CEMENT and CONCRETERESEARCH. Vol. I I , pp. 257-265, 1981. Printed in the USA. 0008-8846/81/020257-09502.

00/0 Copyright (c) 1981 Pergamon Press, Ltd.

PORE STRUCTUREOF AIR-ENTRAINED HARDENEDCEMENTPASTE Umer Z. Cebeci Department of Civil Engineering Middle East Technical University, Ankara, Turkey (Communicated by S. Diamond) (Received Nov. 21, 1980) ABSTRACT The effect of air entrainment on the pore structure of hardened cement paste was investigated. Air-entrained and air-free samples of various water-cement ratios and ages were prepared by a well-defined procedure. The f i r s t and second-intrusion pore-size distribution curves of the samples were determined by mercury intrusion porosimetry. It was observed that sample preparation technique affects the pore-size distributions of hardened cement pastes. The second-intrusion curves indicated a decrease in the total volume and a reduction in the size of pores that are uniform in cross section with decreasing age and water: cement ratio. The second-intrusion curves of air-entrained and air-free pastes of equal water:cement ratio and age matched with each other. I t was concluded that air entrainment introduces only large air voids observable by a naked eye and does not alter the characteristic fine pore structure of hardened cement paste appreciably. BUnyeye hava sUrUkleyen katkl maddelerinin sertlesmi$ cimento hamurunun g~zenek yapls~ Uzerindeki t e s i r l e r i a r a s t l r l l m l s t l r . De~isik su: cimento oranlarlnda, havall ve havasl allnm1$ hamurlar t a r i f edilen tarzda hazlrlanm1$tlr. Baslncll clva porozimetresi yardlml ile numunelerin iki asamada gUzenek bUyUkIU~U da~lllml e~rileri elde edilmist i r . Numune hazlrlama tarzlnln sonuca tesir etti~i gUzlenmistir. Ikinci asamada elde edilen e~riler toplam muntazam gUzenek hacmnda ve muntazam gUzenek bUyUklU~Unde, numuneya$1na ve su:cimento oranlna paralel bir azalma oldu~unu ortaya koymaktadlr. Aynl su:imento oranl ve ya$~ki, havall ve havasl allnmls numunelerden ikinci asamada el de edilen e~riler bUyUk ~IcUde cak1$maktadlr. Dolaylslyla, hava sUrUkl eyici katkllarln sertlesmi$ imento hamurunda sadece iplak g~zle g~rUlebilen hava bo~luklarl meydana getirdi~i ve sertlesmi$ hamurun kendine mahsus mikro-gUzenek yaplslnl dikkate de~er UlcUde de~istirmedici neticesine varllmlstir.

The author is on leave from the Middle East Technical University and at present is with the College of Engineering of King Abdulaziz University, Jeddah, Saudi Arabia. 257

258 O.Z. Cebeci Introduction

Vol. I I , No. 2

A clear picture of the microstructure of hardened cement paste (HCP) is necessary in understanding the structure and properties of concrete. The behavior of concrete can be predicted and controlled i f the structure of the paste is known, because HCP acts as the binding medium in concrete. HCP is known to be a porous material ( I ) . The determination of the pore-size d i s t r i b u tion (PSD) of a porous solid is an important step in the investigation of i t s microstructure. Various techniques, including mercury intrusion porosimetry (MIP), have been used by many investigators to determine and compare PSD's of HCP's ( I - 6 ) . Air-entrained concrete, discovered during the mid-1930's, is one of the most important developments in concrete technology. I n t e n t i o n a l l y entrained a i r does not only increase the d u r a b i l i t y of concrete against freezing and thawing but also improves other properties of both freshly mixed and hardened concrete (7). I n t e n t i o n a l l y introduced a i r is uniformly distributed in spherical bubbles of 0.25 - 0.025 mm diameters, whereas unintentionally included "entrapped" a i r forms much greater voids of random shapes. Figure I shows the a i r voids on fracture surfaces of air-entrained cement pastes. (There are no fine sand p a r t i c l e s to entrain a i r , but the pastes in t h i s study are called "air-entrained" because they were prepared similar to air-entrained concrete; i . e . , by adding an a i r - e n t r a i n i n g agent to the mixing water. The a i r - e n t r a i n i n g agent in t h i s case probably acts to s t a b i l i z e and uniformly d i s t r i b u t e a greater amount of entrapped a i r in spherical voids as shown in Figure I ) . For an i n v e s t i gation of the pore structure of air-entrained HCP, however, instrumental methods should be employed. In a recent study (8), the application of the second-intrusion method in MIP has made i t possible to distinguish the difference in PSD's between airfree and air-entrained HCP's. Theoretical basis of the second-intrusion method has been reported in detail earlier (9). This paper presents the experimental results obtained in this study and their interpretation.

