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CON 123
Cementitious Materials




Session 5
Chemical Properties
Chemical Compounds of Portland
               Cement
   Polished thin-section
    examination of Portland
    clinker shows alite (C3S)
    as light, angular crystals
Chemical Compounds of Portland
               Cement
   The darker, rounded
    crystals are belite
    (C2S)Scanning electron
    microscope (SEM)
    micrograph of alite
    (C3S) crystals in
    Portland clinker.
Chemical Compound Reactions
                                                         Chemical
     Name              Formula         Hydrate
                                                         Reaction
                                   Tricalcium Silicate
Tricalcium Silicate      C3S                              C-S-H
                                   Hydrate
                                   Dicalcium Silicate
Dicalcium Silicate       C2S                              C-S-H
                                   Hydrate
Tricalcium
                         C3A       Ettringite            C6AS3H32
Aluminate
Tricalcium                         Calcium Mono-
                         C3A                             C4ASH12
Aluminate                          sulfoaluminate
                                   Calcium Sulfate
Gypsum                CaSO4:2H2O                          CHS2
                                   Dihydrate
                                   Calcium
Calcium oxide            CaO                               CH
                                   Hydroxide
Magnesium                          Magnesium
                         MgO                               MH
oxide                              Hydroxide
Portland Cements
               Influence of Compounds
   C3S Hydration:
       Heat of Evolution
       Setting characteristics
       Hardening properties
       Early Strength Development
   C2S Hydration:
       Heat of Evolution
       Setting characteristics
       Hardening properties
       Later Strength Development
Portland Cements
            Compound Influence
Fineness
 Finer the cement, the faster the hydration,
  higher initial strength
 3 and 7 day strengths are increased by
  fineness
 Increased water demand of high fineness
  cement may decrease strength
Heat Evolution
Heat evolution as a function of time for cement paste.
 Stage 1 is heat of wetting or initial hydrolysis (C3A and C3S
  hydration).
 Stage 2 is a dormant period related to initial set.
 Stage 3 is an accelerated reaction of the hydration products
  that determines rate of hardening and final set.
 Stage 4 decelerates formation of hydration products and
  determines the rate of early strength gain.
 Stage 5 is a slow, steady formation of hydration products
  establishing the rate of later strength gain.
Heat Evolution
Heat of Hydration
                                       Heat of hydration
 Compound Name        Bogue Compound
                                             Cal/g

Tricalcium Silicate        C3S               120

Dicalcium Silicate         C2S                62
Tricalcium
                           C3A               207
Aluminate
Tetracalcium
                          C4AF               100
aluminoferrite
Relative Volumes
Relative volumes of the
major compounds in the
microstructure of
hydrating Portland
cement pastes (left) as a
function of time and as a
function of the degree of
hydration.
Relative Volumes
Values are given for an
average Type I cement
composition:
C3S=55%, C2S=18%, C3A=10
% and C4AF=8%. “AFt and
AFm” includes ettringite
(AFt) and calcium
monosulfoaluminate (AFm)
and other hydrated calcium
aluminate compounds.
Portland Cements
Chemical Compound Contribution to Strength
Reactivity of Cement Compounds
   Relative reactivity of
    cement compounds.
   The curve labeled
    “overall” has a
    composition of 55%
    C3S, 18% C2S, 10%
    C3A, and 8% C4AF, an
    average Type I cement
    composition.
Compound Influence on Setting Time:
                      Time of Final Set
   C3S is major influence in final set time
   Fineness of cement
   Temperature of mixture
       (Nearly all exothermic reactions are accelerated by heat)
   Admixtures
   Mass of Cementitious Material
   Type of Cementitious Materials
       Fly ash and slag are slower in winter
       Large mass of fly ash may be slower
Setting Time of Cement
Coagulation-Crystalline layer of ettringite is thixotrophic network of high surface area off of
which C-S-H can grow.

                         Coagulation-Crystalline
                                                                            C-S-H
                          network of ettringite

                     H2O
                                                   time



         •C3A
         •C3S                    •C3A

         •C2S                    •Gypsum
         •C4AF                   •H2O
                                                                             C3S+H2O
         •Gypsum
                            Thixotrophic
                                                                          Hardening
                                Mixture
                                                                           Mixture
Time of Set for Portland Cements
Portland Cements
Alkalies (K2O & Na2O) - usually expressed as Na2Oeq
  or total alkalies
 Present in all raw materials
 More soluble alkalies -
                 Shorter set times
                 Higher early strength
                 Lower 28 day strength
                 Lower AEA dose
                 Higher WR dose
   Alkali - reactive aggregates (opal, chert)
   “Low alkali cement” contains less that 0.60% total
    alkalies
                                                         18
Portland Cements
Alkalies (K2O & Na2O) - usually expressed as Na2Oeq or total
alkalies
 Present in all raw materials

