Cement Chemistry
Cement hydration
Reaction of cement with water Exothermic; heat released is called Heat of Hydration Rate of heat evolution is faster if the reaction is quicker Heat evolved depends on heat of hydration of individual compounds, and also on the clinker morphology!
Heat evolution
Heat of hydration of pure cement compounds Compound C3S C2S C3A C4AF HOH (J/g) 502 260 867 419
Bogue: of total heat is evolved between 1 and 3 days, about in 7 days, and 83 91% in 6 months
Calorimeter
Maturity Heat rate, W/kg
Sample Chamber
3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0 50 100 t20 hours 150 C1 C2 200
Polystyrene cover
Taylor, 1996
Suggested new heat evolution pattern that shows an initial endothermic peak due to the dissolution of alkali sulphates Hewlett 2001
Heat peaks
Peak I: Heat of wetting + some early C-S-H formation Dormant period: Very slow rate of heat evolution Peak II: Main peak; associated with the rapid dissolution of C3S to form CSH and CH, and formation of ettringite (AFt) from C3A. A slowdown of the hydration process beyond the main peak leads to lower rates of heat evolution. A broader peak (III) is associated with the conversion of ettringite to monosulphate (AFm).
Points to ponder..
Difficult to obtain the correct relationship between heat evolution and temperature unless the system is perfectly insulated Dependence on the water to cement ratio: Water has a much higher specific heat than cement, thus when more water is present, a higher degree of heat will be required to increase the temperature of the system. Cement contains highly soluble alkali oxides (Na2O and K2O). The dissolution of these compounds is responsible for the high alkalinity (pH 12 13) of the pore solution. Thus, the hydration of cement actually takes place in the pore solution, and not in water.
Dormant period
Several theories proposed These theories basically point to the fact that a layer (either of hydrates or ions) is created on the surface of cement particles Further wetting of the cement particle is possible only by diffusion across this layer Therefore, rate slows down End of dormant periods occurs when: - Barrier gets weakened by aging - Rates of diffusion increase, and - Ionic strength around the hydrating particle reduces
Hydration reactions
Silicates (C3S and C2S) hydrate to produce Calcium-silicatehydrate (C-S-H) gel and calcium hydroxide (CH) 3 times as much CH produced by C3S hydration compared to C2S C-S-H does not have a well-defined composition; C/S varies from 1.5 to 2 Aluminates (C3A and C4AF), in the absence of gypsum, hydrate rapidly to produce Calcium-aluminate-hydrates (C-AH) In the presence of gypsum, ettringite (AFt) and monosulphate (AFm) are produced (depending on the C3A to SO3 ratio) Ettringite formation is known to be expansive (numerous mechanisms suggested)
Reactions - Specifics
2 C3S + 6 H C3S2H3 + 3 CH 2 C2S + 4 H C3S2H3 + CH 2 C3A + 21 H C4AH13 + C2AH8 Flash set reaction! C2AH8 is a metastable phase that deposits as hexagonal platelets (similar to CH). Above 30 oC, it is converted to cubic hydrogarnet (C3AH6). In the presence of gypsum, C3A + 3 CSH2 + 26 H C6AS3H32
Aluminate-sulphate reactions
Nearly all the SO42- gets combined to form ettringite in an ordinary Portland cement. If there is still C3A left after this reaction, it can combine with ettringite to form monosulphate (or AFm phase) which has a stoichiometry of C4ASH12-18. If there is sufficient excess C3A, then C4AH13 can also form as a hydration product, and can exist in a solid solution with AFm. C4AF produces similar hydration products as C3A, with the Al3+ being partly replaced by Fe3+. The final hydration product depends on the availability of lime in the system. In the presence of gypsum, C4AF produces an iron-substituted ettringite. Higher the ratio C4AF/C3A, lower is the conversion of ettringite to monosulphate.
