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CEMENT and CONCRETE RESEARCH. Vol. 17, pp. 349-356, 1987. Printed in the USA. 0008-8846/87 $3.00+00.

Copyright (c) 1987 Pergamon Journals, Ltd.


E. Breve/* Materials Research Laboratory The Pennsylvania State University University Park, PA 16802, USA

(Refereed) (Received Nov. 13, 1986; in final form Jan. 14, 1987)


A cement-based humidities at when complete long hardening

paint coating was h a r d e n e d in air of different relative room temperature. The best properties were obtained carbonation took place at high relative humidities and times.


Cement based paints are commonly used as surface coatings on brick and concrete structures. As such, they need to be adherent and resistant to scratching and other forms of wear. How well a cement-based paint meets these requirements depends on the conditions under which it is hydrated, and hence it is important to determine the hydration conditions leading to optimal hardening of the paint after it is applied. Mechanisms of hydration and carbonation of cement-based paints are poorly documented because such information is often not considered critical for their successful utilization. However, they are well described for cement paste and s i m i l a r materials. For example, Suzuki et al. (1) have enlightened the kinetics of the carbonation process of C-S-H. Young et al. (2) reported improved mechanical properties of cement paste after carbonatlo~ The deposit of CaCO 3 in the cement paste strengthens the material and leads to partly filling up of pores and cracks. The relative humidity in equilibrium with water filled pores depends on the size of the pores according to the Kelvin equation: 27
Ap O(
- R

* P r e v i o u s l y with Surface Coatings 141, DK-2630 Taastr~p, Denmark.



Institute, Box


350 E. Breval

Vol. 17, No. 2

where Ap is the lowering of the vapor pressure inside a curved surface with the radius of curvature R and the water having the surface tension Y. For example, water filled capillaries with the radii of 10, 5, 2 or 1 nm will be in equilibrium with about 90, 80, 60 or 40~ relative humidity respectively. A g e n e r a l l y accepted fact, also reported by Young et al. (2), is that carbonation can not take place when the relative humidity is too low (below ~50%). This favors the theory of carbonation being a t h r o u g h - s o l u t i o n process. They also report that a too high r e l a t i v e humidity (YSO~) also hinders the carbonation process for cement or concrete specimens larger than a few cm. At higher relative humidities more pores are filled according to the Kelvin equation. The diffusion coefficient for CO, in air is of the order of 10-5 m2s 1 whereas it for HCO 3 and C032 in water can be estimated from the figures for similar ions to be of the order of 10-9 m2s -I (S). The water thus acts as a diffusion barrier to CO 2 and if the cement paste product contains few larger but many nanometer size pores the CO 2 is forced to migrate into the cement paste through water. At high relative humidities the outer part of the cement paste will thus carbonate fully but the water filled smaller pores will delay the CO 2 diffusion into the material. The present study describes the way in which both the structure of a commercial cement based paint and various of its wear properties depend on hardenin E conditions.



and Methods

The paint studied. CEMPEXO (R)~. is a powder consisting of 85+5 w/o of white Portland cement having a B l a i n e surface area of ~400 m 2 kg-l-with the balance being TiO 2 pigment having a particle size of 0.1 to 10 pm and proprietary filler, hardener and water repellants. It was applied to the smooth surface (surface roughness !1 mm) of 10 cm x 10 cm pieces of a commercially produced concrete block. The block consisted of an aggregate of variously shaped ~ to.-. size quartz, feldspar and flint grains in a portland cement matrix (Fig. 1). The a p p l i c a t i o n took place at 202eC in air containing 0.08 vol ~ CO 2 at 65~5~ r e l a t i v e humidity and was carried out by moistening the surface with water immediately before application of a well mixed slurry. The slurry consisted of one volume paint powder to one volume water. After 24 hours another coating of a similar freshly prepared slurry was applied. A p p r o x i m a t e l y lg powder was used to coat ~S'lO-Sm 2 which resulted in a paint film 100 to 500 ~m in thickness. The paint was hardened immediately after the second application at 202"C in air containing 0.08 CO 2 at r e l a t i v e humidities of ~ 100, 75, 35 or 15%. Hydration was stopped after times ranging from 24 to 720 hours by placing the specimens in a small desiccator containing silica gel. The equilibrium relative humidity in the desiccator was not measured but the silica gel was specified to keep a relative humidity of 0.13%. The painted surfaces were characterized v i s u a l l y and by optical and scanning e l e c t r o n microscopy and x-ray diffraction. In addition, thin sections were prepared perpendicular to the coating and examined by polarizing microscopy. The wear properties were evaluated qualitatively by rubbing with

