, etc.) have no problem
adding the inhibitor up to 20l/m3, and it means 4.9kg/m3 and 106.5mol/m3. Then the NO2-/Cl-
ratios can be up to 1.38.
It means there is a good possibility using sea water as mixing water with corrosion inhibitor.

4. REINFORCED WITH STAINLESS STEEL OR CORROSION RESISTANT

STEEL BARS

According to the Standard Specification for Concrete Structures（JSCE），critical chloride

ion concentration of carbon steel bars is 1.2kg/m3 [2]. Chloride ion content in sea water
mixing concrete is calculated to be 2.74kg/m3, therefore carbon steel bars can not be used.
Corrosion-resistant steel bars will be used there. There are epoxy-coated bar and stainless
steel bar in corrosion-resistant steel bars. For epoxy-coated reinforcing bar, corrosion occurs
when chloride ion concentration on the steel bar under the epoxy-coating film exceeds
1.2kg/m3 [3]. If there are scratches on the coating, corrosion occurs from the area. Critical
chloride ion concentration for stainless steel bars (Clim) are different depending on the grade
of stainless steel’s corrosion resistance [4].Critical chloride ion concentrations of stainless
steel bars provided in JIS G 4322, as shown in Fig. 5, are much higher than 2.74kg/m3. If
appropiate structure design (cover, W/C, etc.) is performed, the sea water mixing concrete is
considered to be available. In addition in carbonated concrete, critical chloride ion
concentration of SUS410-SD, most cost-effective stainless steel bar, is 3kg/m3, which can be
used in environments with chloride ion concentration does not increase due to salinity ingress
[5]. As mentioned above, for reinforcement corrosion, sea water mixing concrete can be used
by using stainless steel reinforcing bars.

Figure 5. Recomended value of JSCE and experimental result value of critical chloride ion
concentration of stainless steel bars
Clim： threshold chloride ion concentration of stainless steel bars

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 50th ASEP Anniversary International Convention & Exposition, “Safer, Smarter & Greener”
Technical Proceedings ISSN 1656-7757, September 28-30, 2011 Makati City, Philippines

5. HYDRATION PROPERTIES OF CEMENT USING SEA WATER AS MIXING

WATER

As shown in Chapter 2, BFS has an advantage in using sea water as mixing water. So in this
chapter, the reaction ratios, pore volumes and compressive strength of early ages are shown
in the case of BFS with sea water and fresh water.
The results of slag reaction ratio tests of BFS cement (Type C) mixing with sea water and
fresh (tap) water are shown in Fig. 6. Specimens were prepared with BFS cement paste
whose replacement ratio of BFS to OPC was 70% and water cement ratio was 0.5. Size of the
specimens was 10×10×40 mm and pre-curing was carried out for 24 hours. At a set time, the
specimens were crushed to prepare the powder specimens passing through the 150μm sieve
for the each chemical analysis.
Mixing with sea water raises the BFS reaction ratio compared to mixing with fresh (tap)
water for the entire period. The increasing has the largest value at 1st day, since then, reduced
and remained.
The results of mercury intrusion porosimetry of BFS cement mixing with sea water and fresh
(tap) water are shown in Fig.7. Total pore volume was decreased by mixing with sea water
compared to data of 1st day. BFS reaction ratio with sea water was lager than that of fresh
(tap) water . Therefore, total pore volume with sea water decreased compared to fresh (tap)
water.

: Sealed curing after mixing with fresh (tap) water

: Sealed curing after mixing with sea water

Figure 6. Influence of mixing with sea water on slag reaction ratio on BFS cement

: Sealed curing after mixing with fresh (tap) water

: Sealed curing after mixing with sea water

Figure 7. Influence of mixing with sea water on pore volume on BFS cement

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 50th ASEP Anniversary International Convention & Exposition, “Safer, Smarter & Greener”
Technical Proceedings ISSN 1656-7757, September 28-30, 2011 Makati City, Philippines

The results of compressive strength tests of BFS cement mixing with sea water and fresh
(tap) water are shown in Fig. 8. BFS cement was strengthened in entire period by mixing
with sea water. Strength depends on the micropore structure; accordingly, the representative
index is the total pore volume and the pore diameter. It is concluded that mixing with sea
water decreases the amount of pores, and then strength of BFS cement with sea water was
increased.

