CEE 306 - Lecture 04 - Cement

PORTLAND CEMENT
CONCRETE COMPONENTS
CEE 306
CIVIL ENGINEERING MATERIALS
CHANG-SEON SHON, PH.D., ASSISTANT PROFESSOR

DEPARTMENT OF CIVIL & ENVIRONMENTAL ENGINEERING
NAZARBAYEV UNIVERSITY
Lecture 04
1
CEE 306: Civil Engineering Materials
INTRODUCTION
• CONCRETE = CEMENT + WATER + FINE AGGREGATE

+ COARSE AGGREGATE + (ADMIXTURES)
• ADVANTAGES
– Formable
– Components are typically available
• Aggregate / Limestone & clay for cement / Water
– Durable
– Low cost
– Utilize low energy to produce
• MANY TYPES OF CONCRETE
Lecture 04 2
1
INTRODUCTION (CONT’D)
• ENGINEERS ARE DIRECTLY RESPONSIBLE FOR THE

– Design of the mix
– Final quality of concrete
Lecture 04
3
CONCRETE INGREDIENTS
• PORTLAND CEMENT (PC)
• WATER CONCRETE ≠ CEMENT
• AGGREGATES
– Fine aggregate / Coarse aggregate
• ADMIXTURES (SOMETIMES)
• TERMINOLOGY
– Cement Paste = Cement + Water → Glue (binder)
– Mortar = Cement + Water + Fine aggregate
– Concrete = Cement + Water + Fine aggregate + Coarse aggregate
Vconcrete  Vwater  Vcement  Vcoarse aggregate  V fine aggregate  Vair
Lecture 04 4
2
QUALITY OF CONCRETE
• Depends on:
– Cement type – Transporting
(Chemical composition) – Hydration
– Aggregate – Placing
– Water – Vibrating
– Admixtures – Curing
– Proportions
– Mixing
Lecture 04
5
PORTLAND CEMENT CONCRETE

COMPONENTS
Lecture 04 6
3
PORTLAND CEMENT CONCRETE
COMPONENTS
• Concrete = Cement + Water + Fine aggregate

+ Coarse aggregate + (Admixtures)
– Portland cement (7.5% - 15% of vol.)
– Water (16% - 21% of vol.)
– Aggregates (55% - 75% vol.) Typical mixture
• Fine aggregate (25%-30%)
• Coarse aggregate (30%-45%)
– Air voids (1% - 8% of vol.)
– Sometimes admixtures
• Mineral admixture (supplementary cementitious materials)
• Chemical admixture
Lecture 04
7
PORTLAND CEMENT
Lecture 04 8
4
MAJOR CONSTITUENTS OF CEMENT
Oxide Common Name Abbr. Typical Wt. (%)
CaO Lime C 63 (60-75)
SiO2 Silica S 22 (20-24)
Al2O3 Alumina A 6 (4-8)
Fe2O3 Ferro oxide F 2.5 (2-5)
MgO Magnesia M 2.6
K2O Alkali K 0.6
Na2O Alkali Na 0.3
SO3 Sulfate 0.2
Lecture 04
9
RAW MATERIALS TO MANUFACTURE

PORTLAND CEMENT
• RAW MATERIALS
– 2/3 calcareous Raw materials of main component
materials (lime
bearing) -
limestone
– 1/3 argillaceous
materials (silica,
alumina, iron) -
clay
Lecture 04 10
5
CEMENT MANUFACTURING
Quarry
Crush raw materials to 127 to 19 mm(5” - ¾”)

Grind to Powder & Blend (w/ or w/out Water)
Calcinate & Burn

Cool to form clinker (10 mm)
(1400 C~1650 C)
Inter-grind w/ 5% gypsum (1-100mm) 11

CEE 306: Civil Engineering Materials Lecture 04
TRADITIONAL MANUFACTURE OF
PORTLAND CEMENT
• Stone is first reduced to 127 mm (5 in.) size, then to 19

mm (3/4 in.), and stored.
Quarry
Lecture 04 12
6
PORTLAND CEMENT (CONT’D)
• Raw materials are ground to powder and blended*
• Raw materials are ground, mixed with water to form

slurry, and blended
Lecture 04
13
• Burning changes raw mix chemically into cement

clinker
Calcinate (~1200°C) & Burn (1400~1650°C)
Cool to form Clinker (10-19 mm)
Clinker
Lecture 04 14
7
• Clinker with gypsum (5%) is ground into portland cement