~Product of Aalborg Portland, P.O. Box 165, DE-9100 Aalborg, Denmark.



a finger and q u a n t i t a t i v e l y by using a Leitz M i n i l o a d hardness tester to measure Vickers hardness. Three to five indentations were made more than 500 ~m apart at loads of 0.15, 0.25 and 0.5ON. T y p i c a l l y the standard d e v i a t i o n of the hardness measurements was 10% of the mean hardness.

Results The structure and p r o p e r t i e s are summarized in table 1 and the r e s u l t s show that the appearance and the wear properties of the coating can be correlated with its structure. Complete carbonation leads to a shiny surface composed primarily of CaCO 3 (C~) *) which does not chalk when rubbed and which has a Vickers hardness of ~ 100 MPa. This condition is easily identified by p o l a r i z i n g m i c r o s c o p y (figure 1) or by scanning e l e c t r o n m i c r o s c o p y (SEM) (figure 2). In the polarizing microscope, the complete carbonated coating has a light color when observed between crossed nicols due to high birefringence of CaCO~, whereas unhydrated cement, Ca(OH) 2 and CSH have low birefringence or are isometric. In the SEM the surface appears smooth, dense and substantially free of cracks. Figure 2a shows such surface (hardened for 240 hours at ~100% r e l a t i v e humidity). Hardening for the same time at ~75% r e l a t i v e humidity leads to a matt, n o n - c h a l k i n g appearance in which the coating contains a significant number of cracks and elongated pores (Figure 2b). Figure 2c shows a typical chalking surface hardened for 72 hours at ~ 35% relative humidity. This coating has a very loose structure. The same coating is shown in Figure lb in p o l a r i z i n g microscope. The dark c o l o r of the coating as o b s e r v e d between crossed nicols is noticeable. Figure 3 shows the very different appearances of Vickers hardness impressions in (a) completely carbonated and (b) only slightly carbonated surfaces. Cracking occurs about the indentation in the former surface, whereas the i n d e n t a t i o n s in the latter surface are formed by compaction of loose material. The r e s u l t s of the x-ray d i f f r a c t i o n studies serve to identify the chemical reactions during hardening. The dominant phase in the original paint is t r i c a l c l u m s i l i c a t e (C3S). This remains a major phase in the coatings which are soft, matt and chalking and which have the loose structure shown in figure 2c. Also the hydration product Ca(OH) 2 (CH) is present in considerable quantity in such coatings. This shows that neither hydration nor carbonation is complete. Harder, matt, n o n - c h a l k i n g coatings contain less C3S and CH indicating more pronounced but s t i l l i n c o m p l e t e h y d r a t i o n and carbonation. Only when the coating becomes shiny and developes a Vickers hardness > 50 MPa is hydration and carbonation sufficiently complete that neither CH nor C3S can be detected by x-ray diffraction The r e s u l t s in table I show that c o m p l e t e c a r b o n a t i o n occurs at a r e l a t i v e humidity ~100% after more than 24 hours. The surface is shiny and n o n - c h a l k l n g and the V i c k e r s hardness is between ~50 and 120 MPa. After h a r d e n i n g for less than 24 hours at ~100% r e l a t i v e humidity the painted surface has a matt appearance but is non-chalklng and the Vickers' hardness is b e l o w 35 MPa. The cement is not e v e n f u l l y hydrated and the c a r b o n a t i o n is incomplete. The same appearance is obtained between 72 hours and 720 hours at ~75% r e l a t i v e humidity indicating incomplete hydration and carbonation At lower relative humidities and/or shorter hardening times the surface is matt and chalking, the V i c k e r s hardness is b e t w e e n 20 and 40 MPa and there is indication of poor hydration and carbonation

*Cement notation, see footnote to table 1.

