SELF HEALING OF CEMENT PASTE BY CALCIUM ALUMINATE BASED AGENTS

O. Copuroglu *, K. Sisomphon, and S. Komatsu
Delft University of Technology, Faculty CiTG, Materials and Environme nt, Stevinweg 1, 2628 CN, Delft, The Netherlands. *contact author, email: o.copuroglu@tudelft.nl

Introduction
Self-healing of concrete is a h ighly challenging subject mainly because of its multi-component material nature, complex chemical reactions invol ved and continuous interaction of the material with environment. It is therefore important to consider several aspects when attempting to design concrete elements with self-healing ability. One disadvantage of concrete in comparison with relatively uniform materials (e.g. polymers), is its heterogeneous structure. Concrete is basically composed of cement paste, sand, gravel, and interfacial trans ition zones between the solids. Pristine concrete microstructure has a pH of approximately 12,5 -13 depending on the cement type used. Furthermore the paste contains significant amount of capillary porosity, which determines essentially the transport proper ties of concrete. All these parameters amplify the complexity of designing concrete with self -healing ability. Except utilization of biological agents [1], self-healing mechanisms in cementitious materials are currently based on further hydration of unreac ted particles. These particles can be ordinary cement minerals (alite/belite) as well as other types of cementitious particles, which had not been fully hydrated in the initial hydration stage and remained partially hydrated in cement paste. However such a mechanism is not highly promising in healing typical cracks in concrete because of the limited remaining potential and difficulties in optimizing the performance. On the other hand non-native agents such as two component polymer-based agents encapsu lated by glycol dimethycrylate may not be suitable for concrete because one should encapsulate the healing agent and mix the catalyst in the cement paste. This may affect the hydration kinetics and strength development of concrete. High er cost of the se agents is another disadvantage. Therefore the market needs low -cost cement paste compatible self -healing agents for sustainable material use. Attempting to respond these requirem ents, a new project is being initiated at Delft University of Technology. The aim is to use encapsulated inorganic ternary blends for autogenous ettringite mineral production upon crack formation in concrete. The theory behind the he aling agents to be used has been known for decades in the cement and concrete science. However utilization of these agents in the self -healing framework is a relatively new theme.

In addition to its formation during cement hydration.g.3SO 4.SO 4. Also called as “primary ettringite”. shrinkage compensating concrete).3CaO.2H2 O + 26H 2 O→ 3CaO.Al 2 O3 + 3CaSO 4. Figure 1. Al(OH)-4. this mineral is not detrimental to concrete and it is formed according to: 3CaO. and the solubility product of ettringite is about K sp =2. (Left) Photomicrograph of a single imperfect ettringite crystal tip and (right) massive ettringite cluster produced by hydration of calcium -aluminate based agents. it is also being used for favorable purposes.80E-45 [2]. 1] The ettringite crystals are pseudo hexagonal (trigonal) and can be observed in the form of highly elongated needles and rods (Figure 1).This paper reviews existing literature on the self -healing of concrete by calcium aluminate based agents and discusses the potential crack healing capacity of ettringite minerals. Many special concrete applications have been realized by taking advantage of the expansive nature of ettringite formation (e. . Ettringite is stable up to around 90 °C but in cement paste this value is slightly lower. Technical Background Ettringite (6CaO. ettringite can also be produced by external sulfate attack which transforms monosulfoaluminate (Ca 4 Al 2(OH) 12 .Al 2O 3.Al 2O 3. and OH -. which may cause distress in concrete and eventually cause cracking. The crystals can precipitate from a solution bearing Ca2+ . This detrimental formation occurs by the recrystallization of decomposed primary ettringite crystals. This transformation is an increase in solid volume.SO4 . which is observed in steam -cured concrete. Although ettringite is associated with detrimental processes in concrete.6H2O) th at had been produced during the ce ment hydration into ettringite crystals. SO 2-4.32H2O) is a naturally occurring mineral as well as one of the important main hydration products in ordinary portland cement paste. (Images captured in ESEM/GS E mode).32H 2 O [eq. Another form of ettringite damage is known as delayed et tringite formation (DEF).

