### Dr. Kimberly Kurtis School of Civil Engineering Georgia Institute of Technology Atlanta, Georgia 

# Portland Cement Hydration

3CaO•SiO 2 

### 2CaO•SiO 2 

### 3CaO•Al 2 

### O 3 

### 4CaO•Al 2 

### O 3 

### •Fe 2 

### O 3 

### CaCO 3 

### (limestone) 2SiO 2 

### •Al 2 

### O 3 

### (clay, shale) Fe 2 

### O 3 

### (iron oxide) SiO 2 

### (silica sand)

~ 1 4 5 0 o C

Clinker interground Finished cement 

# Cement Composition

Gypsum + 

### CaO•SO 3 

### •2H 2 

### O Kiln

# Cement Composition + impurities (K, Na, Mg, etc)



# • the presence and substitution (e.g., Na + 

### for Ca 2+ 

### ) of impurities can lead to polymorphism, structural “holes”, and greater reactivity



# Cement Hydration Hydration - chemical combination of cement and water Two primary mechanisms: Through solution - involves dissolution of anhydrous compounds to their ionic constituents, formation of hydrates in solution, and eventual precipitation due to their low solubility Topochemical - or solid-state hydration - reactions take place directly at the surface of the anhydrous cement compounds without going into solution

# Cement Hydration When water is added to cement, what happens? 

## • Dissolution of cement grains 

## • Growing ionic concentration in “water” (now a solution) 

## • Formation of compounds in solution 

## • After reaching a saturation concentration, compounds precipitate out as solids (“hydration products”) 

## • In later stages, products form on or very near the surface of the anhydrous cement

Al +3 Al +3 Al +3 Ca +2 Ca +2 Ca +2

OH OH OH SiO SiO 

# Cement Hydration

# Cement Hydration

Taylor, Cement Chemistry 

# Cement Hydration

4% C 4 AF 7% C 3 A 32% C 2 S 54% C 3 S
0% C 4 AF 17% C 3 A 30% C 2 S 52% C 3 S

Image Credit: Bentz at NIST

# Cement Hydration Because the hydration rates of the 4 key phases vary considerably, properties like 

# • time to stiffening 

# • setting time 

# • hardening rate will vary with cement composition.



# Cement Hydration

Taylor, Cement Chemistry

# Cement Hydration

0 20 40 60 80 100 Time (days) 0 10 20 30 40 50Compressive Strength (MPa)

2,000 4,000 6,000 8,000 10,000

0 60 70Compressive Strength (psi)

C 3 A+CSH 2 C 4 AF+CSH 2 C 2 S C 3 S

Compressive Strength development in pastes of pure cement compounds ( Mindess et al, 2003 )

 Hydrates & hardens rapidly  Responsible for initial set and early strength Tricalcium silicate (alite) C 3 S 

# Properties of Hydrated Cement Compounds Hydrates & hardens slowly  Contributes to later age strength (beyond 7 days) Dicalcium silicate (belite) C 2 S  Hydrates & hardens rapidly  Responsible for initial set and early strength Tricalcium silicate (alite) C 3 S 

# Properties of Hydrated Cement Compounds

 Liberates a large amount of heat during first few days  Contributes slightly to early strength development  Cements with low %-ages are more resistant to sulfates Tricalcium aluminate C 3 A  Hydrates & hardens slowly  Contributes to later age strength (beyond 7 days) Dicalcium silicate (belite) C 2 S  Hydrates & hardens rapidly  Responsible for initial set and early strength Tricalcium silicate (alite) C 3 S 

# Properties of Hydrated Cement Compounds Reduces clinkering temperature  Hydrates rapidly but contributes little to strength  Colour of hydrated cement (gray) due to ferrite hydrates Tetracalcium aluminoferrite (ferrite) C 4 AF  Liberates a large amount of heat during first few days  Contributes slightly to early strength development  Cements with low %-ages are more resistant to sulfates Tricalcium aluminate C 3 A  Hydrates & hardens slowly  Contributes to later age strength (beyond 7 days) Dicalcium silicate (belite) C 2 S  Hydrates & hardens rapidly  Responsible for initial set and early strength Tricalcium silicate (alite) C 3 S 