(a)

Before mercury intrusion FIG. l

(b)

After mercury intrusion

Air-voids on fracture surfaces of air-entrained HCP's.

Vol. I I , No. 2 PORE STRUCTURE, AIR ENTRAINMENT, CEMENT PASTE Rationale

259

The theoretical basis of MIP is now widely known (lO). The basic principle is that a non-wetting liquid can enter the pores of a porous solid only under an applied pressure. The relationship between the applied pressure and pore size for various pore geometries has been formulated (8, l l ) . I t has also been shown that, upon removal of the applied pressure, mercury in pores of certain geometry would not be discharged (9). Thus, the ink-bottle pores of a sample can be d i f f erentiated from the "uniform capillary pores" (perfect cylinders or pores which contain small contractions and enlargements along their lengths). Hence the size distribution of the uniform pores of samples containing mixed pores can be determined by re-intruding the samples after the f i r s t intrusion-depressurization cycle. This important development in MIP has been called the secondintrusion method (9). Once intruded and f i l l e d with mercury, the air voids of air-entrained HCP, which are in the ink-bottle pore cathegory, will not release mercury upon depressurization. In effect, these voids behave as solid portions of the sample and they do not show up in further intrusion-depressurization cycles. Hence, the second-intrusion curves of air-entrained pastes should be similar to the second-intrusion curves of pastes containing no entrapped or entrained air (provided that the water:cement (w:c) ratio and age of the two sets of pastes are equal). The present study has confirmed the validity of the above hypothesis and has led to the conclusion that air entrainment introduces only the air voids observable by a naked eye with no other effect on the pore structure of HCP. Materials The cement used in this study was a commercial Type l Portland cement of specific gravity 3.17 and Blaine fineness 3450 cmZ/g. The composition was determined by the Bogue method as 60 % C3S, 15 % C2S, 9 % C3A, and 6 % C4AF. Distilled water was used in preparing the samples and a commercial air-entraining agent (designated as Ad-Aire) was added to obtain air-entrained pastes. Experimental Preparation of Pastes In order to establish a sample preparation method that produces airentrained and air-free pastes consistent among themselves and comparable with each other, a set of preliminary runs were made (8), and as a result the following mixing, molding and curing procedure was established. Air-entrained pastes of 0.4, 0.5 and 0.6 w:c ratios were prepared by mixing 200 g cement with the appropriate amount of water containing the airentraining agent in a kitchen mixer (Kitchen Aid Model K4-3). The air contents of fresh pastes were measured (by a Chace Air Indicator) to be about 6%. However, some a i r bubbles emerged to the surface while transferring the pastes from the mixing bowl to the molds; therefore, the air content of individual samples varied. The fresh pastes were poured into flat-bottom glass test tubes of 1.5 cm diameter and 5 cm height and stored in a humidity room (at 85 I0% relative humidity and 28 2oc).

260 O.Z. Cebeci Samples containing no entrained or entrapped a i r were prepared in a vacuum desiccator modified for t h i s purpose as shown in Fig.2. In a d d i t i o n to the o u t l e t connected to .a mechanical vacuum pump, two holes were bored on the l i d . A Tiernan gauge was connected to the desiccator by a tube fixed to one hole and a mixing paddle was operated through an O-ring seal f i x e d into the second hole. For each sample, 5 g cement was mixed with d i s t i l l e d water in t e s t tubes placed in a holder in the desiccator. The pressure inside the desiccator was maintained below 2.67 kPa (20 mm H g ) t h r o u g h o u t mixing. Microscopic examination of the hardened pastes indicated that t h i s method produced pastes with no entrapped a i r . The pastes were allowed to harden in the tubes placed in the humidity room.

