Construction and Building Materials 25 (2011) 30733077

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Construction and Building Materials

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Dependence of efciency of pressure compaction on the cement type used

Vladimr Zivica , Martin Krizma
Institute of Construction and Architecture, Slovak Academy of Sciences, Dubravska cesta, 9 845 03 Bratislava 45, Slovakia

a r t i c l e

i n f o

a b s t r a c t
The results of the study on the properties of the pastes, with w/c ratio 0.200.10, compacted in the fresh state by the pressures between 27 and 82 MPa are given. The comparison of their properties with those found at the reference non-pressured cement pastes prepared with w/c ratio 0.30 showed the signicantly increased compressive strength. Two effects were the cause: the signicant decrease of the initial porosity due to the extremely low w/c ratios and the mechanical compaction of the fresh pastes. It has been found a signicant increase of the effectiveness of the pressuring by the cement quality decrease. The long-term development of the properties of the pressured cement pastes is similar to the non-pressured cement pastes. At the conservation of the properties differences in the benet of the pressured materials. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 6 July 2010 Received in revised form 15 December 2010 Accepted 24 December 2010

Keywords: w/c ratio Pressure compaction Compressive strength Porosity Hydration products

1. Introduction The dependence of the quality of the engineering properties of concretes and other on the value of watercement ratio (w/c) is very well known. Also the fact of their strength, durability and the quality of other engineering properties increase when the w/c ratio values are decreased [13]. A signicant factor limiting the use of that effect is the decrease of the workability of the fresh concrete mixtures resulting in the engineering properties level decrease. A limited solution enables the use of the plasticizers and superplasticizers. A very interesting solution represents the combination of low w/c ratios and pressure compaction of the fresh concrete mixtures, resulting in a submicroscopic pore structure and in an adequate high quality of the engineering properties of the concretes [46]. The high positive effect of the compaction on the strength shows the results reported by Roy et al. [7,8]. By the compaction pressure of 350 MPa it was possible to reach the hardened cement paste with compressive strength of 645 MPa at the use of w/c 0.21. The detailed relationships among w/c ratios, compaction pressure, time, pore structure, shape and form of the cement hydration products produced in the pressured cement pastes are given in the papers [911]. More detailed information on effects of the mechanical compaction is also reported by Roesler and Odler [12]. According to these authors the major parameter determining the formation and development of pore structure and properties of the cement composites is the initial porosity.
Corresponding author. Tel.: +421 2 539 09 257; fax: +421 2 247 73 548.
E-mail address: usarziv@savba.sk (V. Zivica). 0950-0618/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.conbuildmat.2010.12.061

The relation between initial porosity and compaction pressure is expressed by the empirical equation:

Po AeB CP 21

where Po is the initial porosity %, CP compaction pressure in MPa, A = 29 and B = 0.0054 are empirical constants. It appears that low-porosity cement composites have a great potential of the modication of composition and structure of the cement based materials. An interesting topic is the dependence of the efciency of the pressure compaction on the type of cement used. This paper presents the results of the study on this dependence when cements differing in the standard compressive strength values were used.

2. Experimental The object of the study were the hardened cement pastes prepared from two Portland cements CEM I 52.5, CEM I 42.5 and Portland cement slag blend CEM II 32.5 according to the STN EN 197-1. The w/c ratios 0.20, 0.15 and 0.10 were used and compaction of the fresh pastes by the pressures 27, 48 and 82 MPa. The pressure was deduced at once after the completing the cylinder (the diameter 32 mm and the height 30 mm) forms with the cement mixture. The period of prescription of the pressure was 3 min. For the pressure compaction the laboratory press was used. The reference test specimens were 20 mm-edge cubes prepared from the same cements using w/c ratio 0.30 with the mixing and compaction of the mixtures done by hand.