(fine powder) → small particles produce a large surface
area for more complete hydration
5% gypsum (1-100 μm) Gypsum
Lecture 04
15
CLINKERING PROCESS IN KILN
• Drying
• Calcination (~1200C) CaCO3  CaO  CO2
• Initial Combination by solid state sintering
CaO  Al2O3  3CaO Al2O3  C3 A
2CaO  Fe2O3  4CaO Al2O3 Fe2O3  C4 AF
• Clinker Formation (~1400C) by dissolution &

recrystallization @ lower T due to Al2O3 and Fe2O3
CaO  SiO2  2CaO SiO2  C2 S
2CaO SiO2  CaO  3CaO SiO2  C3 S
• Cooling from Partial Melt
Lecture 04 16
8
LINKER PRODUCTION
• TYPICAL ROTARY CEMENT

KILN EQUIPPED WITH
PREHEATER AND
PRECALCINER
Lecture 04
17
CLINKER COMPOSITION
Lecture 04 18
9
CEMENT COMPOSITION
Gypsum affects the solubility of aluminate
Lecture 04
19
CHEMICAL COMPOSITION OF CEMENT
• Main compounds:
– Tricalcium silicate (C3S)
– Dicalcium silicate (C2S)
– Tricalcium aluminate (C3A)
– Tetracalcium aluminoferrite (C4AF)
• Minor compounds: small percent but can have strong
influences:
– Magnesium oxide
– Titanium oxide
– Manganese oxide
– Sodium oxide
– Potassium oxide
• Alkalis (Na2O, K2O) react with silica causing disintegration
& expansion of concrete
Lecture 04 20
10
MAIN COMPOUNDS OF PORTLAND
CEMENT
Lecture 04
21
ROLE OF MAIN COMPONENTS OF

PORTLAND CEMENT
Main components of Weight Note
portland cement (%) Very Important !!!
Tricalcium silicate (C3S) 50 (45-60) • Very reactive compound
• High early strength
• Reacts with relatively quickly
• Contributes to both set time & high heat of
hydration
Dicalcium silicate (C2S) 25 (15-30) • Low heat of hydration
• Slow reaction
• Contribute to long-term strength
Tricalcium aluminate (C3A) 10 (6-12) • React quickly with water
• Be responsible for the cement set time & high
heat of hydration
• Cause problems with sulfate attack
Tetracalcium aluminoferrite 5 (6-8) • Generates heat in similar quantities as C3S
(C4AF) • Contributes little toward the set and strength of
the cement
Gypsum (C ̅H2) • Used to control the set of cement
Lecture 04 22
11
COMPOUND COMPOSITION
CALCULATION
• Bogue Composition
Lecture 04
23
CALCULATION (CONT’D)
• Bogue Calculation
Lecture 04 24
12
CALCULATION (CONT’D)
• Bogue Calculation
Check
Al2O3/Fe2O3
Lecture 04
25
CEMENT
QUALITY
REPORT
• Cement mill
test report
Lecture 04 26
13
SPECIFIC GRAVITY OF CEMENT
• Gcement ≈ 3.15
– Measured for cement particles without air voids
• Bulk unit weight (weight required to fill a container) is
highly variable.
• Cement should not be measured by volume
Lecture 04
27
HYDRATION OF CEMENT
• CHEMICAL REACTION OF CEMENT WITH WATER
• EXOTHERMIC REACTION BETWEEN CEMENT AND WATER (MAX
HEAT @ 2-4 DAYS)
• TWO PRIMARY MECHANISMS
– Through solution hydration theory
– Topochemical (Solid-state) hydration theory
– Through-solution theory dominates in the early stages of
hydration
– At later, the solid-state hydration process dominates when
the ionic mobility in solution become restricted
Lecture 04 28
14
HYDRATION OF THEORY OF CEMENT
• THROUGH SOLUTION • TOPOCHEMICAL (SOLID-
HYDRATION THEORY STATE) HYDRATION THEORY
– Dissolution of anhydrous – Reaction take place
compounds to their ionic directly at the surface of
constituent the cement grains w/o
– Formation of hydrates in going into solution
solution
– Eventual precipitation due
to their low solubility
Lecture 04
29
ACTUAL HYDRATION MECHANISM

• WHEN WATER IS ADDED TO CEMENT, WHAT HAPPENS?
– Dissolution of cement grains Through
– Growing ionic concentration in “water” (now a solution) solution
hydration
– Formation of compounds in solution theory
– After reaching a saturation concentration, compounds Solid-state

hydration
precipitate out as solids (“hydration products”) theory
– In later stages, products form on or very near the surface of
the anhydrous cement
Lecture 04 30
15
HYDRATION OF CEMENT
• “SHEAF OF WHEAT” HYDRATES ARE FORMING ON THE CEMENT

