Concrete

Hydration of Portland cement CEEN 5303

Presenter: Dr. Francisco Aguiga Assistant Professor of Civil Engineering Texas A&M University Kingsville

Hydration of calcium silicates

Calcium silicates + 6H water -> C3S2H3 + 3CH C-S-H calcium hydroxide C3S2H3 C-S-H + CH calcium hydroxide

2 C3S tricalcium silicate 2 C2S tricalcium silicate

4H water

->

Page 2

Hydration of calcium silicates

The principal product is calcium silicate hydrate

Poorly crystalline material Small particles (< 1mm) in any dimension Composition varies over a wide range

Calcium hydroxide is a crystalline material with a fixed composition Calorimetric curve rate of heat evolution with time Heat flow is proportional to rate of reaction
Page 3

Hydration of C3S

Stage 1
On contact with water calcium and hydroxide ions are released from the surface of C3S grains Rapid heat evolution pH rises over 12 within minutes Ceases in 15 minutes

Page 4

Hydration of C3S

Stage 2

Dormant period Needed to reach critical concentration of calcium and hydroxide ions Hydrolysis slows down in the dormant period Responsible for plastic state of concrete Lasts between 2 and 4 hours Then C3S reacts again
Page 5

Hydration of C3S

Stage 3

Acceleration period Nuclei forms and hydration products (CH, C-S-H) begin to crystallize from solution and the reaction of C3S proceeds rapidly CH crystallizes from solution C-S-H develops at the surface of the C3S grains, developing a coating Maximum rate of heat evolution at 4 to 8 h
Page 6

Hydration of C3S

Stage 4

Stage 5

Rate of reaction slows down Steady state within 12 to 24 h As the coating of the C3S grain (hydrate layer) grows water must flow through the barrier to reach the unhydrated C3S. Eventually, water reaches unhydrated C3S through diffusion Diffusion-controlled reactions are slow Hydration tends to reach 100% completion asymptotically
Page 7

Hydration of C2S

C2S Reacts in the same way as C3S grains Except that the reaction is much slower

Page 8

Hydration of C3A

C3A reacts with sulfate ions supplied by the dissolution of gypsum Primary initial reaction of C3A
-> C6AS3H32 ettringite

C3A + 3CSH2 + 26H tricalcium gypsum water aluminate

Page 9

Hydration of C3A

Ettringite is stable only when there is an ample supply of sulfate If sulfate is consumed before the C3A has completely hydrated Ettringite transforms into monosulfoaluminate
-> 3C4ASH12
Page 10

2C3A + C6AS3H32 + 4H

Hydration of C4AF

Forms same reaction as C3A but to a lesser degree Uses small amount of gypsum C4AF + 2CH + 14H C4(A,F)H13 + (A,F)H3 Ferrite + Calcium Hydroxide + Water
Tetracalcium Hydrate + Ferric Aluminum Hydroxide like monosulfoaluminate amorphous
Page 11

Reaction Rate C3A > C3S >

C4AF > C2S

Page 12

Hydration process

Setting Solidification of the plastic cement paste Initial set beginning of solidification Paste become unworkable loss in consistency - not < 45 min. Final set Time taken to solidify completely Not > 375min. Hardening Strength gain with time after final set
Page 13

Hydration process

Page 14

Hydration of Portland cement

Sequence of overlapping chemical reactions Hydration reactions of individual clinker mineral proceed simultaneously at differing rates and influence each other A complex dissolution and precipitation process Leading to continuous cement paste stiffening and hardening
Page 15

Hydration of Portland cement

Page 16

Hydration of Portland cement

Page 17

Hydration of Portland cement

Page 18

Properties of hydration products

Page 19

Properties of hydration products

Calcium Silicate Hydrate (CSH)

Poor crystallinity unresolved morphology

Calcium Hydroxide (CH)

Monosulfoaluminate - well crystallized hexagonal prisms

Calcium sulfoaluminates
Ettringite hexagonal prisms with high aspect ratio slender needles

Page 20

10

Hydration of Portland cement

Page 21

Microstructure of hydrated cement paste

Specific gravity of hydration products

2.3 hydration products < 3.2 cement grain

CSH
Makes up to 2/3 of the volume dominates the behavior

Spiny appearance

Page 22

11

Formation of CSH

Page 23

CSH Formation

Page 24

12

Model of CSH

Page 25

Formation of Calcium Hydroxide (Monosulfoaluminate)

Ocupies 20 to 25 % of the paste volume

Crystals nucleate and grow within the capillary pore space Grows where free space is available Hexagonal prism morphology

Page 26

13

CH - Monosulfoaluminate
Grows around cement grains

Page 27

Calcuim sulfoaluminates

Ettringite
Make up 10 to 15% of the volume

Page 28

14

Porosity

Classification

Capillary pores

10nm to 10 m

Remnants of waterfilled space between partially hydrated cement grains

Gel pores

0.5 nm to 10nm Part of the CSH

Page 29

Microstructural development

Page 30

15

Model of porosity

Page 31

Model of porosity
Capillary pores

Gel pores

Page 32

16

Pore size distribution

Page 33

Pore size distribution

Page 34

17

Pore size compressive strength - permeability

Page 35

Influence of paste components on paste properties

Page 36

18

Volume changes during hydration

Porosity decreases as hydration advances
Hydration reactions are accompanied by an increase in volume Porosity has a strong influence on strength and durability

CSH and CH will either grow around solid particles or stop growing in that direction when they meet obstacles They only occupy volume which was originally occupied by the mix water Ettringite will make space for themselves when their growth is topped by an obstacle
Page 37

Calculation of volume changes during hydration

Two types of water Evaporable Lost when a saturated paste is heated to Nonevaporable Structurally combined in the hydration
products 1000 C. Water held in capillary and gel pores

Page 38

19

Calculation of volume changes during hydration

Nonevaporable water is proportional to the amount of hydration wn = 0.24 (grams of W/gram of original cement) Where is the degree of hydration Water held in the gel pores wg = 0.18 (grams of W/gram of original cement) Total volume of hydration products (cement gel) Vg = 0.68 (cm3/gram of original cement)

Page 39

Porosity and hydration

Page 40

20

Minimum w/c ratio

Gel porosity = Wg / Vg = 0.26 cm3/g original cement Capillary porosity Pc = w/c 0.36 Minimum w/c ratio Set P = 0 and =1, get w/c min = 0.36 Minimum amount of water Wmin = wn + wg = 0.42 g/g original cement Thus, (w/c)min = 0.42
Page 41

Minimum w/c ratio

Water is lost from concrete by evaporation, absorption by formwork, etc. Effective minimum w/c ratio is higher than 0.42

Page 42

21