Evolution of hydration
Taylor, 1968
Dense
Contains less Al and S Formed with large grains
Kinetics of hydration
The progress of cement hydration depends on: Rate of dissolution of the involved phases (in the initial stages), and at later stages, Rate of nucleation and crystal growth of hydrates Rate of diffusion of water and dissolved ions through the hydrated materials already formed
Some micrographs
Bright particles: Unhydrated cement; Gray regions: C-S-H; white rim around aggregates: CH
Some micrographs
C3S mortar showing white unhydrated cement particles and gray C-S-H, along with white rims of CH
2.
3. 4.
Example 1
w/c = 0.50; Assume 100% hydration and no drying; Calculate the volume of capillary pores. Let mass of cement = 100 g. Hence, Vcem = 100/3.15 = 31.8 ml Mwater = 50 g, therefore Vw = 50 ml. Vbound-w = 23 ml Hence, Vsolid-hcp = 31.8 ml + 23 ml 0.254 x 23 ml = 48.9 ml Porosity = 28% = 0.28 = Vgel-pores / (48.9 ml + Vgel-pores) Vgel-pores = 19.0 ml Hence total hcp volume = 48.9 + 19.0 = 67.9 ml Total reactant volume = 31.8 + 50 = 81.8 ml. Therefore, volume of capillary pores, Vcap-pores = 81.8 67.9 = 13.9 ml Of these, (50-23-19) = 8 ml will be filled with water, and the remaining (5.9 ml) will be empty.
From the above scenario, 23 ml + 19 ml = 42 ml of water is required for complete conversion of 100 g of cement to the hydration product. In other words, a w/c of 0.42 is required. What would happen if the w/c is less than 0.42? Consider the next example.
Example 2
w/c = 0.30; Cement = 100 g, water = 30 g; Assume that p grams of cement hydrates. Hence Vsolid-hcp = p/3.15 + 0.23p 0.254 x 0.23p = 0.489p Porosity = 0.28 = Vgel-pores / (0.489p + Vgel-pores) (1) Total water = 30 ml = 0.23p + Vgel-pores ... (2) Solving 1 and 2, p = 71.5 g, and Vgel-pores = 13.5 ml Thus, Vhcp = 0.489 x 71.5 + 13.5 = 48.5 ml Vunhyd-cem = (100 71.5)/3.15 = 9.1 ml Hence, Vcap-pores = (100/3.15 + 30) (48.5 + 9.1) = 4.2 ml
That means there are 4.2 ml of empty capillary pores. If this cement paste gets any external moisture (for example, from curing) more cement will hydrate and fill up this space.
SE micrograph of paste
Scanning electron micrograph of 7-day old hardened cement paste (3500). Bottom left: cement particle coated with C-S-H surrounded by ettringite needles; Upper left: platelets of monosulfoaluminate; Right: large crystal of calcium hydroxide
CSH
Taylor, 1968
Young et al., 1998 The structure of C-S-H is best described by the Feldman-Sereda model. It consists of randomly oriented sheets of C-S-H, with water adsorbed on the surface of the sheets (adsorbed water) , as well as in between the layers (interlayer water), and in the spaces inside (capillary water).
CSH Properties
The Feldman Sereda model suggests a high surface area for CSH Using water sorption and N2 sorption measurements, a surface area of 200000 m2/kg is reported (ordinary PC has a fineness in the order of 225 325 m2/kg). Small angle X-ray scattering measurements show results in the range of 600000 m2/kg. The corresponding figure for high pressure steam-cured cement paste is 7000 m2/kg, which suggests that hydration at different temperatures leads to different gel structures. The structure of C-S-H is compared to the crystal structure of Jennite and Tobermorite. A combination of the two minerals is supposed to be the closest to C-S-H. High covalent/ionic and Van der Waals forces Occupies a volume of 50-65% of the paste
Calcium Hydroxide
Hexagonal crystals, generally oriented tangentially to pore spaces and aggregates along the longitudinal axis Low surface area (0.5 m2/g) Low Van der Waals forces Volume 20-25%
Calcium sulphoaluminates
Ettringite: Acicular, columnar, hexagonal crystals (seen as prismatic needles). The presence of tubular channels in between the columns can lead to high water absorption and swelling by ettringite. This is one of the theories explaining the expansion caused by ettringite formation. Monosulphate plain hexagonal Volume occupied is 15 20%