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Table 1 Composition and properties of the cement Portland cement 52.5, Portland cement 42.5 and Portland cement slag blend 32.5 used. Chemical composition wt.% CEM 52.5 PC CEM 42.5 PC 0.99 0.86 21.06 5.50 4.75 63.21 1.28 2.21 0.58 25 3240 3531 CEM PC blend 32.5 0.99 1.76 23.39 8.50 2.65 57.93 2.69 2.02 0.89 26 3070

Ignition loss 0.87 Insoluble residue 0.97 SiO2 20.68 Al2O3 6.74 Fe2O3 2.15 CaO 64.72 MgO 1.37 SO3 2.11 CaO free 1.00 Normal consistency, % 27 Specic weight, kg m3 3240 Specic surface area, 359 cm2 g1 Mineral composition (Bogue), wt.% 14.32 C3A C4AF 6.32 C3S 52.30 C2S 19.81 4.54 CaSO4

pore unit 120, under the use of the contact angle 141.3 and surface tension of mercury 0.48 N m1. Water bound content corresponding to the loss on the ignition in the interval 100450 C. Total porosity calculated on bulk and specic weight data, thermal analysis was carried out on the equipment SDT 2960 device T.A.Instruments: the sample mass was 20 mg, heating rate 10 C min1, ramping from ambient temperature to 1000 C in an air atmosphere. TG mass losses and DTA effects were analysed using the T.A.I. Thermal Analyst package. The morphology was studied by scanning electron microscopy using a Carl Zeiss EVO 40 HV microscope. Before the scanning process, all samples were coated with gold to enhance the electron conductivity. The chemical, mineralogic composition and physical properties of the used cements are listed in Table 1. 3. Results and discussion As it can be seen in Fig. 1 after 1 day of the curing the compressive strength of pastes increased with the decreasing values of the w/c ratio used and with the increasing value of the deduced pressure. It is evident that the effect of pressure compaction was increased with decreasing quality of the cement used. It means in the sequence CEM I 52.5, CEM I 42.5 and CEM II 32.5. At the rst cement the compressive strength increase was between 21.7% and 69.4% opposite to the reference paste. At the cement of lower quality 145.5% and at the lowest quality Portland cement slag blend CEM II 32.5 it was 250.0%. After 90 days of the curing it can be seen at the high quality cement CEM I PC 52.5 a further increase of the compressive strength representing 32.8116.0% opposite to the reference paste. On the contrary at the cements of the lower quality CEM I PC 42.5 and CEM II PC slag blend a compressive strength decrease opposite to the level reached after one day of curing. This decrease represents 30.0% at cement CEM I PC 42.5% and 110.8% at CEM II PC slag blend.

6.72 14.09 47.04 24.80 4.75

The test specimens hardened 24 h in the moulds at 20 C, relative humidity of 95% and after the demoulding they were placed in water for 90 days at the same temperature. The test specimens used for the testing were dried 24 h at 105 C and the following properties were estimated: Bulk weight calculated from the estimated weight and dimensions data. Compressive strength using the usual compressive strength test. Specic weight using pycnometer method. Pore structure using the intrusion mercury porosimeter mod. 2000 Erba Science working to the pressure 200 MPa with macro-

Fig. 1. Comparison of compressive strength of the cement pastes with respect to cement type, w/c ratio, compaction pressure and curing time.

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It is evident that the development of compressive strength of these pastes during the long-term curing was retarded. The observed effect of the retardation is identical with that observed at the curing of the cement pastes prepared from 40 to 60 C warm fresh pastes. At these pastes the higher compressive strength increase and the retardation effect has been found at the cement with the lower C3A and higher C4AF content [13]. The similarity of the retardation effect of the both warm and the pressured pastes give evidence for the identity of the principle of the retardation phenomenon. It evidently consists in the reducing and the equalization the difference in phase composition of the hydration products, pore structure and mechanical properties between these pastes and the reference ones. It seems that the expression of the retardation effect was increased with the increase of the greatness in the difference of the compared conditions. In Table 2 the obtained data on mechanical properties, pore structure parameters and bound water of the studied pastes are given. As it can be seen the properties of the pastes were signicantly dependent on the w/c ratio, the applied compaction pressure and time of the curing. With the decrease of w/c ratio and the time progress the bulk weight and compressive strength of the pastes were increased. On the contrary, their total porosity, the pore median value, specic surface area, water bound content in the hydration products and total porosity decreased. It can be also seen that the majority of the mentioned properties were directly or indirectly dependent

on the quantity and the properties of the hydration products formatted and on their changes [14,15]. It is well known that principal property governing the properties of the cement based materials is their pore structure. Mainly, the initial porosity of the fresh mixture is a fundamental and pronounced factor of the development and the nal level of the porosity of the hardened material and the properties of the hardened material. The initial porosity is expressly dependent on the w/c ratio used. In the cement based materials in the absence of air pores, the value of the initial porosity Po is practically identical with the volume value of the water added:

Po

Vw=v 100% Vc Vw=c

where Vc is the cement portion volume and Vw/c is the water volume added is equal to the w/c ratio used. The inuence of w/c ratio, together with the deduced pressure on the initial porosity of the cement paste, can be seen in Table 3. It is evident that the combination of both factors caused the decrease of the initial porosity producing the conditions for the development of the low porosity and high compressive strength of the cement paste. The initial porosity level determined the developing character of the pore structure of the hardening cement paste. This effect can be seen in Figs. 2 and 3.

Table 2 Summary of the study results. Cement w/c Preparation mode Time hardening days Bulk weight (kg m3) Compressive strength (MPa) Specic weight (kg m3) Total porosity (%) Micropores with radius 3.87500 am Pore volume (cm3 g1) 0.11570 0.10035 0.08733 0.08607 Microporosity (%) 20.7 18.4 16.2 17.3 Portion in total porosity (%) 56.2 53.8 53.6 54.6 Pore median (nm) 39 32 25 77 Specic surface area (m2 kg1) Bound water (wt.%)

Portland cem. 52.5

0.30

Current

0.20

Compaction pressure 27 MPa

1 28 90 1

1789 1830 1859 2010

84.90 96.12 131.17 103.42

2831 2780 2665 2943

36.8 34.2 30.2 31.7

3539 4506 6716 3420

7.7 9.2 11.5 5.7

0.15

Compaction pressure 48 MPa

28 90 1

2041 2068 2126

135.21 174.20 126.12

2852 2770 2950

28.5 25.3 27.9

0.07790 0.06335 0.07385

15.9 13.1 15.7

55.8 51.8 56.3

42 32 148

3692 4890 3216

7.2 8.7 5.4

0.10

Compaction pressure 82 MPa

28 90 1

2157 2189 2227

196.20 254.56 144.24

2848 2786 2940

24.3 21.5 24.2

0.06497 0.05573 0.06331

14.0 12.2 14.1

57.6 56.7 58.3

38 22 271

2727 3387 1956

6.7 7.3 4.8

28 90 Portland cem. 42.5 0.30 Current 1 28 90 1

2254 2262 1805 1840 1855 2220

224.22 282.56 44.28 96.23 114.32 107.51

2858 2807 2799 2635 2583 2920

21.3 19.6 35.6 30.2 28.2 24.0

0.05368 0.04509 0.13162 0.10428 0.09032 0.07973

12.1 10.2 23.8 19.2 16.8 17.7

56.8 52.3 66.8 63.6 59.6 73.7

28 20 173 55 47 480

3975 3667 2472 3996 5182 1962

5.9 6.4 5.6 8.0 8.7 3.5

0.10

Compaction pressure 82 MPa

28 90 Portland cem. slag blend 32.5 0.30 Current 1 28 90 1

2262 2270 1739 1795 1826 2170

212.72 240.20 31.81 76.24 101.60 112.38

2829. 2811 2762 2617 2534 2875

20.0 19.3 37.0 31.4 28.0 24.5

0.05923 0.05279 0.16101 0.13036 0.10871 0.09124

134 12.0 28.0 23.4 19.7 19.8

67.0 62.2 75.6 74.5 70.3 79.2

42 36 280 54 42 510

3760 4702 2726 4672 6307 2522

5.4 5.7 4.6 7.3 8.4 3.6

0.10

Compaction pressure 82 MPa

28 90

2215 2252

179.20 243.56

2794 2738

20.7 17.8

0.07088 0.05639

15.7 12.7

80.8 72.2

35 30

3315 3993

4.9 5.5

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Table 3 Initial porosity of the cement pastes before and after pressure compaction. w/c Pressure Compaction (MPa) PC 52.5 0.30 0 0.20 12 0.15 48 0.10 82 PC 42.5 0.30 0 0.10 82 PC blend 32.5 0.30 0 0.10 82 Initial porosity (%) Before compaction 52.73 43.61 37.50 30.01 52.73 30.01 47.90 23.49 After compaction 40.27 32.49 24.14 24.14 18.70 Change of the initial porosity (%)

