506 Vol.24 No.

3 LIU Juanhong et al: Durability and Micro-structure of Reac…

DOI 10.1007/s11595-009-3506-1

Durability and Micro-structure of Reactive

Powder Concrete

LIU Juanhong1, SONG Shaomin2, WANG Lin2

（1. College of Civil and Environmental Engineering, Beijing University of Science and Technology, Beijing 100083, China; 2. College of Civil and Trans-
portation Engineering, Beijing Institute of Civil Engineering and Architecture, Beijing 100044, China）

Abstract: Durability of traditional reactive powder concrete (RPC) with rich cement and high
volume of fly-ash reactive powder concrete (FRPC ) were studied. The X-diffraction and scanning
electron microscope (SEM) measurement was imployed to analyze the microstructure. The results
show that both types of RPC have higher compressive strength, less volume shrinkage ratio and better
carbonation-, chloride-, freezing-resistances than the conventional concrete. The results of
X-diffraction indicate that they basically have C-S-H as the main composition without Ca(OH)2 crystal
and ettringite. SEM results show that hydration products of FRPC is mainly Ⅲ-C-S-H which is piled
up closely like densely arranged stone body and it has very compacted structure, in addition, Ca/Si ratio
of C-S-H gel is lower than 1.5.
Key words: reactive powder concrete; high volume fly-ash reactive powder concrete (FRPC),
durability; microstructure

1 Introduction its physical properties are listed in Table 1.

Silica fume was supplied by Shanghai Elkem in-
Reactive powder concrete (RPC) is a modern ce- ternational trade company. The apparent density was
ment-based composite material with super high com- 2.3 g/cm3. The average grain diameter was 0.12 µm and
pressive strength and high performance which is devel- the specific surface area was 17.6 m2/g. The fly ash used
oped by France Bouygues laboratory according to the was classⅠfly ash. The fineness was 4% (45 µm sieve
principle of close packing by eliminating the coarse ag- residue). The apparent density was 2.25 g/cm3 with the
gregate [1,2]. This research produced traditional RPC by loss of ignition of 4.30%. The water demanding ratio was
using P.O Grade-42.5 Portland cement, silica fume, fly 95.8% and the compressive strength ratio 83%, while the
ash, milled quartz sand, superplasticizer and steel fibers. sand was grinded into two sizes , 0.16-0.315 mm and of
Meanwhile the same time, high-volume fly ash RPC 0.315-0.40 mm, which were mixed at the proportion of
(FRPC) was developed in which fly ash content is up to 1︰1. The superplasticizer was supplied by sika com-
58 wt% of total binding materials. An experimental study pany. The water reduction was 30%, and the density was
on the two types of RPC was made out. 1.05 g/cm3 and the solid content was 30%. Copperized
steel fiber was supplied by Changhong steel fiber factory,
2 Experimental with a diameter of 0.12 mm and a length of 12-13 mm.
2.2 Mixture proportions and sample
2.1 Materials preparation
The cement used was Lafarge P.O Grade-42.5 and Conventional RPC was prepared by increasing the
fineness and activity of components to minimize the
Table 1 Physical properties of cement interior flaws (pores and tiny cracks) and achieve a per-
Compressive Bending Normal fect compaction at proper hydration and hardening con-
Set time /min Fine-ness
strength/ MPa strength/MPa consis- dition to improve microstructure, with aspect ratio and
/%
Initial Final 3 d 28 d 3 d 28 d tency/% content of steel fibers to improve brittleness of RPC.
163 204 28.4 52 6.2 8.8 3 27.2 Detailed mixture proportions are listed in Table 2.
High-volume fly ash reactive powder concrete
(FRPC) was prepared by changing the fly ash content
(Received: May 6, 2008; Accepted: Dec. 20, 2008)
based on the basic principle of RPC. Detailed mixture
LIU Juanhong(刘娟红): Assoc. Prof.; juanhong1966@hotmail.com
proportions are shown in Table 3.
 Journal of Wuhan University of Technolotgy-Mater. Sci. Ed. June 2009 507