Vol. I I ,

No. 2

vacuum pump gau

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FIG.2 Diagram of modified vacuum d e s i c c a t o r used for mixing a i r - f r e e cement pastes.

The samples were removed from the humidity room a f t e r three days of curing. The tubes were broken and a portion of the hardened pastes were dried at I055oc in an oven for at least 48 hours, while the remainino were replaced in the humidity room for curing up to 60 days. Determination of PSD's The PSD's of the hardened pastes were determined by a mercury i n t r u s i o n porosimeter (Model 910 of Micromeritics I n s t . Corp., Norcross, Georgia). This instrument was capable of exerting 345 MPa (50,000 Psi) pressure. The samples tested were I-3 g pieces broken from the hardened pastes by discharding top and bottom portions. They were oven-dried under atmospheric pressure, cooled in a desiccator, and then placed in the porosimetersample c e l l . The samples were evacuated to 0.27 Pa p r i o r to i n t r u s i o n . The f i r s t - i n t r u s i o n and depressurization (to atmospheric pressure) were performed during the day, and the samples were l e f t in the porosimeter overnight to allow completion of the withdrawal of mercury from the pores. Then the sample c e l l was removed from the pressure vessel and some mercury from the c a l i b r a t e d tubing withdrawn by a syringe in order to relocate the meniscus at a lower section of the tubing that was uncontaminated by the hydraulic f l u i d during the f i r s t i n t r u s i o n - d e p r e s s u r i z a t i o n cycle (8,12). The sample c e l l was placed in the pressure vessel, hydraulic f l u i d r e f i l l e d and the second-intrusion t e s t was performed. Blank runs were made to correct f o r the c o m p r e s s i b i l i t y of the system. In converting the t e s t data to PSD curves surface tension of mercury was taken as 48.4 Pa and the contact angle as 117o f o r both i n t r u s i o n s . (Winslow (13) r e c e n t l y observed a contact angle difference between v i r g i n and p o s t - i n t r u s i o n samples of porous alumina subjected to high pressures and subsequent cleaning under heating and evacuation. However the present work is mainly based on the comparison of the second-intrusion curves of a i r - f r e e and a i r - e n t r a i n e d pastes, and therefore the conclusions should not be s i g n i f i c a n t l y affected by the exact value of the contact angle f o r the secondintrusion).

Vol. l l , No. 2 PORE STRUCTURE, AIR ENTRAINMENT, CEMENT PASTE

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262 O.Z. Cebeci Results and Discussion

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The observation of a f r a c t u r e surface through an a i r - e n t r a i n e d paste a f t e r the MIP t e s t (Figure l - b ) shows that the a i r voids, as expected, have been intruded and mercury has been retained in these voids upon depressurization. This indicates the v a l i d i t y of the second-intrusion method for d i f f e r e n t i a t i n g the i n k - b o t t l e pores in samples. The PSD's of the pastes are shown in Figure 3. (The notation used is such that O.4/3d/A designates the paste with 0.4 w:c r a t i o , 3-days age; A means a i r - e n t r a i n e d and AF means a i r - f r e e paste). The curves obtained from single samples representing each type of paste have been reported here because in p r e l i m i n a r y work (8) the r e s u l t s have been found to be reproducible, consistent and comparable. I t should also be pointed out that the specimens used in MIP are so small that great precautions must be taken to see that they are representative of the larger mass being sampled. The pore s t r u c t u r e of HCP is also influenced by the sample preparation technique as regards mixing, molding and curing procedure ( 4 , 5 , 8 ) . Thus, a comparision of the f i r s t - i n t r u s i o n PSD curves of a i r - f r e e pastes with e a r l i e r work is in order p r i o r to the evaluation of the e f f e c t of air-entrainment on PSD of HCP. The f i r s t - i n t r u s i o n PSD curves of a i r - f r e e HCP's of various w:c r a t i o s and ages were determined by Winslow and Diamond e a r l i e r (2). Table 2 shows a comparison of pore volume data obtained from equal w:c r a t i o and age pastes prepared in these two studies. Results of other MIP work on HCP's (3, 4, 5, 6) can not be included in Table 1 because the w:c r a t i o s and ages of the pastes tested by those workers do not match with the pastes compared in Table I . TABLE I . Comparison of Pore Volume Data

