Self-healing blast furnace slag mortar subjected to carbonation and frost salt scaling

K. Sisomphon*, O. opurolu, A.L.A. Fraaij

Faculty of Civil Engineering and Geosciences, Delft University of Technology, Stevinweg 1, 2628 CN Delft, The Netherlands * Contact author. Telephone: +31 (0)15 27 81325, E-mail address: k.sisomphon@TUDelft.nl

1. Introduction Blast furnace slag cement (BFSC) is the most important product of the cement industry in northern European countries. From both environmental and economical points of view, blast-furnace slag (BFS) is a very attractive mineral admixture to use in concrete, particularly in low-heat concrete for massive structures or in high performance concrete. Even though using BFS in concrete has several benefits, it has been found that concrete containing a high amount of BFS has a poor resistance against carbonation due to its significantly low Ca(OH)2 content. The carbonation causes micro-cracking on the surface and reduces the micro-mechanical properties and durability of the BFSC concrete drastically. Frost salt scaling is considered as one of the most dangerous treats on BFSC concrete infrastructure. Due to concrete surface disintegration, also other attacks on the structure have more chance, which can result in a dramatic decrease in durability. Sodium monofluorophosphate (Na-MFP) treatment is one of the corrosion inhibition methods for reinforced concrete widely in use [1-3]. However, it has been recently reported that Na-MFP can also improve surface durability of BFSC concrete. In previous studies [4-5], it was reported that the application of Na-MFP treatment improves the frost salt scaling resistance of carbonated BFSC pastes. The 10% NaMFP solution was used as a surface post-treatment compound on carbonated BFSC paste in the study. In general, the results show that the treatment modifies the mineralogical structure and improves the resistance of carbonated BFSC paste against frost salt attack. The target of this study is to investigate the possibility of a self-healing action in the BFSC concrete structures which can be potentially affected by carbonation and frost salt scaling. The main objective is to research the effectiveness of using Na-MFP as a self healing agent in the cementitous system, which would enable the self-healing of the carbonation microstructure autogenously without any requirement of external application further. 2. Experimental investigation The expanded clay lightweight aggregate (LWA) which has a maximum size of 4 mm was used as healing media. To prepare the encapsulated lightweight aggregate (ELWA), the air-dried LWA was soaked into the 40% Na-MFP solution under vacuum pressure. After 30 minutes impregnation, the soaked LWA was filtrated by a thin filter paper to remove the excess compound solution. The wetted LWA was measured the weight, and hand-mixed with cement powder. The cement-to-wetted LWA ratio of 0.40 was controlled throughout the study. Two types of cement namely ordinary Portland cement (OPC 42,5 R) and BFSC (CEM III /B) were used as coating layer. After 24 hours, the prepared ELWAs were cured at 100%RH for 28 days. The mortars prepared from these ELWAs were designated as E-OPC and E-BFS, respectively.

To produce mortar mixtures, a CEM III /B 42,5 N HSR LH from ENCI cement manufacturer was used. The mortars with w/c ratio of 0.45 were prepared. The control mixture was designed with the sand-to-cement ratio of 2.5 by weight. The other mixtures with presences of ELWA were formulated to maintain the volume fraction of aggregate phase similar to the control mix. The specimens were cast in plastic containers with 55 mm diameter to a height of about 50 mm. Thereafter, the specimens were pre-conditioned at 50-55% RH until an age of 28 days. After that, the circumference surface and the bottom area were coated with low viscosity epoxy. The top trowel surface was only the area which was exposed to carbon dioxide environment. The accelerated carbonation which provides the carbon dioxide concentration of 3% by volume, with 65% RH was set up for the experiment. After the specimens have been carbonated for 14 days, the frost salt scaling test by conforming the ASTM C672 freezing-thawing cycle consisting of 17 h in -20oC freezing and then 7 h at 25oC was conducted. The scaled material was collected by using a filter paper after each cycle. Eventually, it was oven-dried at 105oC and weighted after 24 hours drying. The microstructure of mortars was studied by using environmental scanning electron microscope (ESEM):Philips XL30.The detail of preparation method was described in previous works [4-5]. 3. Results and discussion Fig. 1 presents the frost salt scaling result of mortars up to 7-cycle exposure. It was clearly seen that the control mortar with normal sand was severely attacked. In the experiment, it has been observed that the surface of specimen with normal sand was completely disintegrated after 2 cycles. However, for the mortars with ELWA, the specimens showed better resistance against the frost salt attack. The conditions of mortars after one cycle scaling were shown in Fig. 2. In comparison, the E-OPC mortar performed slightly better than the E-BFS mortar. This would be due to a formation of calcium carbonate which is a product of Ca(OH)2 carbonation. The photomicrographs of carbonated BFSC mortars are presented in Fig. 3. Generally, dark areas show the porosity, while the unreacted slag particle could be seen as light grey areas. Unreacted clinker particles are even lighter. In Fig. 3(a), it is obviously seen at 500 magnification that carbonation induces severely shrinkage which leads to coarsening pore in the matrix phase. Fig. 3(b) shows a photomicrograph of the sand mortar in non-carbonated zone which has much denser microstructure for comparison. After carbonation attack, the pore coarsening would be due to the decomposition of C-S-H phases and formation of porous silica gel.