in the new project. On the Encapsulation of Calcium Aluminate B ased Agents Current techniques have proved that cracks up to 0. providing a cost efficient alternative [7]. They also poi nted out that using carbonates would increase the healing ability.In the recent years. CaO. Therefore. C 3 A was reported to produce the highest expansion among all common calcium aluminates [6]. as a first step. A more challenging second phase of th e project is encapsulating the granules preferably by an inorganic coating that has a lower E modulus in comparison with the surrounding cement paste. insoluble and resistant against high pH of cement paste. which unfortunately leaves extremely limited number of options. Their results revealed that a portion of replacement agent can remain unreacted in the system and can heal an eventual crack formation upon meeting with dormant or streaming water [5].a. performance/price ratio might be the decisive parameter. An ideal encapsulation material should be inorganic. Hosoda et al [3] and Kishi et al [4] studied the use of cementitous expansive agents as cement repl acement material and their potential as self -healing agent. As an alternative. it must be mechanically stable enough to remain intact during the concrete production. In conventional production techniques C 3 A forms at around 1500 °C.Al 2O 3. the healing agent is a ternary blend of different minerals in powder form. However using these agents might pose certain risk regarding uncontrolled expansio n and cracking. It has been reported that the size of the granules can be optimized further with this technique [8]. This is to ensure crack propagation towards the capsules and to expose the healing agents to an . One of these options is a technique called freeze granulation. 2H2O).12H2O]2 .Fe2O 3 can also be used. As stated earlier.Al 2O 3 (a.SO 4). and anhydrate (CaSO 4) minerals. Instead of hauyne. however recent developments reduced this temperature down to 1050 °C. it will be investigated to find out whether or not encapsulating the ettringite-producing agents would provide technical advantages. Regardless what the involved production costs can be. The encapsulation method must be a non -aqueous type in order to avoid early hydration of the agents. granulation of the agents should be realized prior to the enc apsulation stage. which is based on sprayi ng (in this case non -aqueous) suspensions into liquid nitrogen and consequently drying the granules by freeze drying. Need for non -aqueous process throughout the entire sequence must be strictly followed. lime (CaO). Furthermore. The agent generally used for ettringite production is a ternary mineral mixture of hauyne (4CaO.k. 4CaO. There are several challenges against suitabl e encapsulation of exp ansive agents. several other calcium aluminates such as 3CaO.3Al 2O 3. However. Use of calcium aluminate based materials as healing agent has been investigated by a number of researchers.4mm can be autogenously healed by calcium aluminate based agents when used as cement replacement material [5]. C3 A). expansive cements and agents found us e in the projects on self-healing of concrete.Al 2O 3. which is possibly due to the formation of carbonate analog of ettringite ([Ca3 Al(OH) 6 .(CO3)3 .

Hosoda. E. Jonkers. 195 -205.G. 2007. doi:10. 2. Japan. Healing Properties of Self Healing Concrete with Water Passing Through Crack . Soc. Improving Powders with Freeze Granulation. Sulphate attack on concrete: prediction of the aft stability from phase equilibria . 1993: p. Self Healing of Crack and Water Permeability of Expansive Concrete . Kishi.g. and F. et al. Hosoda.12. J. et al. p. Application of bacteria as self -healing agent for the development of sustainable concrete Ecological Engineering.M. 7. T. in First International Conference on Self Healing Materials .P. 29(5): p. Self-Healing Behaviou r by Cementitous Recrystallization of Cracked Concrete Incorporating Expansive Agent . Lattice Model for Simulating Fracture of Concrete. . Springer: Noordwijk aan Zee. 2003. and J. [9]) and the results can be used in pursuit of finding proper encapsulation materials. Ceramic Industry. Am.eventual water canal. Sjöstedt.. This behavior can be simulated by computational fracture models (e.. Rundgren.. 6. Concept for stages of calcium aluminate based agent encapsulation and its use in concrete. Springer: Noordwijk aan Zee. 2853 63. 731 -735. Investigations on cement expansion associated with ettringite formation. Odler. Numerical Models in Fracture Mechanics of Concrete.ecoleng. 4.. 1999. Colan -Subauste. 40 -44. I. O. Chemical Preparation of the Binary Compounds in the Calcia –Alumina System by Self -Propagating Combustion Synthesis. 2009. April: p. 218 -224. K. 8.. 81(11): p. and J. A. References 1.036 Article in Press.2008. in International Congress on the Chemistry of Cement . A. Cement and Concrete Research..1016/j..M. et al. p. in First International Conference on Self Healing 2007. Ceram. 2008: Tokyo.. C. Vanmier. D. et al.. 9. Damidot. Figure 2. Schlangen. Lyckfeldt. 3. 5. 316 –321. Tas. An illustration of the concept for stages of calcium aluminate based agent encapsulation and its possible use in concrete is given in Figure 2. 199 2: New Delhi. H. 1998. an d M.. in 8th International Symposium on Utilization of High -Strength and High Performance Concrete . Glasser.