Sample O.4/3d/AF O.4/3d/AF O.6/3d/AF O.6/3d/AF O.6/28d/AF O.6/28d/AF O.6/60d/AF O.6/60d/AF

Prepared and tested in This study Reference 2 This study Reference 2 This study Reference 2 This study Reference 2

Water Porqsity (cm~/g) 0.250 0.279 0.394 0.373 0.362 0.337 0.331 0.323

Cumulative i n t r u s i o n at 0.008 Nm pore diameter (cm~/g) 0.210 0.194 0.331 0.300 0.295 0.226 0.267 0.204

Table 1 shows that the 0.6 w:c ratio pastes prepared in this study are more porous than those prepared by Winslow and Diamond, whereas the O.4/3d/AF sample of t h i s study has a smaller water porosity but a greater cumulative intrusion than the O.4/3d/AF sample in Reference 2. Regarding the 0.6 w:c r a t i o pastes, the differences between the water porosities, or total pore volumes of the pastes prepared for this study and by Winslow and Diamond are smaller than the difference between the cumulative intrusions, i . e . , the differences between the corresponding pastes shown in the t h i r d coulmn are

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PORE STRUCTURE, AIR ENTRAINMENT, CEMENT PASTE

smaller as compared with the differences in the last column (Table l ) . Hence, the different methods of mixing and curing affect total porosity less than the porosity in the pores greater than 0.008 N diameter. This is another m demonstration of the influence of the sample preparation technique on the PSD's of HCP's and confirms Sellevold's statement that "These inconsistencies emphasize the great importance of the specimen preparation procedures" (4). Although the P D curves obtained in this study are not exactly the same S as those reported by Winslow and Diamond the general concept that "as a paste hydrates the total pore volume decreases and a general reduction in pore size takes place" (2) is confirmed by Figs.3 (a)-(c). The same trend is observed with decreasing w:c ratio in Figs.3(d), (e) and (a). The results of this study confirm the existence of a threshold diameter and i t s decrease with decreasing w:c ratio. Second-lntrusion P D Curves S The size distribution of the uniform pores that are present in HCP's were determined by the second-intrusion method. The second-intrusion PSD's are drawn on the same figures with the first-intrusion curves (Fig.3). The second-intrusion PSD's of the pastes have similar characteristics as the f i r s t - i n t r u s i o n curves; i . e . , with increasing age and decreasing w:c ratio the total volume of pores that are uniform in cross section decreases and a general reduction in the diameters of these pores takes place. The secondintrusion threshold diameter is equal to or smaller than the first-intrusion threshold diameter. The major fraction of the difference between the f i r s t and second-intrusion pore volumes is within a short range of pore diameters slightly smaller than the threshold diameter, which means that a large volume of ink-bottle pores have entrances in this range. The diameter of the inkbottle pores are always larger than the entrances; hence, i t would be incorrect to state that an air-free H P does not contain pores of sizes greater than the C threshold diameter. Effect of Air Entrainment The most important observation concerning the pore structure of airentrained HCP's is achieved by a comparison of the second-intrusion curves of air-entrained pastes with the corresponding air-free samples. Table 2 shows that the total second-intrusion volumes of corresponding air-entrained and air-free pastes agree within O.Oll cm3/g which means that air-entraining agent makes no systematic change in the portion of the porosity of H P that C is uniform in cross section. Hence, air-entrainment introduces mainly large a i r voids in H P and does not affect the characteristic porosity observed in C pastes containing no entrained or entrapped air. I~ other words, i f an airfree paste contains x cmJ/g uniform pores and y cmJ/g ink-bottle pores, the corresponding air-entrained paste ( i . e . , of equal w:c ratio and age with the 3 air-free paste) also contains x cm /g uniform pores as revealed by similar 3 second-intrusion curves. Thus the air-entrained paste must also contain y cm /g ink-bottle pores similar to the air-free paste and an additional z cm~/g air voids introduced by the air-entraining agent. Obviously, the difference between the f i r s t - i n t r u s i o n c~rves of corresponding air-free and air-entrained pastes must be equal to z cmJ/g. Fig.3 shows that the second-intrusion PSD's of air-free pastes with 0.4 and 0.5 w:c ratios indicate slightly larger pore sizes than the corresponding

