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HYDRATION OF CEMENT

 Presented To:
            Dr. M. Irfan Ahmad Khokhar
Presented By:
• M. Rizwan Riaz           2011-MS-CES-01
                        (rizwansamor@gmail.com)

• Muhammad Safdar       2011-MS-CES-11
• Fatima Mehvish        2011-MS-CES-30
                                              2
CONTENTS
The discussion is divided into the following sections :


• Introduction

• Hydration Process
• Heat of Hydration
• Factors Affecting Hydration

• Measurement of Cement Hydration

• Approaches to Control Hydration

• References
                                                          3
Hydration
• Series of irreversible exothermic chemical reactions
  between cement and water
• Cement-water paste sets and hardens, “gluing” the
  aggregate together in a solid mass

Formation of hydration products over time leads to:
• Stiffening (loss of workability)
• Setting (Solidification)
• Hardening (Strength gain)

                                                      4
Why is it Important?

Understanding the basics of hydration is important to

• Ensure the strength and durability of concrete
• Recognize and mitigate the stresses to prevent
  cracking
• Appreciate the importance of good curing and
  construction practices



                                                    5
Composition of Cement Clinker
Consists primarily of calcium aluminates and calcium silicates
 Calcium aluminates
   – Tricalcium aluminate (C3A)
   – Ferrite (C4AF)
 Calcium silicates:
   – Alite (C3S)
   – Belite (C2S)


 Gypsum is added to avoid
  the uncontrolled setting
  resulting from C3A reaction
  with water.
                                                                 6
Cement Components
Alite or 3CaO•SiO2 or C3S

  −Hydrates & hardens quickly
  −High early strength
  −Higher heat of hydration (setting)

Belite or 2CaO• SiO2 or C2S

  −Hydrates & hardens slower than Alite
  −Gives off less heat
  −High late strength (> 7 days)
                                          7
Cement Components
Aluminate or 3CaO• Al2O3 or C3A

  −Very high heat of hydration
  −Some contribution to early strength
  −Low C3A for sulfate resistance

Ferrite or 4CaO• Al2O3 • Fe2O3 or C4AF

  −Little contribution to strength
  −Lowers clinkering temperature
  −Controls the color of cement
                                          8
Hydration Process
There are two types of reaction underlying the hydration
  process:

• Through-solution hydration
• Solid-state hydration or Topochemical hydration




                                                      9
Hydration Process




                    10
Stage 1: Mixing/ Dissolution Stage
               (< 15 minutes)
Sulfate reacts with aluminate and water to form C-A-S-H, a precursor to
Ettringite.
The gel limits water’s access to aluminate
Reactions slow. Heat drops


Too little sulfate:   flash set
Too much sulfate:     false set




                                                                 11
Stage 2: Dormant/ Induction Period
               (2–4 hours)
During this dormant period, the silicates (alite and belite) slowly
dissolve, releasing calcium ions in solution




During dormancy; before initial
set; the mix can be
transported, placed, finished, an
d textured.




                                                                      12
Stage 3: Hardening/ Acceleration Stage
             (2–4 hours)
C-S-H, fiber-like particles & CH forms and give concrete its strength
Heat is generated causing thermal expansion

Initial and Final Set occur

The gel-like C-A-S-H transforms
 into a needle-like solid
(ettringite) that contributes
somewhat to early strength.

Curing necessary right after
finishing

                                                                  13
Stage 4: Cooling/ Deceleration Stage
             (several hours)
After final set, the buildup of C-S-H and CH begins to limit access of
water to undisclosed cement

Silicate reactions slow.

Heat peaks and begins to drop

Concrete cools and contracts

Cracking can occur




                                                                   14
Stage 5: Densification/ Steady Stage
         (can continue for years)
Start of belite reactions and they can continue for years
Belite reactions also produce C-S-H and CH, forming a solid mass


Longer length of this stage gives:
•Greater concrete’s strength
•Lower permeability
•Greater durability

To promote continued
hydration, moisture must be
retained in the slab as long as
possible.
                                                               15
5 Stages of Hydration




                        16
Hydration Reactions




                      17
Characteristics of hydration
    cement compound




                               18
Heat of hydration
• Heat liberated when cement comes in contact with
  water as a result of the exothermic chemical reaction
  between cement and water.

Significance:
• Can result in thermal cracking which can reduce
  concrete durability.
• Significantly influences lift thickness which impacts
  economic savings and construction period.
                                                 19
Cement Hydration Mapped on a Heat vs. Time Curve




                                           20
Effect of member thickness on
   temperature of concrete




                                21
Mechanism of heat generation
Reaction of calcium silicates:

• 2C3S + 7H → C3S2H8 + 3CH          ΔH=-500J/g

• 2C2S + 7H → C3S2H8 + CH           ΔH=-250J/g

Reaction of tri-Calcium Aluminate

• C3A + 3CŠH2 + 26H → C6AŠ3H32      ΔH=-1350J/g
                                             22
Measurement of Heat of
                Hydration
Standards:
 ASTM C 186
we measure the heat of solution of;




 Dry cement.           Partially hydrated cement.
                                                      23
Use & Significance
• Cement specification.

