ACBM

VIDEO:
Hydration of Cement

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Cement Hydration

Water + Cement

chemi cal reaction

(Cement grains dissolve, di ffuse and precipitate)

Reaction is exothermic (heat released)

Heat signature can be i mportant to
characterize material development

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Rate of Heat
Evolution

Heat of Hydration
Final set
hydrolysis

C3S reacts

III

nucleation
dissolution

II

IV
diffusion control

Initial set

Time
Stage I

Rapid Heat Evolution

(<15 mins)

Stage II

Dormant Period

Important for transportation

(2-4 hrs)

Stage III

Accelerating Stage

Begins with initial set

(4-8 hrs)

Stage IV

Deceleration Stage

No longer workable

(12-24 hrs)

Stage V

Steady State

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Typical Setting Times for Portland

Cements

Vicat apparatus
(Gebhardt 1995 and PCA 1996).

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Conceptual View of Hydration

Initial

During
Hydration

w/c>0.32
100% Hydration

w/c < 0.32

100% Hydration

Portland Cement Grain (Un hydrated)

Water Filled Capillary pores
C-S-H
Note: Calcium Hydroxide and Calcium Sulfoaluminates not shown

For complete hydration 1 g of PC requi res 0.32 - 0.36 g of water

(i.e., equal volumes)

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Structure of H ydrated Cement Paste

Calcium Silicate
Hydrate (C-S-H)
50-67% of solids volume
(major product)
C/S ranges f rom 1.5~2
Morphology - poorly
crystalline to reticular
network
Resembles tobermorite
(naturally occurrin g mineral)

Image is from Paul Stutzman, 2003

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Structure of H ydrated Cement Paste

Calcium Hydroxide - (CH, Portlandite)

20-25% of solids volume

Known stoichiometry Ca(OH) 2
Morphology - hexagonal crystal plates
Adverse effect on durabilit y

C-SH

C 3S
CH
10 mm
Image is from Jennings, 2003

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Structure of H ydrated Cement Paste

Calcium Sulfoaluminates (ettringite)

15-20% of solids volume

Minor role in structural behavior
Hexagonal plate crystal
Ettringite (Aft) formation

Unhydrated clinker grains

Cores of larger particles
Morphology - resembles clinker

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Relative Volume of Major

Compounds in Hydrated Paste s

Function of Time

Locher, Richartz, and Sprung 1976

Function of Degree of Hydration

Tennis and Jennings 2000

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Water In H ydrated Cement Past e

X
X X
OO X
X
X X
X X X O O X
X
XX X
X XX X OO O
X OO
OO
X X X
X X X X X
X
X
X
O O OO
O
O
O
O O OO O
O
X
O OO
X X XX
O
X
X X
O
X X X
O O
O O OO O O
O OO
X
X X
X X
O
O O
X
X X X
O
O X
O O
O O O
X
O
O OOO X X X
OO
X
**After Feldman and Serada 1970

Interlayer water (X)

- Associated with C-S-H structure
- Lost on drying below 11 %

Capillary water
- Large voids
- Free water, pores > 50 nm
- Capillary tension, pores 5-50 nm

Adsorbed water (O)

- Held close to solid surface
- Up to approx imately 6 layers

Chemicall y combined w ater

- Integral part that is not lost on heating

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Voids in H ydrated Cement Past e

Interlayer space in C-S-H (gel void) nm level

Small voids - probably 5-25

Capillary voids mm level

Popularly called porosity

Air voids mm level

Generally round
Entrapped air (as large as 3mm)
Entrained air (50 -200mm)

Capillary
Porosity

Hydration
Products

Unhydrated
Grain

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Dimensions of Solids & Pores

Interparticle
Spacing Between
C-S-H Sheets

Hexagonal
Ca(OH) 2 Crystals

Entrapped Air

Entrained Air

Capillary Void
Aggregation of
C-S-H Particle
0.001mm 0.01mm 0.1mm

**After Monterio and Mehta Fig 2-7

1mm

10mm

Max Air Spacing

100mm

1mm

10mm

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Volume of Products
Effect of Time

Consider 100 cm3 of cement with w/c = 0.63 (by wt.)

