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Lecture 2: Hydration

Typical Constituent Materials of Cement

Name Lime Silica Alumina Ferric Oxide Magnesia Carbon Dioxide Water Sulfur Trioxide Oxide CaO SiO2 Al2O3 Fe2O3 MgO CO2 H2O SO3 Shorthand Typ. Weight % C S A F M C H S 63% 22% 6% 2.5% 2.6% -

Typical Cement Composition (Compounds)

Chemical Name
Tricalcium Silicate (alite) Dicalcium Silicate (belite) Tricalcium Aluminate (celite) Tetracalcium Aluminoferrite Gypsum

Formula
3CaO*SiO2 2CaO*SiO2 3CaO*Al2O3 4CaO*Al2O3*Fe2O3 CaSO4*2H2O

Shorthand Weight
C 3S C 2S C 3A C4AF CSH2 50% 25% 12% 8% 3.5%

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Typical Cement Particle Size Distribution

Cement Type

Cement Types (ASTM C-150)

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Cement Types (ASTM C-150)

Cement Types (ASTM C-150)

Cement Types (ASTM C-150)

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Cement Types (ASTM C-150)

Cement Types (ASTM C-150)

Type I Type II - normal Portland cement - moderate sulfate resistance limit C3A < 8% low heat option C3S+C3A < 58% Type III - high early strength, C3A < 15% Type IV - low heat C3S < 35%, C3A < 17%, C2S > 40% Type V - sulfate resistance, C3A < 5%
NOTE: Rate of hydration: C3A > C3S > C4AF > C2S Heat of Hydration (J/gram): see Table 4.3 Hydration product of C3A may react with sulfate from the environment, causing expansion and cracking.

Physical Requirements of Cement

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Other Requirements of Cement

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Type II & Type V Sulfate Resistant Cements

Type III High Early Strength Cements

Type IV Moderate and Low Heat Cements

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Cement Hydration
Water + Cement chemical reaction

(Cement grains dissolve, diffuse and precipitate)

Reaction is exothermic (heat released) Heat signature can be important to characterize material development

Hydration of Cements
Calcium Silicates
calcium silicate hydrate (C-S-H)

Fast Slow

2 C 3S + 6 H C 3S 2 H 3 + 3 C H 2 C 2 S + 4 H C 3S 2 H 3 + C H

Tricalcium Aluminates

Very Fast C 3 A + 3 C S H 2 + 2 6 H C 6 A S 3 H 3 2
gypsum
If more C3A left:

Ettringite (AFt)

2C 3 A + C 6 A S 3 H 32 + 4 H 3C 4 A S H 12
AFt Monosulfoaluminate (AFm)

If there is sulfate C 4 A S H 12 from outside after concrete hardens: AFm

+ 2 C S H 2 + 16 H C 6 A S 3H 32
From environment

AFt reformation: sulfate attack

Hydration of Cements
Tetracalcium Aluminoferrite

C 4 AF + 3C S H 2 + 21 H C 6 (A, F) S3 H 32 + ( F,A ) H 3 C 4 AF + C 6 (A, F) S 3H 32 + 7 H 3C 4 (A, F) S H 12 + (F, A)H 3

F plays same role as A (interchangeably) Reaction slower than aluminate phase NO late ettringite reformation: better sulfate resistance

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Some Words About Hydration Products

Some Words About Hydration Products

Some Words About Hydration Products

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Compressive Strength Development

60 C3S
Compressive strength (MPa)

45 C2S

30

15 C3A+CSH 2 0 0 20 40 60 Time (days) 80 100

C3A reacts instantaneously Final strength determined by C3S and C2S For high early strength, increase C3S

Remember: Rate of hydration: C3A > C3S > C4AF > C2S C-S-H is THE hydration product providing strength of concrete

Cement Types
Type I Normal 50 25 12
Type III Type I
30

C3S C2S C3A

Adiabatic temperature (C)
45

Compressive Strength (MPa)

Type III HES 60 15 10

Type IV Low Heat 25 50 5

45 40 35 30 25 20 15 10 5 0 0 3 6 9 12 15 18 21 24

Type IV

Type I Type III

Type IV
15

0 0 10 20 30

Age (months)

Time (days)

Max Content for Each Phase (ASTM C150)

Type C3S(%) C2S(%) C3A(%) C4AF(%) BF(m2/kg) I II III IV V 55 51 56 28 38 19 24 19 49 43 10 6 10 4 4 7 11 7 12 9 370 370 540 380 380

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Physical States Change

True fluidity

True rigidity

Hardening

Setting

Initial set

Final set

Setting Period
Initial set the time at which fresh concrete can no longer be properly handled and placed Final set the time at which hardening begins

Vicat Needle Test (ASTM C191-99)

weight
40 35 settlement (mm) 30 25 20 15 10 5 0 0 2 4 ti age (hours) 6
tf initial setting final setting Plain paste w/c=0.4

Graduated scale

Needle dia=1mm Ring container

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Heat of Hydration (C3S)

Rate of Heat Evolution
Final set hydrolysis C3S reacts

nucleation dissolution

III
Initial set

IV
diffusion control

II

V Time

Stage I Stage II Stage III Stage IV Stage V

Rapid Heat Evolution Dormant Period Accelerating Stage Deceleration Stage Steady State Important for transportation Begins with initial set No longer workable

(<15 mins) (2-4 hrs) (4-8 hrs) (12-24 hrs)

Hydration Movie

Early Hydrates forming during the pre-induction period

Soft X-Ray Microscopes, courtesy of Prof. Monteiro at UC Berkeley

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Early Hydrates forming during the pre-induction period

In-situ Massive precipitation

In-situ Massive precipitation

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In-situ Massive precipitation

The induction period is ended by the massive precipitation of C-S-H (needles) The early hydrate layer covering the cement grains transforms during the acceleration period

More Advanced Theory

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Cement Fineness
Grinding - last step in processing Measuring fineness:
Specific surface (total surface area of 1g or 1kg of particles) Particle size distribution

Blaine fineness - measures air permeability to get specific area Typical surface areas:
normal ~ 350 m2/kg high early strength ~ 500 m2/kg

Blended Cements (ASTM C595)

DEFINITION a hydraulic cement consisting of two or more inorganic constituents, which contribute to the strength gaining properties of cement.

Blended Cements (ASTM C595)

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Blended Cements (ASTM C595)

Blended Cements (ASTM C595)

Advantages: Lower Heat of Hydration
Increased Durability Increased Strength Energy Saving Disadvantages: Requires Increased Quality Control Slow Strength Development

Blending Components

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The Pozzolanic Reaction

Pozzolanic reaction - siliceous or siliceous and aluminous material that possesses no cementing property but reacts with calcium hydroxide when moist Recall portland cement reactions
weak strong 2 C 3 S + 6 H Fast C 3S 2 H 3 + 3 CH

2 C 2 S + 4 H Fast C 3S 2 H 3 + CH
strong weak

C 3S + H C S H + CH
strong

Fast

Pozzolan + CH + H Slow C S H

Specialty Cements
White cement
Architectural concretes (no C4AF)

Calcium aluminate cements

High early strength in cold weather repairs with superior durability

Expansive cements
Drying crack resistance, chemical prestress

Rapid set/High Early Strength (HES)

High strength in a few hours Emergency repair, precast-prestressed concrete

Reading Assignment
3.2, 3.3 (general), 3.4(general), 3.5 4.1

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