• For research purposes at any age.

• Helpful for calculating temperature rise in
  mass concrete


                                                24
Apparatus
• Calorimetric apparatus.




                            25
Cont…




        26
Cont…




        27
Cont..
•   Mixer
•   Storage
•   Mortar
•   Drying oven
•   Weighing bottles
•   Stop watch
•   Sieves
•   weights
                       28
Cont…
Plastic vials   Muffle furnace




                                 29
Cont…
crucibles   Analytical balance




                                 30
Reagents &Materials
• HF

• HNO3

• WAX

• ZnO
                               31
Determination of heat capacity of
           apparatus
• Take total weight of the solution to 425g
• Assemble calorimeter
• Start stirring motor (20 mint)
• Allow system to become uniform
• Introduce ZnO
• Read the temperature OF;
solution period
rating period                                32
Cont..
• Calculate the corrected temperature rise
  as follows:




                                             33
Cont..
• Calculate the heat capacity of the calorimeter and
  contents as follows:




                                                       34
Sampling & Test Specimens
• Preparation of Cement Paste

• Preparation of Partially Hydrated
  Sample for Heat of Solution Test




                                      35
Procedure:
• Calorimetric Procedure
Determine the heat of solution of the dry
  cement sample.
Determine the heat of partially hydrated
  sample.
• Determine loss on Ignition

•
                                             36
Calculations.
• Heat of Solution of Dry Cement




                                   37
• Heat of Solution of Partially Hydrated
  Sample




                                           38
• Heat of Hydration




                      39
Approaches to control heat of
            hydration
•   Control of Cement Amount
•   Use of low-heat Cement
•   Use of Pozzolans
•   pre-cooling
•   post-cooling



                                    40
Factors Affecting Hydration
Major factors:
•   Chemical Composition of Cement
•   Cement Type
•   Sulfate Content
•   Fineness
•   Water/Cement Ratio
•   Curing Temperature
•   Effects of SCMs and Admixtures
                                       41
Chemical Composition of Cement




                             42
Cement Type




              43
Cement Type




              44
Sulfate Content




                  45
Fineness of Cement




                     46
Water/Cement Ratio




                     47
Curing Temperature




                     48
Supplementary Cementitious Materials
How they work
• SCMs convert CH (a somewhat less desirable product of
  hydration) into C-S-H (which gives concrete its strength).




How SCMs may affect hydration
• Often slow hydration, extending working time and delaying
  set, strength gain.
• Reduce heat peak.
• Extend heat generation.                            49
Fly Ash Replacement Effect




                             50
Water Reducers
How they work
• Disperse cement clusters, freeing trapped water
  which can then react (hydrate) with cement.

• How they affect hydration
• More of the mix cement is hydrated, resulting in a
  greater volume of hydration products.


                                                    51
Water Reducers
How they work
• Coats cement particles so they dissolve more slowly.

How they affect hydration
• Slow hydration.
• Reduce heat peak and extend hydration and heat
  generation (similar to water reducers).

                                                52
Set Accelerators
How they work
• Reduce time required for super saturation of calcium
  ions.

How they affect hydration
• Earlier initial and final sets.
• Increased heat generation; higher maximum peak on
  the hydration curve.
                                                53
References
• Technical summary 4-a, National concrete pavement technology center,
  IOWA State University, August 2007.
• Wolfgang B., Concrete an example for complex porosity, Institute of
  building materials research (IBAC), RWTH Achen university, Germany.
• Dr. K. Kurtis, Cement and Hydration, School of civil engineering, Georgia
  Institute of technology, Atlanta, Georgia.
• Feng Lin, Modelling of hydration kinetics and shrinkage of Portland cement
  paste, Coloumbia University, 2006.
• S. G. kim, Effect of heat of hydration on mass concrete placement, IOWA
  state university, 2010.
• A.S.M abdul Awal & M. Warid Husain, Effect of palm oil fuel ash in
  controlling heat of hydration of concrete, University of technology, Johor
  Malaysia.
• P. Juilland et al., Effects of mixing on early hydration of alite and OPC
  system, Cement and Concrete Research, 2012.                         54
References
• Concrete technology today, Vol. 18, Portland Cement Association, July
  1997.
• A.K Schindler & K. J. Folliard, Heat of hydration Model for cementitious
  materials, ACI Material Journal.
• L. E. Copeland et al. Chemistry of hydration of Portland Cement, Search
  Department, Bulletin 153.
• Jochen Stark, Recent Advances in field of cement hydration and
  microstructure analysis, cement and Concrete Research, 2011.
• J. W. Bullard et al., Mechanism of Cement Hydration, Cement Concrete
  Research, 2011.
• H. F. W. Taylor, Cement Chemistry, Academic Press London, 1990.
• Mindess et al., Properties of hydrated Cement Compounds, 2004.
• Standard Test Method for Measurement of Heat of Hydration (ASTM C
  186)
• Class Notes                                                     55
56