GRAINS DURING THE FIRST MINUTES
• 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
Lecture 04
31
ROLE OF MAIN COMPONENTS OF

PORTLAND CEMENT
Main components of Weight Note
portland cement (%) Extremely Important !!!
Tricalcium silicate (C3S) 50 (45-60) • Very reactive compound
• High early strength
• Reacts with relatively quickly
• Contributes to both set time & high heat of
hydration
Dicalcium silicate (C2S) 25 (15-30) • Low heat of hydration
• Slow reaction
• Contribute to long-term strength
Tricalcium aluminate (C3A) 10 (6-12) • React quickly with water
• Be responsible for the cement set time & high
heat of hydration
• Cause problems with sulfate attack
Tetracalcium aluminoferrite 5 (6-8) • Generates heat in similar quantities as C3S
(C4AF) • Contributes little toward the set and strength of
the cement
Gypsum (C ̅H2) • Used to control the set of cement
Lecture 04 32
16
CEMENT HYDRATION &
CHEMICAL REACTION
Extremely Important !!!

cement
Chemical Reaction
2C3S + 6H → C3S2H3 + 3CH + 120 cal/g
+ dissolution precipitation
2C2S + 4H → C3S2H3 + CH + 62 cal/g
C3A + CŜH2 + H → Ettringite + 300 cal/g
water
Note:
C-S-H: Calcium silicate hydrate
CH: Calcium hydroxide
CŜH: Calcium sulfo hydrate
Lecture 04
33
CEMENT HYDRATION & CHEMICAL

REACTION (CONT’D)
Lecture 04 34
17
HYDRATION
Lecture 04
35
REACTIVITY OF CEMENT COMPOUNDS
Lecture 04 36
18
STRENGTH CONTRIBUTION OF
CEMENT COMPOUNDS
Lecture 04
37
HYDRATION PRODUCTS
Solids in cement paste Main Characteristics
Very Important !!!
Calcium Silicate Hydrate • C/S ratio: 1.5 to 2.0
(C-S-H) • High surface area (100 to 700 m2/g)
• High Van der Walls force (Strength)
• Thin layered structure, amorphous
• 50% ~ 60% Vol.
Calcium Hydroxide (portlandite) • Low Van der Walls force
(CH) • Problem with durability & strength
• Large hexagonal plates
• 20% ~ 25% Vol.
Calcium Sulfoanluminate • First: ettringite (needles)
Hydrates (C4A ̅H12) • After: monosulfate hydrated (thin
irregular plates)
• 15% ~ 20% Vol.
Tetracalcium aluminate Hydrate • Similar to monosulfate hydrated
Ferric-Aluminum Hydroxide • Amorphous
[C4(A,F)H13]
Lecture 04 38
19
DEGREE OF HYDRATION VS. VOLUME
OF HYDRATION PRODUCTS
Hydration
products
Cement
compounds
Lecture 04
39
SOLID COMPONENTS OF
HARDENED CEMENT PASTE
Lecture 04 40
20
INFLUENCE OF CEMENT COMPOUNDS
ON CONCRETE PROPERTIES
Lecture 04
41
VOIDS IN HYDRATED CEMENT
Lecture 04 42
21
(CONT’D)
(C-S-H layer space)
Lecture 04
43

(CONT’D)
• INTERLAYER HYDRATION SPACE (GEL PORE)
– Space between atomic layers
– Size: 5 ~ 25Å
– Drying shrinkage if humidity <11%
• CAPILLARY AIR VOIDS
– W/c ratio too high
– > 50nm: Decrease strength and increase permeability
– < 50 nm: Important to drying shrinkage and creep
• TRAPPED AIR VOIDS
– Large pockets caused by handling (~ 3mm)
– Decrease strength and increase permeability
• ENTRAINED AIR VOIDS
– Microscopic bubbles caused by admixtures (50 ~ 200mm)
– Increases durability
Lecture 04 44
22
DEGREE OF HYDRATION VS.
CAPILLARY POROSITY
Lecture 04
45
STRENGTH VS. PERMEABILITY
• IN GENERAL, EACH 1% OF AIR