# Properties of Hydrated Cement Compounds0 5 30 1 2 6 1 2 7 28 90 Minutes Hours DaysAmount

0 5 30 1 2 6 1 2 7 28 90 Minutes Hours DaysAmount Porosity

CH Ettringite0 5 30 1 2 6 1 2 7 28 90 Minutes Hours DaysAmount Porosity

CH Ettringite C-S-H

0 5 30 1 2 6 1 2 7 28 90 Minutes Hours DaysAmount Porosity

CH Ettringite C-S-H C-(A,F)-H0 5 30 1 2 6 1 2 7 28 90 Minutes Hours DaysAmount

Porosity CH

Ettringite C-S-H

C-(A,F)-H Monosulfate



# Cement Hydration

• Is the chemical combination of cement and water to form hydration products 

## • Takes time 

## • May not proceed to 100% completion Formation of hydration products over time leads to: 

## • Stiffening (loss of workability) 

## • Setting (solidification) 

## • Hardening (strength gain) Let’s look at the hydration reactions in more detail...

# Hydration of the Calcium Silicates 2C 3 

### S + 7H → C 3 

### S 2 

### H 8 

### + 3CH ∆ H=-500J/g 2C 2 

### S + 7H → C 3 

### S 2 

### H 8 

### + CH ∆ H=-250J/g



## • Both produce C-S-H and CH as reaction products 

## • C 2 

### S produces less CH (important for durability in sulfate rich environments) 

## • More heat is evolved during C 3 

### S hydration 

## • C 3 

### S hydration is more rapid, contributing to early age strength (2-3h to 14 days) 

## • C 2 

### S hydration occurs more slowly to contributing to strength after ~7-14 days.


# Hydration of the Calcium Silicates Like most chemical reactions, the rate of cement hydration is influenced by temperature.

# C-S-H
• Calcium silicate hydrate 

## • C/S varies between 1.1-2; ~1.5 is typical 

## • H is even more variable 

## • Structure ranges from poorly crystalline to amorphous - highly variable and poorly understood 

## • Occupies 50-60% of the solid volume of the hydrated cement paste (hcp) 

## • Huge surface area (100-700 m 2

### /g) 

## • Strength due to covalent/ionic bonding (~65%) and Van der Waals bonding (~35%) within the complex structure 

## • Primary strength-giving phase in portland cement concrete image credit: Dr. Eric Lachowski, S.Y. Hong, and F.P. Glasser via Concrete Microscopy Library at UIUC 

# C-S-H The structure of C-S-H is poorly understood. 16 hr. C 3 

### S paste

wet dry S H2O 

### = 200 m 2

### /g S N2 

### = 5-50 m 2

### /g S neutrons 

### = 50 m 2

### /g Variations in surface area, depending on technique used

# C-S-H

Figure credit: M&M text



# Some other models for C-S-H Adapted from Powers (1960’s) Feldman and Sereda (1970)

Munich model, Wittman (1979) Colloid model Figure credit: M&M text

# Microscopical Evidence

Fine, fibrillar structure, similar to Power’s model (typical of Ca/Si>1.5) Foil-like structure, similar to Feldman-Sereda model (typical of lower Ca/Si) Figure credit: Richardson, in Structure and Performance of Cements, Bensted and Barnes (Eds), Spon 2002.

Calcium silicate sheets 

# Some other models for C-S-H

Clay-like structure Aluminosilicate sheets

# Some other models for C-S-H

Original Image High X-ray Absorption by Ca

Low X-ray Absorption by Ca Ca Map 345eV 347eV 517eV

E. Gartner, K.E. Kurtis, and P.J.M. Monteiro, Cement and Concrete Research , May 2000, V30 (5):817-822.


# Some other models for C-S-H At low C/S, C-S-H resembles tobermorite At high C/S, C-S-H resembles jennite Higher C/S ratios are obtained by 3 principle mechanisms.