Total Volume of Paste (cc)

VWater

VCementrCement w 100cc(3.14g / cc )
=
=
0.63 = 200cc
r Water
c
1.0g / cc

300

Capillary
Pores

200

Hydration
Product

100
0

Initial

Day 7
50% hyd.

Day 28
75% hyd.

Day 365
100% hyd.

Anhydrous
Cement

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Volume of Products
Effect of w /c Ratio

Capillary Pores

37%
300

30%

22%

Hydration Product

11%

200

0%

100

Strength

Total Volume of Paste (cc)

Consider 100 cm 3 of cement with 100% hydration

Complete Reaction = 200 cm 3

0
0.32

w/c 0.7
Vol. 320

0.6
288

0.5
257

0.4
225

0.32
200

w/c

Conclusion: lower w/c has lower porosity, greater strength

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Calculation of Volume Changes

Empirical equations deri ved by T.C. Powers from experiments

Evaporable Water - Lost at 105C
Capillary and gel pores (interlayer pores)
Non-Evaporable Water (wn) - Lost at 1000C
Approximate measure of combined water
Capillary
pores

Increasing Hydration

Gel pores

Evaporable
Water

Hydration
products (gel)

Total Solid
Volume

Unhydrated cement

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Calculation of Volume Changes

Assumption: 1 g of cement requires 0.36 g of w ater for

complete hydration ( 1 g of cement = 0.32 cm 3)
Volume of gel: Vg = 0.68a cm 3/g, where a = % hydration
Capillary Porosit y: VCP = w/c - 0.36a
= 0.63 - 0.36*1 = 0.27 cm 3/g
(if w/c = 0.63 and a = 1)

Volume of CP = CP*rcement = 0.27*(100)*3.15 @ 85 cm 3

(for 100 cc of cement)

Gel Space ratio = Volume of gel/Space ava ilable for gel

= 0.68a/(w/c + 0.32a)
Note: because of space requirements minimum w /c = 0.42
Solid space = 1 - capillary porosity

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Porosity, Gel Space,

Strength, and Permeability
Typical Capillary
Porosity

Typical Capillary
Porosity
Hydration

Capillary Porosity
120

20

80

10

40

0
1.0

0.9

0.8 0.7

0.6

0
0.5 0.4

Solid/Space Ratio (1-P)

Water/Cement Ratio

30

100% 75%
0.3

0.6

-12 )

0.45

(cm/secx10

0.3

Permeability Coefficient

(x10 3 psi)

Compressive Strength

50% 25%

0.4

0.5

0.6

0.7
0

0.1 0.2 0.3

0.4 0.5 0.6

Capillary Porosity, Vol. Fraction P

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Ways to Measure Porosity

Electrical Measurements
Image Analysis
Nuclear Magnetic Resonance (NMR)
Weight Loss
Computer Simulations ( Virtual Cement and Concrete
Testing Laboratory-VCCTL)

Mercury Intrusion Porosimetry

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Mercury Intrusion Porosimetry

(MIP)

Penetration Volume (cc/g)

Hydration

Pore Volume

Pore Diameter

0.5

28 Days

AGE

0.4

90 Days

INCREASING w/c
0.3

365 Days

0.2
0.1
0
5000 2000 1000 500

200 100

Pore Diameter A

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Chemically
Combined Water

C
B

Adsorbed and
Interlayer
Water

Free
Water

Shrinkage

Water Loss

Water and Shrinkage

100%

Relative Humidity

Loss of Water

Note: Relationship between shrinkage and water loss is

not unique, it depends on age and degree of hydration

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VIDEO:
Microstructure of Concrete
Images from Paul Strutman, 2003

Clinker, HF-etch, 300 mm

FW

0.45 w/c, 7 d 30 mm FW

0.45 w/c, 1 d, 50 mm FW

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Key Ideas

How long are the stages of the hydrati on

reaction?
What is the relative sizes of C-S-H
crystals, capillary voids, entrained air and
entrapped ai r?
What effect does w/c have on the
microstructure and other properti es?