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Hydration of cement

  • 1. 1
  • 2. HYDRATION OF CEMENT Presented To: Dr. M. Irfan Ahmad Khokhar Presented By: • M. Rizwan Riaz 2011-MS-CES-01 (rizwansamor@gmail.com) • Muhammad Safdar 2011-MS-CES-11 • Fatima Mehvish 2011-MS-CES-30 2
  • 3. CONTENTS The discussion is divided into the following sections : • Introduction • Hydration Process • Heat of Hydration • Factors Affecting Hydration • Measurement of Cement Hydration • Approaches to Control Hydration • References 3
  • 4. Hydration • Series of irreversible exothermic chemical reactions between cement and water • Cement-water paste sets and hardens, “gluing” the aggregate together in a solid mass Formation of hydration products over time leads to: • Stiffening (loss of workability) • Setting (Solidification) • Hardening (Strength gain) 4
  • 5. Why is it Important? Understanding the basics of hydration is important to • Ensure the strength and durability of concrete • Recognize and mitigate the stresses to prevent cracking • Appreciate the importance of good curing and construction practices 5
  • 6. Composition of Cement Clinker Consists primarily of calcium aluminates and calcium silicates  Calcium aluminates – Tricalcium aluminate (C3A) – Ferrite (C4AF)  Calcium silicates: – Alite (C3S) – Belite (C2S)  Gypsum is added to avoid the uncontrolled setting resulting from C3A reaction with water. 6
  • 7. Cement Components Alite or 3CaO•SiO2 or C3S −Hydrates & hardens quickly −High early strength −Higher heat of hydration (setting) Belite or 2CaO• SiO2 or C2S −Hydrates & hardens slower than Alite −Gives off less heat −High late strength (> 7 days) 7
  • 8. Cement Components Aluminate or 3CaO• Al2O3 or C3A −Very high heat of hydration −Some contribution to early strength −Low C3A for sulfate resistance Ferrite or 4CaO• Al2O3 • Fe2O3 or C4AF −Little contribution to strength −Lowers clinkering temperature −Controls the color of cement 8
  • 9. Hydration Process There are two types of reaction underlying the hydration process: • Through-solution hydration • Solid-state hydration or Topochemical hydration 9
  • 11. Stage 1: Mixing/ Dissolution Stage (< 15 minutes) Sulfate reacts with aluminate and water to form C-A-S-H, a precursor to Ettringite. The gel limits water’s access to aluminate Reactions slow. Heat drops Too little sulfate: flash set Too much sulfate: false set 11
  • 12. Stage 2: Dormant/ Induction Period (2–4 hours) During this dormant period, the silicates (alite and belite) slowly dissolve, releasing calcium ions in solution During dormancy; before initial set; the mix can be transported, placed, finished, an d textured. 12
  • 13. Stage 3: Hardening/ Acceleration Stage (2–4 hours) C-S-H, fiber-like particles & CH forms and give concrete its strength Heat is generated causing thermal expansion Initial and Final Set occur The gel-like C-A-S-H transforms into a needle-like solid (ettringite) that contributes somewhat to early strength. Curing necessary right after finishing 13
  • 14. Stage 4: Cooling/ Deceleration Stage (several hours) After final set, the buildup of C-S-H and CH begins to limit access of water to undisclosed cement Silicate reactions slow. Heat peaks and begins to drop Concrete cools and contracts Cracking can occur 14
  • 15. Stage 5: Densification/ Steady Stage (can continue for years) Start of belite reactions and they can continue for years Belite reactions also produce C-S-H and CH, forming a solid mass Longer length of this stage gives: •Greater concrete’s strength •Lower permeability •Greater durability To promote continued hydration, moisture must be retained in the slab as long as possible. 15
  • 16. 5 Stages of Hydration 16
  • 18. Characteristics of hydration cement compound 18
  • 19. Heat of hydration • Heat liberated when cement comes in contact with water as a result of the exothermic chemical reaction between cement and water. Significance: • Can result in thermal cracking which can reduce concrete durability. • Significantly influences lift thickness which impacts economic savings and construction period. 19
  • 20. Cement Hydration Mapped on a Heat vs. Time Curve 20
  • 21. Effect of member thickness on temperature of concrete 21
  • 22. Mechanism of heat generation Reaction of calcium silicates: • 2C3S + 7H → C3S2H8 + 3CH ΔH=-500J/g • 2C2S + 7H → C3S2H8 + CH ΔH=-250J/g Reaction of tri-Calcium Aluminate • C3A + 3CŠH2 + 26H → C6AŠ3H32 ΔH=-1350J/g 22