(a)

(b)

(c)
Fig.1 Frost scaling of mortars Fig.2 Condition of mortars after 1-cycle scaling (a) Sand mortar; (b) E-OPC; (c) E-BFS

Unlike the carbonation on calcium hydroxide (CH), carbonation on hydrated phases does not show any significant problem on alkalinity reduction. However the reaction yields the reduction in volume of the matrix which is normally called carbonation shrinkage. Due to a low CH content in the BFSC paste, carbonation process induces to a coarser and even weaker microstructure compared with the OPC matrix [5]. However, it was obviously seen in Fig. 3(c) and (d) that the utilization of ELWA dramatically decreases the total porosity of the carbonated matrix. The pore size was significantly refined with presences of ELWA. After carbonation, the porosity coarsening would take place not only at the matrix zone, but also on the coating layer. This phenomenon would induce a carbonation triggered mechanism which allows the encapsulated Na-MPF released to the matrix after the coating paste layer has been attacked by CO2. The influence of carbonation attack on the pore structure of coating layer and interfacial transition zone (ITZ) can be obviously seen in Fig. 4.

(a) Carbonated sand mortar

(b) Non-carbonated control mortar

(c) Carbonated E-OPC

(d) Carbonated E-BFS

Fig.3 - Photomicrographs of mortars

Matrix Coating

ELWA

Coating ELWA Matrix

(a) Non-carbonated E-OPC

(b) Carbonated E-OPC

ELWA

Matrix Coating Coating

Matrix
(c) Non-carbonated E-BFS (d) Carbonated E-BFS Fig.4 - Photomicrographs of ITZ

ELWA

The EDX analysis was performed on polished specimens to investigate the leaching of encapsulated healing compound. At 500x magnification, the concentration of phosphorous in the matrix area at the position about 500 m apart from the LWA surface was determined. The concentration was measured at 20 different randomly selected paste locations through the area. The result indicated that the ELWA released a significant amount of Na-MFP. There is no noticeable different between the mortars with OPC and BFSC coating layer. The phosphorous concentration of about 13-17% by weight can be detected in carbonated area, while the slightly lower concentration (7-11% by weight) was observed in the non-carbonated area. This result would confirm the triggered mechanism of encapsulation system. The encapsulated compound was released after the matrix and coating layer has been attacked by carbon dioxide. It would be remarked that the phosphorous concentration determined from the control mortar was only about 2-3% by weight. 4. Conclusion A self-healing system using encapsulated lightweight aggregate for carbonated blast furnace slag mixtures subjected to frost scaling attack was proposed. The results from freezing and thawing test show that the mortars with encapsulated lightweight aggregate revealed an excellent frost salt durability. The photomicrographs showed an improvement of pore structure of the carbonated matrix particularly on the interfacial transition zone between sand and matrix. After carbonation attack, the pore structure of coating layer was coarsened which allows the encapsulated compound to be released to the matrix. From EDX results, phosphorous leached from ELWA to the matrix can be observed. For the mortar with ELWA coated with OPC, the healing mechanism would be due to the combination of treatment by NaMFP solution and also calcium hydroxide supplied from the coating Portland cement paste layer. Acknowledgement Authors would like to thank SenterNovem for the financial support granted for the project: SHM0616. References 1. Ngala VT, Page CL, Page MM, Corrosion inhibitor systems for remedial treatment of reinforced concrete: Part 2. Sodium monofluorophosphate, Corrosion Science 45 (2003) 1523-1537. 2. Alonso C, Adrade C, Argiz C, Malric B, Na2PO3F as inhibitor of corroding reinforcement in carbonated concrete, Cement and Concrete Research 26 (1996) 405-415. 3. Andrade C, Aloso C, Acha M, Malric B, Preliminary testing of concrete Na2PO3F as a curative corrosion inhibitor for steel reinforcements in concrete, Cement and Concrete Research 22 (1992) 869-881. 4. opurolu O, Fraaij ALA, Bijen JMJM, Effect of sodium monofluorophosphate treatment on microstructure and frost salt scaling durability of slag cement paste, Cement and Concrete Research 36 (2006) 1475-1482. 5. Sisomphon K, opurolu O, Fraaij ALA, Transport properties and frost salt scaling resistance of carbonated blast-furnace slag mortars after sodium monofluorophosphate treatment, to be published in Proc. the 2nd International RILEM Workshop on Concrete Durability and Service Life Planning, Haifa, Israel, 2009.