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F I G U R E 1. T h i n s e c t i o n of c e m e n t - b a s e d p a l n t on c o n c r e t e o b s e r v e d in a p o l a r l z l n g m i c r o s c o p e b e t w e e n c r o s s e d nlcols. The p a i n t is m a r k e d w i t h arrows. A w e l l hardened paint (240 h, ~ 100~ relative humidity) is shown in (a). The light color of the paint indicates pronounced carbonation. A poorly hardened paint (72h, ~ 35~ relatlve humidity) is shown in (b). The dark color of the paint is a sign of llttle carbonatior~




F I G U R E 2. S u r f a c e s of c e m e n t - b a s e d paints observed in scanning electron microscope. The dense structure shown in (a) is obtained by extensive carbonation (240 h o u r s , ~ 100% relative humidity). The p a r t l y carbonated coating (240 hours, ~ 75% relative humidity) s h o w n in (b) exhibits cracks and pores. (c) Shows a t y p i c a l c h a l k i n g s u r f a c e w i t h the v e r y l o o s e s t r u c t u r e characteristic of little carbonation. (72 hours, ~ 35% relative humidity.)

354 E. Breval

Vol. 17, No. 2


Characteristics of Cement-Based Paint Hardened at Room Temperature in Air of Different Relative Humidities.







Surface Appearance Surface Durability

Matt, Not Chalking

Shiny, Not Chalking


Shiny, Not Chalking 110

Shiny, Not Chalking 120

~ 100

Vickers Hardness (MPa)

CU +++ CH + C3S + Matt, Chalking

Phases (X-Ray) Surface Appearance Surface Durability

C ~ +++ CH C3S Matt, Not Chalking Matt, Not Chalking Matt, Not Chalking


Vickers Hardness (MPa)

CO +++ CH ++ C3S ++




Phases (X-Ray) Surface Appearance Surface Durability

Matt, Chalking

Matt, Chalking

Matt, Chalking

Matt, Chalking


Vickers Hardness (MPa) Surface Appearance Surface Durability



Matt, Chalking

Matt, Chalking

Matt, Chalking

Matt, Chalking


Vickers Hardness (MPa)



C = CaO S = SiO 2 H = Ctt~O

+++ = strong x-ray signal ++ = medium x-ray signal + = weak x-ray signal = no x-ray signal

Chalking = paint adheres to finger after even light rubbir~.



Disoussion E x t e n s i v e hardening of cement paint coating takes p l a c e o n l y at high relative humidities (approximately 80-100%) which seem to favor both complete hydration and complete carbonation This favors the theory of carbonation as a through-solution process, in accord with the ideas of Suzuki et al. (1) who have studied the carbonation process in detail of the cement hydration product C-S-H. At l o w e r r e l a t i v e h u m i d i t i e s (below ~80%) the paint coating can p a r t i a l l y dry out. The h y d r a t i o n is i n c o m p l e t e as both C3S and CH are present, however, some c a r b o n a t i o n can s t i l l take place p a r a l l e l to the hydration process. Water thus plays a role in the carbonation process even of the partly drled-out cement paint and in this case the through-solution theory may still be valid. The present r e s u l t s are a l s o in agreement with the r e s u l t s of Young et al. (2), who found that cement products d e v e l o p e d high strength in the presence of water and CO 2. However, they found that o n l y the outer part of their specimens to be fully carbonated at high relative humidities, probably because the pores were filled with water which acts as a diffusion barrier to CO 2. However, as a cement paint coating s e l d o m is more than $00 ~m thick it seems r e a s o n a b l e that c o m p l e t e c a r b o n a t i o n can take place e v e n at ~ 100% r e l a t i v e humidity. The present r e s u l t s point out the i m p o r t a n c e of the e n v i r o n m e n t during the first few days after a p p l i c a t i o n of a cement based surface coating.

FIGURE 3. Hardness i n d e n t a t i o n s on surfaces of cement based paints. (a) s h o w s the same surface as shown in Figure 2a. The surface coating is smooth and hard and cracks are formed around the indentations. (b) shows the same surface as shown in Figure 20. The coating is very soft and seems to be easily compacted. No cracks are visible near the indentations.

356 E. Breval

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The author wishes to thank N. H. Macmillan, F. Larsen, and P. Bastholm, for helpful discussions. The study was supported by the Danish Council of Technology and The F.L. Smidth Donation Fund.


1. 2. 3.

K. Suzuki, T. Nishikawa, and S. Ito, Cem. Contr. Res., 15, 213 (1985). J.F. Young, R.L. Berger, and J. Breese, J. Am. Ceram. Soo. 57, 394, (1974). Handbook of Chemistry and Physics, p. F47, Chem. Pub. Co., 50th Ed. 196970.

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