CE 6110 Advanced Concrete Technology

Cement Chemistry

Jan 7, 2014

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 C3 S C2 S C3 A 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

Secondary Water Tank

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

Interface Circuits and Relays

Adiabatic calorimeter at WITS, South Africa

Signal Conditioning Unit

Heat evolution pattern Ramesh Babu, 2008

Isothermal calorimeter at EPFL, Switzerland

IIT Madras Calorimeter

Views of specimen chamber

Prasath, 2012

Top: Schematic diagram Bottom: Overview

Specimen chamber inside tank

Heat evolution pattern

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.

Effect of w/c

Mix

Peak Heat rate (W/kg)

Time to peak (hr)

Duration of dormant period (hr) 1.5 3 3 3 4

Total heat at 3 day (kJ/kg)

Peak temperatur e (C)

Compressive strength (MPa) 3 7 days 28 days days

Prasath, 2012

0.40 w/c 0.45 w/c 0.50 w/c 0.55 w/c 0.60 w/c

7.72 6.19 4.77 4.40 4.19

5.75 8.25 9.25 9 9.5

289 281 262 242 227

70.2 65.9 60.3 60.5 59.8

44.4 35.1 29.3 22.1 15.0

50.4 45.3 36.6 27.9 24.0

64.4 61.2 47.1 36.9 29.1

Effect of pozzolans

De Schutter, G. (1999), Hydration and temperature development of concrete made with blast-furnace slag cement, Cement and Concrete Research, Vol. 29, pp. 143 -149.

Mix

Peak Heat rate (W/kg) 4.77 4.47 4.25 3.25 2.46

Time to peak (hr)

Control CCFA 20% CCFA 30% CFFA 20% CFFA 30%

9.25 8.5 8.25 9 11.5

Duration of dormant period (hr) 3 4.75 3.5 4.25 7

Total heat at 3 day (kJ/kg) 262 264 258 181 141

Peak temperatur e (C)

Compressive strength (MPa) 3 days 7 days 28 days 29.3 26.5 22.0 18.7 17.3 36.6 35.8 32.3 25.6 22.6 47.1 44.8 40.1 36.8 32.6

60.3 62.0 61.0 52.1 44.5

Prasath, 2012

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 C2 S 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
http://iti.northwestern.edu/cement/monograph/Monograph5_3.html

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

Young et al. 1998

Evolution of hydration products

Taylor, 1968

Inner and Outer CSH

Inner CSH (Phenograin CSH) Dense Contains less Al and S Formed with large grains

Outer CSH (Groundmass CSH) Less dense (has more pores) Contains more Al and S (AFm) Formed with small grains

Inner and outer products

Paul Stutzman http://iti.northwestern.edu/cement/mono graph/Monograph5_4_2.html

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

Factors affecting hydration rate

1. 2. 3. 4. 5. 6. 7. The phase composition of cement The amount and form of gypsum in the cement: Whether gypsum is present in the dihydrate, hemihydrate, or the anhydrite form. Fineness of cement: Higher the fineness, higher the rate of reaction due to availability of a larger surface area. w/c of mix: At high w/c, hydration may progress till all of the cement is consumed, while at low w/c the reaction may stop altogether due to lack of water. Curing conditions: The relative humidity can have major effects on the progress of hydration. Hydration temperature: Increase in temperature generally causes an increase in the rate of the reaction, although the hydrated structure can be different at different temperatures. Presence of chemical admixtures: For example, set controllers, and plasticizers.

Composition of pore solution

The evolution of pore solution composition for a typical cement (0.6% equivalent Na2O, 3% SO3, 0.5 w/c) is shown here. By 1 week, the only ions remaining in appreciable concentration are Na+, K+, and OH-. The concentration of OH- is almost a mirror image of that of SO42-, due to considerations of ionic balance within the pore solution. Ground clinker would typically have a lower ionic concentration in the pore solution due to the absence of SO42-.

Hydrated cement paste

Hydrated cement paste is composed of capillary pores and the hydration product. The pores within the structure of the hydration product are termed gel pores. This hydration product includes C-S-H, CH, AFt, AFm, etc. Gel pores are included within the structure of hydrated cement. According to Powers, 1/3 of the pore space is comprised of gel pores, and the rest are capillary pores.

Some micrographs

Gel-like C-S-H observed

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

Porosity of paste in concrete is visible in this picture

Water within cement paste

1. Capillary water: Present in voids larger than 50 Ao. Further classified into: (a) free water, the removal of which does not cause any shrinkage strains, and (b) water held by capillary tension in small pores, which causes shrinkage strains on drying. Adsorbed water: Water adsorbed on the surface of hydration products, primarily C-S-H. Water can be physically adsorbed in many layers, but the drying of farther surfaces can occur at about 30 % relative humidity. Drying of this water is responsible for a lot of shrinkage. Interlayer water: Water held in between layers of C-S-H. The drying of this water leads to a lot of shrinkage due to the collapse of the C-S-H structure. Bound water: This is chemically bound to the hydration product, and can only be removed on ignition. Also called non-evaporable water.

2.

3. 4.

2 and 3 are together called gel water.

Calculation of hcp structure

Theoretically, 0.23 g of bound water is required to completely hydrate 1 g of cement. The remaining water fills up the pores within the structure of the hydrated cement paste (hcp), called the gel pores, as well as the pores external to the hcp, called the capillary pores. Upon hydration, a volume decrease in the amount of 25.4% of the bound water occurs in the solid hydration product. The characteristic porosity of the hydrated gel is 28%.

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.

Paste composition
Phase data for a Type I OPC paste made with a w/c of 0.45.
a

Formula 1.7C-S-4H.

Formula 1.7C-S-1.6H.

Phase C3S C2S C3A C4AF Gypsum (C H2) C-S-H (solid)a C-S-H (with gel pores)b Portlandite (CH) Ettringite (AFt) Monosulfoaluminate (AFm) Water Gel porosity Capillary porosity

Density (g/cm3) 3.15 3.28 3.03 3.73 2.32 2.65 1.90 2.24 1.78 2.02 1.00 ---

Volume % Mature Paste At Mixing 23.40 7.35 4.42 2.87 3.47 0 0 0 0 0 58.49 0 58.49 1.17 0.78 0.00 1.39 0.00 29.03 49.99 13.96 6.87 15.12 31.69 20.96 10.73

http://iti.northweste rn.edu/cement/mon ograph/Monograph 5_6.html

Structure of hydration products

Visit: http://cementlab.com/cementart.htm

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 Young et al. 1998

CSH

Taylor, 1968

Mehta and Monteiro 1993

CSH formed on C3S

cementlab.com

CSH Structure Feldman Sereda model

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%

Mehta and Monteiro, 1993

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%

Ettringite and monosulphate

Ettringite Monosulfoaluminate

Mehta and Monteiro, 1993 Mindess and Young, 1981

Pores and Air Voids

Mehta and Monteiro, 1993

Types of pores

http://iti.northwestern.edu/cement/monograph/Monograph7_2.html