  • 23. Measurement of Heat of Hydration Standards: ASTM C 186 we measure the heat of solution of; Dry cement. Partially hydrated cement. 23
  • 24. Use & Significance • Cement specification. • For research purposes at any age. • Helpful for calculating temperature rise in mass concrete 24
  • 26. Cont… 26
  • 27. Cont… 27
  • 28. Cont.. • Mixer • Storage • Mortar • Drying oven • Weighing bottles • Stop watch • Sieves • weights 28
  • 29. Cont… Plastic vials Muffle furnace 29
  • 30. Cont… crucibles Analytical balance 30
  • 31. Reagents &Materials • HF • HNO3 • WAX • ZnO 31
  • 32. Determination of heat capacity of apparatus • Take total weight of the solution to 425g • Assemble calorimeter • Start stirring motor (20 mint) • Allow system to become uniform • Introduce ZnO • Read the temperature OF; solution period rating period 32
  • 33. Cont.. • Calculate the corrected temperature rise as follows: 33
  • 34. Cont.. • Calculate the heat capacity of the calorimeter and contents as follows: 34
  • 35. Sampling & Test Specimens • Preparation of Cement Paste • Preparation of Partially Hydrated Sample for Heat of Solution Test 35
  • 36. Procedure: • Calorimetric Procedure Determine the heat of solution of the dry cement sample. Determine the heat of partially hydrated sample. • Determine loss on Ignition • 36
  • 37. Calculations. • Heat of Solution of Dry Cement 37
  • 38. • Heat of Solution of Partially Hydrated Sample 38
  • 39. • Heat of Hydration 39
  • 40. Approaches to control heat of hydration • Control of Cement Amount • Use of low-heat Cement • Use of Pozzolans • pre-cooling • post-cooling 40
  • 41. Factors Affecting Hydration Major factors: • Chemical Composition of Cement • Cement Type • Sulfate Content • Fineness • Water/Cement Ratio • Curing Temperature • Effects of SCMs and Admixtures 41
  • 49. Supplementary Cementitious Materials How they work • SCMs convert CH (a somewhat less desirable product of hydration) into C-S-H (which gives concrete its strength). How SCMs may affect hydration • Often slow hydration, extending working time and delaying set, strength gain. • Reduce heat peak. • Extend heat generation. 49
  • 50. Fly Ash Replacement Effect 50
  • 51. Water Reducers How they work • Disperse cement clusters, freeing trapped water which can then react (hydrate) with cement. • How they affect hydration • More of the mix cement is hydrated, resulting in a greater volume of hydration products. 51
  • 52. Water Reducers How they work • Coats cement particles so they dissolve more slowly. How they affect hydration • Slow hydration. • Reduce heat peak and extend hydration and heat generation (similar to water reducers). 52
  • 53. Set Accelerators How they work • Reduce time required for super saturation of calcium ions. How they affect hydration • Earlier initial and final sets. • Increased heat generation; higher maximum peak on the hydration curve. 53
  • 54. References • Technical summary 4-a, National concrete pavement technology center, IOWA State University, August 2007. • Wolfgang B., Concrete an example for complex porosity, Institute of building materials research (IBAC), RWTH Achen university, Germany. • Dr. K. Kurtis, Cement and Hydration, School of civil engineering, Georgia Institute of technology, Atlanta, Georgia. • Feng Lin, Modelling of hydration kinetics and shrinkage of Portland cement paste, Coloumbia University, 2006. • S. G. kim, Effect of heat of hydration on mass concrete placement, IOWA state university, 2010. • A.S.M abdul Awal & M. Warid Husain, Effect of palm oil fuel ash in controlling heat of hydration of concrete, University of technology, Johor Malaysia. • P. Juilland et al., Effects of mixing on early hydration of alite and OPC system, Cement and Concrete Research, 2012. 54
  • 55. References • Concrete technology today, Vol. 18, Portland Cement Association, July 1997. • A.K Schindler & K. J. Folliard, Heat of hydration Model for cementitious materials, ACI Material Journal. • L. E. Copeland et al. Chemistry of hydration of Portland Cement, Search Department, Bulletin 153. • Jochen Stark, Recent Advances in field of cement hydration and microstructure analysis, cement and Concrete Research, 2011. • J. W. Bullard et al., Mechanism of Cement Hydration, Cement Concrete Research, 2011. • H. F. W. Taylor, Cement Chemistry, Academic Press London, 1990. • Mindess et al., Properties of hydrated Cement Compounds, 2004. • Standard Test Method for Measurement of Heat of Hydration (ASTM C 186) • Class Notes 55
  • 56. 56