0 7.66 13.36 19.56 0 19.56 0 20.39

It is evident that the lower values of the initial porosity and pore median show the higher pore structure quality of the hardened CEM I PC 52.5 cement paste opposite to the hardened CEM II PC 32.5PC slag blend. The showed effect and the difference in the quality of the pore structure is undoubtedly a consequence of the difference in the w/c ratio used, pressure compaction and the type of the cement used [1719]. The differences in the pore structure development of the pressure compacted cement paste and the reference one can be observed at the comparison of Figs. 4 and 5. It is evident that the decrease of w/c from 0.60 to 0.075 resulted in a signicant draft of the pore distribution curves in the area of the ner pores. At the same time the draft by the increase of the sheerness of the distribution curves is conducted. The scanning microscopy results are in a good relations with those of porosimetry analysis. The SCAN results showed that the crystal form of the hydration cement products particles became less expressed and their form became more uniform as the w/c 0.60 to 0.075 decreased. At w/c 0.075 the hydration products occurred in the form of very ne, irregular spherical or cylindrical particles, tightly connected in a compact material. It evidently indicated the increase of the neness of the produced pore structure indentically with the pore structure analysis results.

Fig. 2. Pore size distribution for the hardened PC 52.5 cement paste, w/c 0.15, initial porosity 32.49%.

Fig. 4. Pore size distribution curves of the PC 52.5 cement paste with w/c ratio 0.60 in the dependence on its time of the hardening.

Fig. 3. Pore size distribution curves for the hardened PC blend 32.5 cement paste, w/c 0.30, the initial porosity 47.90%.

Fig. 2 shows the pore size distribution curves for the hardened CEM I PC 52.5 cement paste, w/c 0.15, with the initial porosity 32.49% and pore median 280 nm (1 day curing), 54 nm (28 days), 42 nm (90 days). Fig. 3 represents pore size distribution curves for the hardened CEM II PC blend 32.5 cement paste, w/c 0.30, with the initial porosity value 47.90% and pore median 148 nm (1 day), 38 nm (28 days), 22 nm (90 days).

Fig. 5. Pore size distribution curves of the PC 52.5 cement paste with w/c ratio 0.075 in the dependence on its time of the hardening.

 V. Zivica, M. Krizma / Construction and Building Materials 25 (2011) 30733077 Table 4 Compressive strength increment of the cement pastes after 28 days of their hardening. Cement type Compaction Pressure (MPa) w/c Increment (MPa) PC 52.5 PC 42.5 PC blend 32.5 0 0.30 7.90 82 0.10 17.60