CAUSES 5% LOSS IN STRENGTH
Lecture 04 46
23
WATER INSIDE THE PORES
Lecture 04
47
DIMENSIONAL RANGE OF SOLID AND

PORES IN A HYDRATED CEMENT PASTE
Lecture 04 48
24
INFLUENCE OF PORE SIZES ON PROPERTIES
OF HYDRATED CEMENT PASTE
Lecture 04
49
SETTING AND HARDENING
• DRYING: LOOSING WATER = EVAPORATION

– Stop reaction / stop strength gain
• STIFFENING: LOSS OF CONSISTENCY BY THE PLASTIC CEMENT
PASTE & IT IS ASSOCIATED WITH THE SLUMP LOSS PHENOMENA
IN CONCRETE
• SETTING: SOLIDIFICATION OF THE PLASTIC CEMENT PASTE (LOSE
OF FLUIDITY & GETTING STIFFENING)
– Initial set: Beginning to stiffen (Type I cement: >45 min.)
– Final set: Beginning to harden (Type I cement: 5-8 hrs)
• HARDENING: LASTS FOR MONTHS OR YEARS
Hardening ≠ setting or drying
Lecture 04 50
25
SETTING &
HARDENING
Lecture 04
51
OTHER FACTORS AFFECTING

HYDRATION
• INCREASED CEMENT FINENESS

– Accelerate set & strength gain
• HIGH WATER CONTENT
– Slow set
• HIGH AMBIENT TEMPERATURE
– Accelerate set
• OPTIMUM GYPSUM
– Slow set, limit expansion & unsoundness
Lecture 04 52
26
OTHER FACTORS AFFECTING
HYDRATION (CONT’D)
• WATER TO CEMENT RATIO

– The most important property of hydrating cement
– Water needed for hydration, w/c = 0.22-0.25
• EXTRA WATER IS NEEDED FOR WORKABILITY, BUT
CAUSES VOIDS
– Decreases strength
– Decreases durability
– Decreases bond between successive layers
– Decreases bond between concrete and rebar
– Increases permeability
– Increases volume change from wetting and drying
Lecture 04
53
ASTM PORTLAND CEMENTS
• TYPE I: GENERAL PURPOSE

• TYPE II: MODERATE HEAT OF HYDRATION AND SULFATE
RESISTANCE (C3A < 8%)
– General construction, sea water, mass concrete
• TYPE III: HIGH EARLY STRENGTH (C3A < 15%)
– Emergency repairs, precast, winter construction
• TYPE IV: LOW HEAT (C3S < 35%, C3A < 7%, C2S > 40%)
– Mass concrete
• TYPE V: SULFATE RESISTANT (C3A < 5%)
– Sulfate in soil, sewers
Lecture 04 54
27
APPLICATION OF COMMONLY USED
CEMENTS
Pozzolans: Mineral
admixtures containing
reactive silica & alumina
which on their own have
little or no binding
properties
P stands for pozzolan
while S stands for slag
Lecture 04
55
TYPES OF PORTLAND CEMENTS
Lecture 04 56
28
ASTM CHEMICAL AND FINENESS
REQUIREMENTS FOR CEMENT (ASTM C 150)
ASTM General description Maximum compound Blaine Fineness
Type composition (%) (m2/kg)
C3S C2S C3A C4AF
I General purpose 45-55 20-30 8-12 6-10 370
II General purpose with moderate 40-50 25-35 5-7 6-10 370

sulfate resistance & moderate
heat of hydration
III High early strength 50-65 15-25 8-14 6-10 540
IV Low heat of hydration 28-35 40-49 5-6 10-12 380
V High sulfate resistance 45-50 25-35 0-4 10-20 380
ASTM ALSO HAS TYPES I-A, II-A, III-A -- CEMENTS WITH AIR ENTRAINMENT
MAX. & MIN. REQUIREMENT (E.G. 35, 40)
Lecture 04
57
TYPES OF PORTLAND CEMENTS
Lecture 04 58
29
HEAT EVOLUTION : EFFECT OF CEMENT
TYPE & CEMENT COMPOSITION)
Decreasing C3S + C3A

content
Lecture 04
59
COMPRESSIVE STRENGTH
Lecture 04 60
30
EXPANSION OF CONCRETE
• EXPANSION OF CONCRETE PREPARED WITH DIFFERENT CEMENTS
AFTER IMMERSION IN SULFATE SOLUTION
Lecture 04
61
POROSITY EVOLUTION
Lecture 04 62
31
OTHER HYDRAULIC CEMENTS
• BLENDED PORTLAND CEMENT

