Construction and Building Materials 23 (2009) 3579–3582

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Construction and Building Materials

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Effects of the very low water/cement ratio

Vladimír Živica *
Institute of Construction and Architecture of Slovak Academz of Science, Dúbravská cesta 9, 84 503 Bratislava 45, Slovak Republic

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

Article history: The subject of paper are the results of the study on the hardened cement paste prepared with very low
Received 8 April 2008 w/c ratios from 0.115 till 0.075 and pressure compaction till 300 MPa. Well known and often reported the
Received in revised form 5 March 2009 significant compressive strength increase and the total porosity and pore median decrease was found. But
Accepted 12 March 2009
other significant effects have been found: an increase of the CaO:SiO2 and the decrease of H2O:SiO2 ratios,
Available online 8 September 2009
their consequence were the particles morphology changes shown as a gradual loose of the crystal char-
acter under the formation of the finer spherical and cylindrical particles of the hydration products show-
Keywords:
ing the increase in the biding capacity and the increase of the homogeneity of the pore structure. These
Water–cement ratio
Pressing
factors seem to be the principle of the extreme effects of the very low w/c ratio and pressure compaction
Mechanical properties used. In the final consequence the fine-grain character and form and dimension increased homogeneity
Pore structure enabling the formation of the amount of the strength connection among the individual particles into and
Hydration products extraordinary dense structure seem to be the principle effect of the very low w/c ratio and pressure com-
Composition paction of the cement mixtures.
Morphology Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction 2. Experimental

The dependence of the engineering properties of concretes and
other cement composites of the value of water/cement ratio (w/c)
is very well known. Also the fact that their strengths, durability
and the quality of other engineering properties are increased when
the w/c values are decreased [1–3]. A significant factor limiting the
use of this positive effects is the fact that by the decrease of the w/c
ratios, the workability of the fresh composite mixture and the
resulting engineering properties of the hardened composite are de-
creased. A limited solution enables the use of the plasticizers or of
the superplasticizers. A very attractive solution represents the
combination of super low w/c ratios, under w/c 0.1 and deeper,
resulting in a submicroscopic pore structure and an adequate high
quality of the engineering properties of the composite [4–10]. It
appears that the low porosity cement composites have a great po-
tential of reconsideration and modification if composition and
structure. It represents also a serious research topic for the verifi-
cation of long-term stability of the properties of low w/c ratio ce-
ment composites compacted by the pressure [11,12].
The subject of the paper are the results of the study of the ef-
fects on the hydration products produced, pore structure and
mechanical properties of the cement pastes prepared with very
low w/c and compacted by the pressure.
* Tel.: +421 2 53909 257; fax: +421 2 54773 548.
E-mail address: usarziv@savba.sk
The subjects of the study were the hardened cement pastes prepared from Port-
land cement with w/c ratios 1.115, 0.095 and 0.075 prepared by the pressing of
their fresh mixtures at so called ‘‘optimal pressure” estimated experimentally. It
represented the pressure when the added water from the paste was not drawn
out. At the paste with w/c 0.115 it was the pressure 46 MPa, at w/c 0.095
102 MPa, and at w/c 0.075 210 MPa. The prepared test specimens were cylinders
with diameter and height 30 mm. For the comparison the reference test specimens
20 mm – edge cubes were used, prepared under the use of w/c 0.40 and by current
mode.
The preparation of the fresh mixtures represented the addition of the given
water amount to the cement an intensive mixing 3 minutes at the reference mix-
ture and 8 minutes at the mixtures with the low w/c values using an electrical mix-
er. The press compaction represented this procedure. When the cylinder form was
filled by the cement mixture then it was exposed to the pressing reaching the val-
ues 130000, 290000 and 540000 MPa, with the endurance of the press 5 minutes.
The prepared test specimens hardened 24 hours in the forms, at temperature
20 °C and relative humidity 95%, after the demoulding in water at the same
temperature.
The test specimens used for the testing were dried at 105 °C and their following
properties were observed:
Bulk weight and compressive strength using current methods, specific
weight (pycnometric method), hydration products occurred (DTA and GTA), pore
structure (intrusion mercury porosimetry) and morphology of the hydration
products (scan microscopy), water bound and calcium hydroxide content and to-
tal ignition loss (GTA), calculation of the total porosity from bulk and specific
weight data.
For DTA and GTA the thermal analysis equipment MOM Budapest was used. For
pore structure analysis was used the intrusion mercury porosimeter mod. 2000
Erba Science working to the pressure 200 MPa, under the used of the contact angle
141.3° and surface tension of mercury 0.48 N.m 1. The used scanning microscope
was the equipment SEM Carl Zeis EVO 40 HV.
For chemical analysis of the used Portland cements CEM I 42.5 the current
chemical methods were used. Its chemical composition in Table 1 is given.