 More soluble alkalies -
                   Shorter set times
                   Higher early strength
                   Lower 28 day strength
                   Lower AEA dose
                   Higher WR dose
   Alkali - reactive aggregates (opal, chert)
   “Low alkali cement” contains less that 0.60% total alkalies
Portland Cements
Sulfate Attack
   Sulfate attack is often the
    most severe at the location
    of the most wetting and
    drying, which is usually near
    the soil line.
   Here concrete posts have
    been attacked by sulfates
    near the soil line. The
    concrete is in better
    condition deep within the
    soil where it is moist.
Effect of C3A on Sulfate Resistance
Sulfate Attack 4 Month % Expansion


                                               Y = 0.116075 - 3.71E-02X + 5.80E-03X**2
                                                           R-Sq = 0.320
                                     0.8
                                     0.7
                                     0.6
                                     0.5
                                     0.4
                                     0.3
                                     0.2
                                     0.1
                                     0.0
                                           4     5     6     7 8          9    10 11 12
                                                             C3A
Alkali-Silica Reactivity
                                             ASR Expansion vs. Total Equivalent Alkali
             ASR 12 Week Percent Expansion



                                              0.5                     Y = -3.2E-02 + 7.88E-02X + 0.417862X**2
                                                                             R-Sq = 84.1 %
                                              0.4


                                              0.3


                                              0.2


                                              0.1


                                              0.0

                                                    0.0   0.1   0.2    0.3    0.4   0.5   0.6    0.7   0.8      0.9   1.0
                                                           Total Equivalent Alkali Content (%)




Alkali Silica correlation at 14 weeks is not as great as at greater ages.
Fly Ash and Natural Pozzolans
   Reduced Permeability & Diffusivity
   Resistance to ASR
       Consumption of Ca(OH)2
       Reduction in water mobility
   Resistance to Sulfate (Low CaO pozzolans)
       Dilution of C3A
       Consumption of Ca(OH)2
       Iron stabilizing effect
Blast Furnace Slag Impact
   Reduced Permeability & Diffusivity
   Resistance to ASR (>35%)
       Reduction in water mobility
   Resistance to Sulfate
       Dilution of C3A
       Iron stabilizing effect
Silica Fume Impact
   Higher Strength
   Reduced Permeability & Diffusivity
   Resistance to ASR
       Consumption of Ca(OH)2
       Reduction in water mobility
   Resistance to Sulfate (Low CaO pozzolans)
       Consumption of Ca(OH)2
Chemical Properties

Please return to Blackboard and watch the
following video:
 Video 1: Cement Hydration

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CON 123 - Session 5 - Chemical Properties