Table 2 Mixture proportions of RPC(kg·m－3)

Cement Silica fume Fly ash Sand Water Superpl-asticizer Steel fibers
788 197 158 985 170 34 200

Table 3 Mixture proportions of FRPC(kg·m－3)

Cement Silica fume Fly ash Sand Water Superpl-asticizer Steel fiber
394 197 552 985 170 34 200

Horizontal uniaxial forced concrete mixer was used. Table 4 Compressive strength
First, cement, silica fume and fly ash were mixed for Concrete Load/kN Compressive strength/MPa
3 min till uniformity. Second, fine sand was added into RPC 1 650 165
mixture and they were mixed for another 3 min. Then, 2/3 FRPC 1 250 125
water and the superplasticizer were added in, and the left
1/3 water was added into the mixture. Finally, mix them
3 Results and Discussion
round to make sure concrete have a certain fluidity and
add steel fibers into mixture, and mix round for 5 min to
make them dispersed uniformly. The mixtures were 3.1 Volume shrinkage
handled into moulds and vibrated on a vibrostand for The shrinkages of concrete at natural condition
5 min (vibration frequency 50 Hz). After 24 h, they were without outside force were measured. RPC can be re-
demoulded and placed in the condition of 90 ℃ steam for garded as mortar for there are no coarse aggregate. The
24 h, then placed in 90 ℃ hot water till to room tem- specimens with 25 mm×25 mm×285 mm dimensions
perature. In Table 4, the compressive strength is listed were prepared for shrinkage. The results are shown in
after steam curing. Table 5.
Table 5 Early-age shrinkage of RPC and FRPC
Age /d 1 3 7 14 28 45 60 90
RPC Shrinkage(E－6) －158.36 －218.19 －285.05 －302.65 －306.17 －316.72 －323.76 －327.28
FRPC Shrinkage(E－6) －112.79 －144.51 －158.61 －183.28 －190.34 －204.43 －204.43 －207.96

From the data above, the shrinkage of RPC is less
than ordinary concrete (in general, limit of ordinary
concrete shrinkage is 0.05%-0.09%) as steel fibers re-
stricted the shrinkage like aggregate in concrete. In ad-
dition, the hydration rate of fly ash is very slow, though it
is a kind of active admixture. It is responsible for in-
creasing effective w/c ratio at early stage and has some
restraining effect on early-age shrinkage of concrete.
Especially for FRPC there is relatively less cement con-
tent and higher volume of fly ash. Though the w/b ratio is
very low, at early-age effective water cement ratio of
FRPC is relatively high. It is beneficial to hydrating suffi-
ciently to fill pores and provide more C-S-H[3].
3.2 Chlorine ion permeation experiment
Strong alkali brought by cement hydration promotes
the reinforcing steel bars in concrete to form a dense
passivation layer on the surface that protecting them from
rusting. The passivation layer becomes unstable when
pH<11.5. When pH<9.88, it is very hard to protect steel
－
from rusting. Cl ions have extremely strong activation,
which can decrease alkalinity and demolish the passiva-
－ zation depth of RPC and FRPC are zero. The carbonization
tion layer around the surface of steel bars where Cl ions
arrive. Otherwise, Chlorine ions are very easy to perme-
ate into concrete because of its small ion diameter.
The coefficient of Cl－ ions diffusion was obtained
by the method of NEL-PD electricity apparatus. The
results was compared with that of C80 high strength
concrete, shown in Table 6.
Table 6 Coefficient of chlorine ion diffusion
－ －
Concrete Coefficient of Cl ion diffusion/(cm2/s 1)
－8
RPC 0.405×10
FRPC 0.508×10－8
C80 1.08×10－8
The coefficients of chlorine ion diffusion of RPC
and FRPC are somewhat similar which is about half of
C80 high strength concrete. It is obvious that RPC has
excellent chlorine ions diffusion resistance for the low
water to binder ratio of RPC[4-6]. The w/b ration of RPC is
extremely low and the redundant water in concrete is very
little. The porosity of concrete decreases and the whole
compaction is improved. At the same time, silica fume
and fly ash fill in the interface transition zones and the
interstice between grain particles. The whole structure
are greatly dense, so that the Cl－ ion permeation resis-
tance of concrete is vey well.
3.3 Carbonization resistance of RPC
Quick carbonization method was used to determine
the carbonization resistance of RPC. The specimens of
RPC were placed in carbonization box after steam curing.
CO2 concentration is 20% and the temperature was 20 ℃.
After 28 d, carbonization depth was measured. The carboni-
takes place just on the surface rather than in concrete interior.
In general, carbonization rate of concrete is propor-
tional to the square root of CO2 concentration. When
concrete is exposed to environment of carbon dioxide
with concentration of 20%, at 20 ℃, RH 70% for 28 d, its
carbonization degree corresponds to carbonization at
natural conditions for 50 years. RPC has excellent car-
508 Vol.24 No.3 LIU Juanhong et al: Durability and Micro-structure of Reac…