0950-0618/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2009.03.014
3580 V. Živica / Construction and Building Materials 23 (2009) 3579–3582
Table 1
Chemical composition of Portland cement CEM I 42.5 – wt.%.
Loss on ignition Insoluble residue SiO2
0.87 0.97 20.68
3. Results and discussion
Fig. 1 shows the influence of the level of the pressure compac-
tion on the development of compressive strength of the hardened
cement pastes (HCP). It is evident that increase of compaction
pressure resulted in the increase of the compressive strength of
HCP. This increase represented opposite to the reference HCP
298.6%, 399.4% and 607.7% at the compaction pressures 46, 102,
and 210 MPa. At the same time an inverse influence of compaction
pressure on the development of total porosity of the HPC can be
seen. In the same relation the decrease of total porosity repre-
sented 44.3, 49.6 and 55.0% and the decrease of pore median with
the values 25.4, 22.5 and 19.4%. Further, it can be seen in Fig. 1 that
all these effects were tightly connected with the used very low w/c
ratios showing it as a significant and deciding circumstance of the
resulted effects. An immediate and significant consequence of the
used low w/c was the resulted pore structure. An example is shown
in Figs. 2 and 3. At their comparison it can be seen that with the
decrease of w/c from 0.40 to 0.075 a significant draft of the pore
Fig. 1. Dependence of compressive strength and total porosity of the cement pastes
on the w/c ratio and applied pressure after 1 day of the hardening.
Fig. 2. Pore size distribution curves of the cement paste with w/c ratio 0.40 in the
dependence on the time of the hardening.
Al2O3 Fe2O3 CaO MgO SO3 CaO free
6.74 2.15 64.72 1.37 2.11 0.50
distribution curves in the direction of the area of the finer pores
with the expression of the sheerness and the coming together of
the distribution curves.
SEM microscopy of the reference HCP with w/c 0.40 shown well
developed table crystals of calcium hydroxide and calciumalumi-
natehydrates and the C-S-H hydrates occurring in the pores like fi-
brous and needle crystals (Fig. 4). As it was shown, SEM
microscopy with the decrease of w/c ratio the crystal form of the
particles became less expressed and their dimension became more
uniform (Figs. 5 and 6). At w/c ratio 0.075 the C-S-H products
occurred in the form of very fine, irregular spherical or cylindrical
particles, tightly connected in a compact material (Fig. 7).
The significant difference of the character of the pore structure
of the HCP prepared with the low w/c ratios and those of the refer-
ence HCP is also confirmed in Fig. 8. It shows at the reference HCP a
parabolic dependence of its compressive strength on the pore med-
ian values. But at the lower w/c ratios a linear one. This may be
attributed to the differences in the pore structure shown by SEM
microscopy.
Fig. 3. Pore size distribution curves of the cement paste with w/c ratio 0.075 in the
dependence on the time of the hardening.
Fig. 4. SEM of cement paste, w/c 0.40 after 360 days of the hardening.
 V. Živica / Construction and Building Materials 23 (2009) 3579–3582 3581

Fig. 5. SEM of cement paste, w/c 0.115 after 360 days of the hardening.

Fig. 8. Relationship between pore median and compressive strength of the

hardened cement pastes.

Fig. 6. SEM of cement paste, w/c 0.095 after 360 days of the hardening.

Fig. 9. Relationship between compressive strength and product of bound water and
bulk weight.