SiO 2 

### bridging tetrahedra SiO 2 

### pairing 

### tetrahedra Tobermorite (C/S~0.8)

CaO sheet

Long single silicate chains 

### Composite layer structure 1 Replacement of bridging tetrahedra for interlayer calcium. Tobermorite-like C-S-H(I)



### 2 Replacement of H on Si-OH with interlayer calcium. Jennite-like C-S-H

3 Replacement of silicate chains with hydroxyls, producing Ca-OH. Ca-OH Jennite-like environments

5 A

# Summary of Models for C-S-H Table 6: Summary of models for the structure of C-S-H. Name of Model Primary Experimental Basis Type of Model Selected Characteristics of Model Powers Water sorption Colloid All products are gel Volume of pores Particle radius, 5 nm Gel pore volume, 28% Taylor X-ray Imperfect Atomic structure of C-S-H TGA Tobomerite Jennite Brunauer Water Sorption 2-3 layers Structure changes upon drying Feldman-Sereda Nitrogen sorption Layers Crumpled and folded layers with Length vs. RH interlayer water reversibly Modulus vs. RH removed upon drying Weight vs. RH Wittmann Modulus vs. RH Colloid Structure not defined Jennings Density vs. RH Colloid Fractal: density and surface area Composition vs. RH depend on length scale Surface area


# Inner vs. Outer Product C-S-H Outer product (early) C-S-H/ groundmass 

## • forms during early hydration 

## • C-S-H forms away from the cement particle surface, filling water-filled space 

## • higher porosity 

## • contains high levels of impurities 

## • probably admixed with nanoscale C 4

### AŠH 12

# Inner vs. Outer Product C-S-H Inner product (late) C-S-H/ phenograins 

## • forms during later hydration, when the process is diffusion controlled 

## • C-S-H grows inwards and outwards from the C-S-H “barrier” 

## • C-S-H formed takes shape of cement grains 

## • lower porosity, more dense 

## • fewer impurities 

## • more resistant to physical change on drying 

## • more abundant as hydration ↑ or as w/c ↓ 

# C 3 

# S Hydration

1 Day 3 Days
28 Days

# CH
• Calcium hydroxide or Ca(OH) 2 

## • Definite stoichiometry 

## • Variable morphology - from large, hexagonal prisms to thin, elongated crystals 

## • Size of the crystals depends on the amount of space available 

## • Occupies 20-25% of the solid volume in the hcp 

## • Much lower surface area than C-S-H 

## • Does not contribute much to strength 

## • Keeps the pore solution alkaline (pH 12.4-13.5) 

# Hydration of the Calcium Aluminates

• Reaction of C 3

### A with water occurs very quickly and liberates much heat - “Flash Set” 

## • Gypsum (CŠH 2 

### ) is added to the cement to control the hydration of C 3 

### A C 3

### A + 3CŠH 2 

### + 26H → C 6 

### AŠ 3 

### H 32 

### ∆ H=-1350J/g

Dormant Period Setting

# Role of Gypsum

Role of Gypsum

# Hydration of the Calcium Aluminates When more C 3

### A remains, C 6 

### AŠ 3 

### H 32 

### + 2C 3

### A + 4H → 3C 4

### AŠH 12


## • Reaction of C 4

### AF occurs more slowly C 4

### AF + 2CH + 14H → C 4 

### (A,F) H 13 

### + (A,F)H 3



# Hydration of the Calcium Aluminates

• Reaction of C 4

### AF (ferrite) phase are slower and evolve less heat than C 3

### A 

## • Also heavily retarded by gypsum C 4

### AF + 3CŠH 2 

### + 21H  C 6 

### (A,F)Š 3 

### H 32 

### + (F,A)H 3 

### C 4

### AF + C 6 

### (A,F) Š 3 

### H 32 

###  3C 4 

### (A,F)ŠH 12 

### + (F,A)H 3


## • Products of C 4

### AF are more resistant to sulfate attack than those of C 3

### A hydration

# Hydration of the Calcium Aluminates C 6 

## AŠ 3 

## H 32 

## (Ettringite, Aft 

## )
• Needle-like morphology • Needles interlock, take up much water • contributes to stiffening of mixture • some early strength