bonization resistance. The 28 d carbonization depth of dently because secondary hydration of fly ash at early
RPC and FRPC is zero for high compaction of concretes stage develops slowly.
themselves, although the initial alkalinity of FRPC is 3.5 Freezing resistance of RPC
lower. Extremely low w/b ratio, fine active particles, and Specimens with 100 mm×100 mm×400 mm in
hydration products filling in cement gel pores and tiny dimensions were used to investigate the freezing resis-
cracks reduce the pore diameter of RPC, change pore tance. Specimens were immersed in water for 4 d after
configuration, increase concrete compaction, and make it steam curing, and then were placed in the apparatus of
hard for carbon dioxide to enter concrete interior and to rapid freezing and thawing. Specimens were taken out
react with Ca (OH) 2. Moreover, it is almost entirely ex- after every 100 cycles of freezing and thawing for
hausted after steam curing and there is too little water for measuring weight change and dynamical elastic modulus.
CO2 and Ca (OH)2 to react.
The results are shown in Figs.2, 3.
3.4 Sulphate resistance of RPC
Specimens with 100 mm×100 mm×100 mm were
used for sulphate resistance test. The specimens were
immersed in saturated solution of sodium sulphate, then
dried in an oven at 90 ℃ for 48 h. Surface corrosion
degree of RPC was observed and weights of specimens
were measured after each cycle. Weight changes of speci-
mens are shown in Fig.1. Compressive strength after 10 cy-
cles, 20 cycles, and 30 cycles are listed in Table 8.