  • 2. Chemical Compounds of Portland Cement  Polished thin-section examination of Portland clinker shows alite (C3S) as light, angular crystals
  • 3. Chemical Compounds of Portland Cement  The darker, rounded crystals are belite (C2S)Scanning electron microscope (SEM) micrograph of alite (C3S) crystals in Portland clinker.
  • 4. Chemical Compound Reactions Chemical Name Formula Hydrate Reaction Tricalcium Silicate Tricalcium Silicate C3S C-S-H Hydrate Dicalcium Silicate Dicalcium Silicate C2S C-S-H Hydrate Tricalcium C3A Ettringite C6AS3H32 Aluminate Tricalcium Calcium Mono- C3A C4ASH12 Aluminate sulfoaluminate Calcium Sulfate Gypsum CaSO4:2H2O CHS2 Dihydrate Calcium Calcium oxide CaO CH Hydroxide Magnesium Magnesium MgO MH oxide Hydroxide
  • 5. Portland Cements Influence of Compounds  C3S Hydration:  Heat of Evolution  Setting characteristics  Hardening properties  Early Strength Development  C2S Hydration:  Heat of Evolution  Setting characteristics  Hardening properties  Later Strength Development
  • 6. Portland Cements Compound Influence Fineness  Finer the cement, the faster the hydration, higher initial strength  3 and 7 day strengths are increased by fineness  Increased water demand of high fineness cement may decrease strength
  • 7. Heat Evolution Heat evolution as a function of time for cement paste.  Stage 1 is heat of wetting or initial hydrolysis (C3A and C3S hydration).  Stage 2 is a dormant period related to initial set.  Stage 3 is an accelerated reaction of the hydration products that determines rate of hardening and final set.  Stage 4 decelerates formation of hydration products and determines the rate of early strength gain.  Stage 5 is a slow, steady formation of hydration products establishing the rate of later strength gain.
  • 9. Heat of Hydration Heat of hydration Compound Name Bogue Compound Cal/g Tricalcium Silicate C3S 120 Dicalcium Silicate C2S 62 Tricalcium C3A 207 Aluminate Tetracalcium C4AF 100 aluminoferrite
  • 10. Relative Volumes Relative volumes of the major compounds in the microstructure of hydrating Portland cement pastes (left) as a function of time and as a function of the degree of hydration.
  • 11. Relative Volumes Values are given for an average Type I cement composition: C3S=55%, C2S=18%, C3A=10 % and C4AF=8%. “AFt and AFm” includes ettringite (AFt) and calcium monosulfoaluminate (AFm) and other hydrated calcium aluminate compounds.
  • 12. Portland Cements Chemical Compound Contribution to Strength
  • 13. Reactivity of Cement Compounds  Relative reactivity of cement compounds.  The curve labeled “overall” has a composition of 55% C3S, 18% C2S, 10% C3A, and 8% C4AF, an average Type I cement composition.
  • 14. Compound Influence on Setting Time: Time of Final Set  C3S is major influence in final set time  Fineness of cement  Temperature of mixture  (Nearly all exothermic reactions are accelerated by heat)  Admixtures  Mass of Cementitious Material  Type of Cementitious Materials  Fly ash and slag are slower in winter  Large mass of fly ash may be slower
  • 15. Setting Time of Cement Coagulation-Crystalline layer of ettringite is thixotrophic network of high surface area off of which C-S-H can grow. Coagulation-Crystalline C-S-H network of ettringite H2O time •C3A •C3S •C3A •C2S •Gypsum •C4AF •H2O C3S+H2O •Gypsum Thixotrophic Hardening Mixture Mixture
  • 16. Time of Set for Portland Cements
  • 17. Portland Cements Alkalies (K2O & Na2O) - usually expressed as Na2Oeq or total alkalies  Present in all raw materials  More soluble alkalies -  Shorter set times  Higher early strength  Lower 28 day strength  Lower AEA dose  Higher WR dose  Alkali - reactive aggregates (opal, chert)  “Low alkali cement” contains less that 0.60% total alkalies 18
  • 18. Portland Cements Alkalies (K2O & Na2O) - usually expressed as Na2Oeq or total alkalies  Present in all raw materials  More soluble alkalies -  Shorter set times  Higher early strength  Lower 28 day strength  Lower AEA dose  Higher WR dose  Alkali - reactive aggregates (opal, chert)  “Low alkali cement” contains less that 0.60% total alkalies
  • 20. Sulfate Attack  Sulfate attack is often the most severe at the location of the most wetting and drying, which is usually near the soil line.  Here concrete posts have been attacked by sulfates near the soil line. The concrete is in better condition deep within the soil where it is moist.
  • 21. Effect of C3A on Sulfate Resistance Sulfate Attack 4 Month % Expansion Y = 0.116075 - 3.71E-02X + 5.80E-03X**2 R-Sq = 0.320 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 4 5 6 7 8 9 10 11 12 C3A
  • 22. Alkali-Silica Reactivity ASR Expansion vs. Total Equivalent Alkali ASR 12 Week Percent Expansion 0.5 Y = -3.2E-02 + 7.88E-02X + 0.417862X**2 R-Sq = 84.1 % 0.4 0.3 0.2 0.1 0.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Total Equivalent Alkali Content (%) Alkali Silica correlation at 14 weeks is not as great as at greater ages.
  • 23. Fly Ash and Natural Pozzolans  Reduced Permeability & Diffusivity  Resistance to ASR  Consumption of Ca(OH)2  Reduction in water mobility  Resistance to Sulfate (Low CaO pozzolans)  Dilution of C3A  Consumption of Ca(OH)2  Iron stabilizing effect
  • 24. Blast Furnace Slag Impact  Reduced Permeability & Diffusivity  Resistance to ASR (>35%)  Reduction in water mobility  Resistance to Sulfate  Dilution of C3A  Iron stabilizing effect
  • 25. Silica Fume Impact  Higher Strength  Reduced Permeability & Diffusivity  Resistance to ASR  Consumption of Ca(OH)2  Reduction in water mobility  Resistance to Sulfate (Low CaO pozzolans)  Consumption of Ca(OH)2
  • 26. Chemical Properties Please return to Blackboard and watch the following video:  Video 1: Cement Hydration

Editor's Notes

  1. Sulfate attack is often the most severe at the location of the most wetting and drying, which is usually near the soil line. Here concrete posts have been attacked by sulfates near the soil line. The concrete is in better condition deep within the soil where it is moist.