: Sealed curing after mixing

with fresh (tap) water
: Sealed curing after mixing with sea water

Figure .8 Influence of mixing with sea water on compressive strength on BFS cement

6. HYDRATION PROPERTIES OF CEMENT USING SEA WATER AS CURING

WATER

In this chapter, the reaction ratios, pore volumes and compressive strength of early ages are
shown in the case of BFS with sea water and fresh water as curing water.
The results of slag reaction ratio tests of BFS cement (Type C) curing with sea water and
fresh (tap) water are shown in Fig. 9. Specimens were prepared with same condition as
chapter 5.
Curing with sea water raises the BFS reaction ratio compared to curing with fresh (tap) water
after 7th day. The BFS reaction ratio cured with sea water was increasing after 7th day while
that with fresh (tap) water remained after 7th day.
The results of mercury intrusion porosimetry of BFS cement curing with sea water and fresh
(tap) water are shown in Fig.10. Total pore volume was decreased by curing with sea water
compared with fresh (tap) water. BFS reaction ratio with sea water was lager than that of
fresh (tap) water. Therefore, total pore volume with sea water decreased compared to fresh
(tap) water. WW: Underwater curing after mixing with fresh (tap) water
WS: Seawater curing after mixing with fresh (tap) water

Figure 9 Influence of curing with Figure 10 Influence of curing with

seawater on slag reaction ratio on seawater on pore volume on BFS
BFS cement cement

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 50th ASEP Anniversary International Convention & Exposition, “Safer, Smarter & Greener”
Technical Proceedings ISSN 1656-7757, September 28-30, 2011 Makati City, Philippines

The results of compressive strength tests of BFS cement curng with sea water and fresh (tap)
water are shown in Fig. 11. The compressive strength with sea water was slightly larger than
that with fresh (tap) water. Strength depends on the micropore structure; accordingly, the
representative index is the total pore volume and the pore diameter. It is concluded that
curing with sea water decreases the amount of pores, and then strength of BFS cement with
sea water was increased.
The investigations about the long-term compressive strength (after 91st day) and hydration
properties with sea water could be needed, in order to apply the sea water as curing water in
an effective way.

WW: Underwater curing after mixing with fresh (tap) water

WS: Seawater curing after mixing with fresh (tap) water

Figure 11 Influence of curing with sea water on compressive strength on BFS cement

7. CONCLUSIONS

From the test results and discussions shown above. The authors are confident to safely use
sea water as mixing water. The countermeasures of using sea water as mixing water are as
follows;
1) Use BFS cement or other blended cement instead of OPC
2) Use corrosion inhibitor.
3) Reinforced with stainless steel or corrosion resistant reinforcement.
Nowadays, the design method is changing to “Performance based design”, so if the
performance in the expected life can be proved over the required level, the concrete mixed
with sea water can be used.
Of course, there are some problems which need more research.

REFERENCES

Japan Society of Civil Engineers, Standard Specifications for Concrete Structures, Design,
2007(in Japanese).

Japan Society of Civil Engineers, Concrete Library 112, “Recommendations for design and
construction of concrete structures using epoxy-coated reinforcing steel bars”, 2003(in Japanese).

Japan Society of Civil Engineers, Concrete Library 130, “Recommendations for design and
construction of concrete structures using stainless steel bars (Draft)”, 2008 (in Japanese).

T. Fukute, K. Yamamoto, H. Hamada: Study on the Durability of Concrete Mixed with Sea water,
Report of the Port and Harbour Research Institute, Vol.29, No.3, 1990 (in Japanese).

Y.Tadokoro, M.Kojima, N.Otsuki: Corrosion propagation behavior of stainless steel reinforcing

bars in concrete, Zairyo-to-kankyo, Vol.59, No.5, pp.179-186, 2010 (in Japanese).

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 50th ASEP Anniversary International Convention & Exposition, “Safer, Smarter & Greener”
Technical Proceedings ISSN 1656-7757, September 28-30, 2011 Makati City, Philippines

ABOUT THE AUTHORS

Author One is the professor of Tokyo Institute of Technology Japan since 1995. E-mail
nobuakiotsuki2000@yahoo.co.jp

Author Two is the master course student of Tokyo Institute of Technology Japan since 2009. E-mail
furuya.d.aa@m.titech.ac.jp

Author Three is the assistant professor of Tokyo Institute of Technology Japan since 2007. E-mail
saito.t.ac@m.titech.ac.jp

Author Four is the worker of Nippon Steel ＆ Sumikin Stainless Steel Corporation. E-mail
tadokoro.yutaka@ns-sc.co.jp

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