264 O.Z. Cebeci

Vol. I I , No. 2

air-entrained pastes, whereas the reverse is true for the 0.6 w:c ratio pastes of three different ages. Therefore, with increasing w:c r a t i o , the portion of the pore space that is uniform in cross section is distributed s l i g h t l y toward larger pore sizes in air-entrained pastes as compared to air-free pastes. TABLE 2. Comparison of Total Uniform and I n k - B o t t l e Pores

Sample O.4/3d/AF O.4/3d/A O.5/3d/AF 0.5/36/A O.6/3d/AF O.6/3d/A O.6/28d/AF O.6/28d/A O.6/60d/AF O.6/60d/A

Total Volume intruded ( c m 3 / g ) First-intrusion Second-intrusion .196 .219 .265 .301 .332 .344 .300 .351 .271 .320 .139 .138 .196 .190 .244 .248 .225 .214 .186 .197

Retention factor (%1 29 37 26 37 27 28 25 39 31 38

The ratio of the ink-bottle pores to the total pore volume intruded is expressed as the retention factor in Table 2. In air-free HCP's the ink-bottle pores constitute 25 to 31% of the total intrusion, whereas in air-entrained pastes this fraction is greater by the volume of a i r voids entrained into each sample. Conclusion Pore structure of air-entrained HCP was investigated by determining the f i r s t - and second-intrusion PSD's with mercury intrusion porosimeter. The analysis of the PSD curves led to the following conclusions : I. Sample preparation technique affects the PSD of HCP's. In order to obtain consistent and comparable results in different studies, the mixing, molding and curing procedures must be standardized and carefully selected representative samples must be tested. 2. Similar to the f i r s t - i n t r u s i o n , the second-intrusion PSD's of HCP's show a decrease in total volume of pores that are uniform in cross section and a reduction in the size of pores that are uniform in cross section with increasing age and decreasing w:c ratio. 3. Approximately three-quarters of the total intrusion volume of an a i r free paste is due to pores that are uniform in cross section and the remaining to ink-bottle pores. The major fraction of the total volume of ink-bottle pores is intruded through entrances of sizes s l i g h t l y smaller than the threshold diameter. 4. The second-intrusion PSD curves of air-entrained HCP's containing different amounts of a i r match with the second-intrusion curves of corresponding a i r - f r e e pastes. Therefore, air-entraining only introduces the large a i r voids observable by a naked eye, and does not a l t e r the characteristic fine pore structure of HCP appreciably.

Vol. I I , No. 2 PORE STRUCTURE, AIR ENTRAINMENT, CEMENTPASTE Acknowledgement

265

The experimental work was carried out with the support of Enqineering Research Institute, during the author's graduate study at Iowa State University, Ames, Iowa, U.S.A. Many thanks are due to ProfEssors T. Demirel and R.A. Lohnes for their encouragement, assistance and friendship during this period. References I. 2. 3. 4. 5. 6. 7. 8. 9. IO. II. 12. H.F.W. Taylor, The Chemistry of Cements, Vol.l, Academic Press, New York (1964) D.N. Winslow and S. Diamond, Journal of Materials, JMLSA 5, 564 (1970). S. Diamond, Cem. Concr. Res. ~, 533 (1971). E.J. Sellevold, Cem. Concr. Res. 4, 399 (1974). D.H. Bager and E.J. Sellevold, Cem. Concr. Res. 5, 171 (1975). A. Auskern and W. Horn, Journal of Testing and Evaluation, JTEVA ~, 74 (1975) G.E. Troxell, H.E. Davis and J.W. Kelly, Composition and Properties of Concrete, 2nd. ed., McGraw-Hill Book Co., New York (1968). U.Z. Cebeci, Ph.D. dissertation, Iowa State University (1977). U.Z. Cebeci, T. Demirel and R.A. Lohnes, Transp. Res. Rec. No.675, 15 (I.978). C.Orr, Jr., Powder Tech. 3, ll7 (1969). ~.Z. Cebeci, J. Colloid Interface Sci., in print (1980). J.A. Lee and W.C. Maskell, Powder Tech. 7, 259 (1973).

13. D.N. Winslow, J. Colloid Interface Sci. 67, 42 (1978).