Fig.2 Weight change of specimens

Fig.1 Weight change of specimens

Table 7 Strength change of test cubes cured in saturated solu-
tion of sulphate
Initial Strength after Strength after Strength after
Concrete strength 10 cycles 20 cycles 30 cycles
/MPa /MPa /MPa /MPa Fig.3 Dynamic elastic modulus of concrete
When the cycle times of RPC reach 1 600, there
RPC 165 181 193 199
were no evident cracks on the surface and the loss of
FRPC 130 179 186 191 weight is zero. RPC have high durability for combination
Table 8 Compressive strength of test cubes cured in water of steel fibers and silica fume. On one hand, steel fibers
Initial After 10 After 20 After 30 not only restrict enlarge the plastic cracks at early age,
Concrete strength cycles cycles cycles
but also restrain interior cracks created by frost-heave
/MPa /MPa /MPa /MPa
force. On the other hand, high reactive silica fume fills in
RPC 165 170 170 172
interstices between cement grains, reacts with Ca(OH)2
FRPC 130 130 132 138
in pores of hardened cement paste and creates more
The results indicate that weights of RPC and FRPC C-S-H gel[7]. In addition, silica fume improves the inter-
slightly change, less than 2%, and trend to be stable with face zone structure and strengthens the bongding be-
strength enhancing all along and the surface of cubes
remains intact after 20 cycles. tweem cement-matrix with steel fibres.
High volume active admixtures can largely improve 3.6 Analysis of X-ray diffraction
the sulphate resistance of RPC. Silica fume improves the X-ray diffraction was employed to analyze the hy-
interface structure between aggregate and cement paste dration compositon of RPC and FRPC.
and solve the problem of Ca(OH)2 concentrating. Low Figs.4 and 5 indicate that RPC and FRPC almost
w/b ratio and compacted structure of concrete improve have the same composition of quartz sand SiO2, C-S-H,
impermeability and restrict sulphate solution. Moreover, C2SH, few C-A-H and some unhydrated cement particles
fly ash and silica fume reduce Ca(OH)2 content in hard- without Ca(OH)2 crystal and ettringite. Because much
ened cement paste. Thus , the sulphate corrosion of con- Ca(OH)2 reacts with fly ash, the Ca(OH)2 crystal can not
crete only takes place on the surface instead of the inte-
rior. The strength of RPC increases continuously for the be produced under the low w/b. Meanwhile, ettringite at
hydration still takes place. In addition, the high tem- 70 ℃ will decompose, so ettringite can not exist stably in
perature of 90 ℃ accelerates the secondary hydration, the cement under hot curing. CaO and the siliceous ma-
and the strength keeps on increasing. However, the terial will fully integrate under the wet-hot curing for a
strength of concrete cured in water doesn’t increase evi- long time at 90 ℃. Hydrated product will transform to the
single crystallization, so that the amount of ettringite will
 Journal of Wuhan University of Technolotgy-Mater. Sci. Ed. June 2009
reduce and it’s difficult to ettringite crystallizes perfectly. In
addition, Aft crystal is very difficult to obtain at low w/b[8, 9].
Fig.4 X-radial diffraction atlas
Fig.5 XRD-pattems
3.7 Analysis of EMS
SEM images of FRPC are shown in Fig.6. The
whole structure is compact and aggregates, and ce-
ment-matrix are boned perfectly. The hydration products
are mainly some irregular-shaped, and flat particles
compacted closely, whose appearance approaches in Ⅲ
C-S-H gel. The gel is similar to typeⅠC-S-H gel in some
pores in Fig.7(b). The results show that the structure is
quite dense, without space for typeⅠC-S-H gel to grow,
which just exists in some small pores.
Fig.6 SEM images of FRPC(a) aggregates and cement-matrix
surface, (b) different types of C-S-H gel
Fig.7 Energy dispersive spectroscopy (EDS) of four points in Fig.6(b)
According to energy dispersive spectroscopy
analysis, C-S-H gel of four points produced in the pore is
not completely amorphous materials, and C-S-H gel
phase are clostridium with the Ca/Si of about 1.41.
509
4 Conclusions
a) The shrinkage of RPC is approximate to ordinary
concrete at early age, the shrinkage at 28 d is less than
0.04%, and shrinkage tends to be stable after 28 d curing.
The coefficient of diffusion of RPC is 0.405×10 8 cm2/s,
－
and the coefficient of diffusion of FRPC is 0.508×10 8 cm2/s.
－
Both of them are about half of C80 high strength concrete
(1.08 × 10 8 cm2/s). RPC and FRPC have excellent
－
permeability resistant. Carbonization depth of RPC and
FRPC is almost zero in the condition of carbon dioxide
concentration of 20%, 20 ℃, RH 70%. The concrete will
be prevented from carbonization harm for more than 50
years at natural condition.
b) RPC has a strong sulphate resistance, and corro-
sion takes place on the surface. RPC has a super-high
freezing resistance. When freeze-thawing cycles reach
1 600 times, weight and dynamic elastic modulus of speci-
mens vary little.
c) Similar compositions are found in RPC and FRPC,
including quartz sand SiO2, C-S-H, C2SH, few C-A-H
and some unhyratedcement particles without Ca(OH)2
crystal and ettringite, and hydration products of FRPC
are mainly type-ⅢC-S-H, which are piled up closely and
very compact, while Ca/Si of C-S-H gel is below 1.5.
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