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0 0.30 0.30

27 0.20 9.90

48 0.15 19.50

82 0.10 27.50

0 0.30 9.60

82 0.10 26.30

It has been found the dependence of the effectivity of the combination of low w/c ratios and pressure compaction on the type cement used. In the sense of the effectivity increase of the combination with the decrease of the quality of the cement used. The possibilities of the pressure technology are broader than it was shown in this article. Its combination with the effect of the increased temperature seems to be a promising way for the preparation of the cement based materials with the extreme strength, and the increased quality of the other their engineering properties, mainly durability. Acknowledgement The author would like to thank to Slovak Grant Agency VEGA for its support towards this work (Grant No. 2/0088/09). References
[1] Schulze J. Inuence of watercement ratio and cement content of the properties of polymer modied mortars. Cem Concr Res 1999;29:90915. [2] Naragaj TS, Zahida Banu TS. Generalization of Abrahms law. Cem Concr Res 1996;26:93342. [3] Appa Rao G. Role of waterbinder ratio on the strength development in mortars incorporated with silica fume. Cem Concr Res 2001;31:4437. [4] Freidin C. Cementless pressed blocks from waste products of coal-ring power station. Cem Concr Res 2007;21:128. [5] Zhongzi Xu, Yongmei Deng, Xuequan Wu, Mingshu Tang. Inuence of various hydraulic binders on performance of very low porosity cementitious systems. Cem Concr Res 1993;23:46270. [6] Zhongzi Xu, Mingshu Tang, Beaudoin JJ. Relation between composition, structure and mechanical properties of very low porosity cementitious systems. Cem Concr Res 1993;23:18795. [7] Roy DM, Gouda GR, Borovsky A. Very high strength cement pastes prepared by hot pressing and other high pressure techniques. Cem Concr Res 1972;2:80720. [8] Roy DM, Gouda GR. High strength generation of cement pastes. Cem Concr Res 1973;3:34966. [9] Bajza A. On the factors inuencing the strength of cement compacts. Cem Concr Res 1972;2(1):6778. [10] Bajza A, Salaj A, Gebe S, Kusy D. Autoclaved compressed cement pastes. Cem Concr Res 1975;5(5):6778. [11] Bajza A. Structure of compacted cement pastes. Cem Concr Res 1983;13(2):23245. [12] Roessler M, Odler I. Investigation on the relationship between porosity, structure and strength of hydrated Portland cement pastes. I. Effect of porosity. Cem Concr Res 1985;15:32030. [13] Zivica V. Inuence of the increased temperature in the initial sate of the preparation of the cement pastes on the mechanism and kinetics of the formation of the binding phases, their structure and physico-mechanical properties. Scientic Report, Institute of Construction and Architecture of SAS, Bratislav; 1973 [in Slovak]. [14] Jambor J. Study of the relationship among phase composition, pore structure and physico mechanical properties of the hardened binding pastes. Research Report Institute of Construction and Architecture, Slovak Academy of Sciences, Bratislava, 1976 [in Slovak]. [15] Jambor J. Relationships among porosity, pore structure, strength and other engineering properties of the cement composites. Research Report, Institute of Construction and Architecture, Slovak Academy of Sciences, Bratislava, 1984. [16] Zivica V. Effects of the very low watercement ratio. Constr Build Mater 2009;23(12):357982. [17] Jambor J. Pore structure and strength development of cement composites. Cem Concr Res 1990;20:94854. [18] Wensheng Zh, Beixing L, Hongxia W, Jiangxiong W, Yimin Ch. Analysis of pore structure and their relations with strength of hardened cement paste. J Wuhan Univ Technol Mater Sci Ed 2005;20(1):1147. [19] Kondraivendhan B, Bhattacharjje B. Effect of age and watercement ratio on size and dispersion of pores in ordinary Portland cement paste. ACI Mater J;2010 [March, 20].

It is very well known that the strength increase by the decrease of the porosity is conditioned and conducted. A quantitative evaluation of these dependence enables the ratio of the compressive strength increase (compressive strength increment) coming to a dened porosity decrease, for example porosity decrease of 1%. It is evident that the porosity decrease is caused by the hydration products content increase [14]. The values of the calculated compressive strength increment values are given in Table 4. A clear dependence of the compressive strength increment on the w/c ratio and compaction pressure values can be seen. It means that at the same hydration products content increase (porosity decrease) a different compressive strength increase (compressive strength increment) conducted. Such effect is possible only due to the formation of the different hydration products distinguished by their binding capacity [14,15]. Taking into the consideration these results and those given in Table 2 these factors seem to be the cause of the increased binding capacity of the hydration products: formation of calcium silicate hydrates with lowered content in the bound water and increased calcium oxide content causing their following shape properties [1416], formation of very ne pore structure with the high degree of homogeneity [16], a direct consequence the formation of signicantly more stable pore structure with the low porosity and low pore median values with a nal effect observed as an increase of the compressive strength of the pressure compacted cement pastes. 4. Conclusions The results of the study on the properties of the pastes prepared from Portland cements class CEM I 52.5 and CEM I 42.5 and CEM II Portland cement slag blend 32.5, with w/c ratio 0.20, 0.15 and 0.10 compacted in the fresh state by the pressures 27, 48 and 82 MPa are given. A signicantly increased compressive strength was found as a consequence of the use of low w/c ratio and pressure compaction. These factors can be responsible for the found effects: (i) densifying of the fresh mixture and the decrease of the initial porosity favouring the process of the hydration, hardening and of the packing of the individual particles of the hydration products, (ii) positive effect of the low w/c ratio on the rate and level of the development of the properties of cement composites, (iii) formation of more dense pore structure with high degree of its homogeneity.