An interesting information in Fig. 9 is shown. It shows a linear

dependence of compressive strength on this represents of bulk
Fig. 7. SEM of cement paste, w/c 0.075 after 360 days of the hardening. weight and bound water content in the HCP. The product
3582 V. Živica / Construction and Building Materials 23 (2009) 3579–3582

Table 2
Characteristics of the hardened cement pastes.

w/c 40 0.115 0.095 0.075

Applied pressure Without press. comp. 46.1 102.8 211.0
Compr. strength (%)a 69.5 reference 187.0% 229.4% 262.8%
Total porosity (%)a 34.5 22.0 20.1 17.9
Pore median (nm)a 420 270 240 212
Difference of initial (1 day) and final (360 or 60 days) pore median (nm) 1050 31 25 46
Initial porosity (%)d 37.9 22.6 15.2 12.7
Quantity the hydration productsc 13.40 12.10 11.60 10.30
b
Binding ability DMPa
% MPa
4.24 29.1 34.3 46.5
CaO:SiO2 ratio 1.60 2.40 – 2.68
H2O:SiO2 ratio 2.42 1.47 – 1.09
Particles morphology A gradual loosing of crystal habitus and the formation of the finer spherical and cylindrical
particles
a
After 28 days of the hardening.
b
Compressive strength increment at the total p porosity decrease by 1% 28 days.
c
Product of water bound content and bulk weight.
d
Calculated from specific weight of the cement and the given portion of water.

represents an approximate content of the hydration products in the
HCP [13]. It shown a significant increase of the sheerness of the
individual straight lines and their gradual shift in the area demar-
cated by decreasing values of the product and increasing values of
compressive strength. It represents an increase of compressive
strength of the HCP as the amount of the hydration products pro-
duced was decreased. This phenomenon is probably a consequence
of two factors conducting the effects of w/c ratios decrease:
(i) Less amount of the hydration products for the filling of the
pore space in the HCP is necessary.
(ii) Principal changes of pore structure and matrix with the
decrease w/c ratios used.
The main results of the study are summarized in Table 2. Beside
the known effect of the w/c ratio decrease shown as compressive
strength increase it was shown the decrease in the difference be-
tween initial and final pore median values. It shows the increase
of the homogeneity of the pore structure of the HCP with w/c ratio
values decrease and compaction pressures; increase. The last rep-
resented the principal factor causing that the incoherent cement
mixtures with low w/c ratios was transformed into a compact
and dense cement system, making possible the manifestation of
the potential of the positive effects of the use of very low w/c ratio
on the development of the properties of the HCP. A significant po-
sitive effects, which the pressure compaction made possible was
the significantly decreased initial porosity and at the same time a
significant increase of the biding ability as can be seen in Table
2. At the use of w/c 0.075 the initial porosity decreased by 66.5%
opposite to the reference mixture with w/c 0.40. Table 2 also
shows that the lowering of w/c ratio resulted also in the formation
of the hydration products with increased molar ratio CaO:SiO2 and
lowered H2O:SiO2 ratios [10] conducting by the given morphology
changes.
4. Conclusion
The cement pastes with very low w/c ratios from 0.115 till
0.075 under the unavoidable condition of the converting of these
loose and incoherent cement systems by their pressure compac-
tion into the dense material shown these effects:
Well known and very often reported decrease of the total poros-
ity and pore median and the increase of strength.
But other significant conducting effects have been estimated:
The increase of the CaO:SiO2 and the decrease of H2O:SiO2 mo-
lar ratios, their consequence were the particles morphology
changes shown as a gradual loose of the crystal character under
the formation of the finer spherical and cylindrical particles of
the hydration products showing the increase in binding capacity
and the increase of the homogeneity of the pore structure based
on the formation of the fine-grained and form of the hydration
products enabling the conditions for the increase of strength con-
nection among the individual particles into an extraordinary dense
structure. These factors seem to be the principle of the effects of
the very low w/c ratio and pressure compaction used.
Acknowledgement
The author wish to thank the Slovak grant agency VEGA (Grant
02/6106/6) for its support towards the work.
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