# Hydration of the Calcium Aluminates Ettringite crystal structure as part of a single column projection where A=Al, C=Ca, H=O of an OH group, W=O of an H 2 O molecule. Hydrogen atoms have been omitted, as are the H 2 O molecules attached to the calcium atoms lying in the central vertical line of the figure. (based on Taylor, 1997) W W

W W W
W W W H H C H H H A C C W W W W W W A H H H C H H Ac/2 = 1.075nm

W W H H C C

# Hydration of the Calcium Aluminates Ettringite stability in alkaline environments as a function of pH and sulfate ion concentration. (adapted from Hampson and Bailey, 1982) . - 2
- 3
- 4 - 5 11 12 13 Ettringite

Hydrogarnet Portlandite Al-Hydroxide Gypsum

pHlog(SO42-) Log [SO 4 -2 ]



# Hydration of the Calcium Aluminates C 4 

## AŠH 12 

## (monosulfate, Afm 

## ) • hexagonal plate morphology arranged in “rosettes” during early hydration • become more “platey” with continued hydration • can contain impurities • vulnerable to sulfate attack

# Calcium Aluminates and Calcium Sulfoaluminates
• Includes ettringite, monosulfate hydration, calcium aluminate hydrates, and ferric-aluminum hydroxide gels 

# • Comprise 15-20% of solid volume of hcp 

# • Do not contribute much to strength 

# • Formation of ettringite, in particular, does influence setting time 

# • High heat of hydration for C 3 

## A can be favorable or unfavorable, depending upon application


# Hydrated Cement Paste (hcp)

# Hydrated Cement Paste (hcp)

Hydrated Cement Paste (hcp)

## Formation of hydration products over time leads to: 

# • Stiffening (loss of workability) 

# • Setting (solidification) 

# • Hardening (strength gain)



# Cement Hydration

, sulfate attack

# Heat of Hydration

• Cement hydration is exothermic 

# • Concrete is an insulator Heat of hydration can be: - detrimental (thermal gradients --> cracking) - helpful (heat provides activation energy when concreting in cold weather; higher early strength)



# Heat of Hydration Heat evolution can be used to map the progress of hydration: (1) Initial dissolution of solids (increasing ionic concentration) (2) Induction period (3) Acceleration (4) Deceleration (5) Steady state

## • Popular model for describing hydration during the acceleration periods (Stages 2&3) -ln(1- α )=[ k( t-t o 

### )] m 

### or when α is small, α = k t m Where α is degree of hydration t is time of hydration, where t o corresponds to the length of induction period k is a rate constant for a nucleation-controlled process m = [(p/s)+q], where p= 1 for1D growth (needles/fibers) m ~ 1-3 for C 3 S 2 for 2D (sheets/plates) 3 for 3D isotropic growth (sphere) s=1 for interface or phase-boundary-controlled growth =2 for diffusion-controlled growth and q=0 for no nucleation (nucleation saturation) 1 for continuous nucleation at a constant rate 

# Cement Hydration: Avrami Model*

* Avrami, M. J. Phys. Chem. , 7, 1103 (1938), 8, 212 (1940).



# • k , then, is a combined rate constant, accounting for rate of nucleation, rate of product growth, and other factors not accounted for (e.g., changing diffusion coefficients) 

### • Can calculate the rate constant k from calorimetry data and the Avrami equation: 

### -ln(1- α )=[ k( t-t o 

### )] m 

## • when modeling as a function of time rather than degree of hydration: 

### d α /dt=Am k m 

### (t-t o 

### ) m-1 

### exp{-[ k (t-t o 

### )] m 

### } Where A is a preexponential factor. 

# Cement Hydration: Avrami Model

Figure credit: Gartner et al, in Structure and Performance of Cements, Bensted and Barnes (Eds), Spon 2002. Thomas and Jennings, Chem. Mat. , 11:1907-14, 1999.

# Cement Hydration: Avrami Model

• Can also determine the activation energy (E a ) for the reaction, which can be used to assess the temperature-dependence of the reaction: 

### k

(T)=A exp(-E a 

### /RT) Where T is absolute temperature (K), R is gas constant,

Thomas and Jennings, Chem. Mat. , 11:1907-14, 1999. 

# Cement Hydration: Jander Equation*

• In the deceleration period, the Jander equation for diffusion controlled processes has been used to model the reaction of cement during this period: [1-(1- α ) 1/3 

### ] 2 

### = k D 

### Where k D 

### is the rate constant for diffusion controlled processes.

* Jelenic, Adv. Cem. Tech . Gosh (Ed), p.397, Pergamon, 1987. Bezjak and Jelenic, Cem. Conc. Res. , 10:553, 1980.

# Cement Hydration: Simple Kinetic Models

• Can estimate α based upon the available water-filled porosity ( φ w ):
where k 1 is analogous to a first-order rate constant and depends on the specific cement composition, particle size distribution, curing temperature, etc. 

### • This approach, based upon first order "physical" kinetics and described by Bentz*, assumes hydration rate is simply proportional to the volume fraction of this water-filled porosity 

### • Other models** relate the kinetics of hydration to the changing radius of an idealized cement particle or particle distribution *D. P. Bentz, “Influence of Water-to-Cement Ratio on Hydration Kinetics: Simple Models Based on Spatial Considerations” at http://ciks.cbt.nist.gov/~garbocz/hydration_rates/index.html **J.M. Pommersheim, J.R. Clifton, Mathematical modeling of tricalcium silicate hydration. Cem Concr Res 9 (1979) 765-770. T. Knudsen, The dispersion model for hydration of portland cement 1. General concepts, Cem Concr Res 14 (1984) 622-630. B. Osbaeck, V. Johansen, Particle size distribution and rate of strength development of portland cement. J Am Ceram Soc 72 (2) (19 89) 197-201. 

# Cement Hydration: Simple Kinetic Models Substituting into Powers equation for water-filled porosity the result can be integrated and solved with the boundary condition that α (0)=0 to yield: (the minimum function assures that α < 1) 

## • Although derived from a different perspective, the above is similar in form to kinetics equations often derived considering nucleation and growth kinetics for cement hydration (so-called Avrami behavior) ƒ exp is the volumetric expansion coefficient for the "solid" cement hydration products relative to the cemen t reacted (often taken to be =1.15), CS is the chemical shrinkage per gram o cement (often taken to be 0.07 mL/g)

# Heat of Hydration For the usual portland cement: 

# • ~ 1/2 total heat is evolved in 1-3 days 

# • 3/4 at 7 days 

# • 83-91% at 180 days



# Heat of Hydration The RATE of heat evolution is related to 

# • cement composition 

# • cement fineness 

# • cement content 

# • casting temperature The total heat evolved is related to 

# • cement composition 

# • degree of hydration 

# • cement content

# Heat of Hydration

Heat of Hydration: Influence of Cement Composition

# Heat of Hydration: Influence of Cement Composition

Heat of Hydration: Influence of Cement Composition

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5

0 6 12 18 24 30 36 42 48 54 60 66 72 Age (h)Heat evolved (mW/g)

0 50 100 150 200 250 Cement 1 Cement 2 Cement 3 Cement 4 Cement 5Cumulative Rate evolution (J/g) 10 12.2 8.6 9.1 11 C4AF 9 7.1 10.1 7.5 4 C3A 26 20.6 7.9 19 16 C2S 42 50.4 62.9 55.9 59 C3S Cement 5 Cement 4 Cement 3 Cement 2 Cement 1

# Heat of Hydration: Influence of Cement Fineness

Heat of Hydration: Influence of Ambient Temperature

# Estimating Heat of Hydration Verbeck and Foster estimated that the overall heat of hydration of a cement is near the sum of the heats of hydration of the individual components. H = aA + bB + cC + dD H 3days 

### = 240(C3S) + 50(C2S) + 880(C3A) + 290(C4AF) J/g H 1yr 

### = 490(C3S) + 225(C2S) + 1160(C3A) + 375(C4AF) J/g A,B,C,D are % by wt of C3S, C2S, C3A, C4AF a,b,c,d are coefficients representing the contribution of 1% of the corresponding compound to the heat of hydration