– Type I-P
• P stands for pozzolan
• It contains 25 to 30% of fly ash
• It has low heat of hydration, develops strength over time
– Type I-S
• S stands for slag
• It contains 50 to 60% of Blast Furnace Slag
Lecture 04
63
OTHER HYDRAULIC CEMENTS
• MODIFIED PORTLAND CEMENT

– Type K: shrinkage compensating cement
– Jet set cement: Fast Setting (3-5 min)
– Oil well cement: Drilling of oil wells, incl. organic reatarder
– White cement
• NON-CALCIUM SILICATE CEMENTS (CALCIUM ALUMINATE
CEMENT)
– High early strength
– Hardening even at low temperatures
– Fast hydration
– Superior durability to microbial/biogenic corrosion
Lecture 04 64
32
OTHER HYDRAULIC CEMENTS: EFFECT
OF POZZOLAN ON HEAT OF HYDRATION
Pozzolans: Mineral admixtures containing reactive silica & alumina which on their own have little or
no binding properties
Lecture 04
65
OTHER HYDRAULIC CEMENTS:

COMPRESSIVE STRENGTH
20%
30%
Lecture 04 66
33
EVALUATION OF PORTLAND CEMENT
(TEST METHOD)
Lecture 04
67
FINENESS OF CEMENT
• SMALLER CEMENT PARTICLES HAVE MORE SURFACE AREA TO
REACT WITH WATER
– Fineness controls the rate of hydration (heat & strength
gain)
– Too fine is more expensive and can be harmful
• SURFACE AREA MEASURED INDIRECTLY (cm2/g)
Wagner
Turbidimeter
Brain test
Lecture 04 68
34
TESTS FOR INITIAL AND FINAL SET
• PENETRATION OF WEIGHTED NEEDLE
Lecture 04
69
SOUNDNESS OF CEMENT
• ABILITY TO RETAIN ITS VOLUME

AFTER SETTING
– Expansion after setting is
measured in the autoclave test
at 215.6 oC & 2034 kPa (420 oF
& 295 psi)
– Frame for measuring length of
sample before and after
autoclave conditioning
Lecture 04 70
35
COMPRESSIVE STRENGTH OF MORTAR
(ASTM C 109)
• AVERAGE OF THREE 50mm (2“) MORTAR CUBES

• PROPORTIONAL TO COMPRESSIVE STRENGTH OF CYLINDERS
• COMPRESSIVE STRENGTH OF CONCRETE CANNOT BE ACCURATELY
PREDICTED FROM CEMENT STRENGTH
Lecture 04
71
ALKALI-SILICA REACTIVITY
Lecture 04 72
36
SUMMARY
• VOLUMETRIC MIXTURE DESIGN

Vconcrete  Vwater  Vcement  Vair  Vcoarse aggregate  V fine aggregate
• 4 MAJOR COMPOUNDS/REACTANTS IN CEMENT

• 5-6 HYDRATION PRODUCTS W/ DIFFERENT PROPERTIES FORMED
W/ WATER
• % OF EACH COMPOUND DIFFERS IN EACH ASTM C150 CEMENT
TYPE
– Different properties for each type
• EFFECTS OF PORES
Lecture 04
73
37

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PORTLAND CEMENT

CHANG-SEON SHON, PH.D., ASSISTANT PROFESSOR

• CONCRETE = CEMENT + WATER + FINE AGGREGATE

• ENGINEERS ARE DIRECTLY RESPONSIBLE FOR THE

Vconcrete  Vwater  Vcement  Vcoarse aggregate  V fine aggregate  Vair

PORTLAND CEMENT CONCRETE

• Concrete = Cement + Water + Fine aggregate

CaO Lime C 63 (60-75)

SiO2 Silica S 22 (20-24)

Al2O3 Alumina A 6 (4-8)

Fe2O3 Ferro oxide F 2.5 (2-5)

MgO Magnesia M 2.6

K2O Alkali K 0.6

Na2O Alkali Na 0.3

SO3 Sulfate 0.2

RAW MATERIALS TO MANUFACTURE

Crush raw materials to 127 to 19 mm(5” - ¾”)

Calcinate & Burn

Inter-grind w/ 5% gypsum (1-100mm) 11

• Stone is first reduced to 127 mm (5 in.) size, then to 19

• Raw materials are ground, mixed with water to form

• Burning changes raw mix chemically into cement

Calcinate (~1200°C) & Burn (1400~1650°C)

Cool to form Clinker (10-19 mm)

• Clinker with gypsum (5%) is ground into portland cement

5% gypsum (1-100 μm) Gypsum

CLINKERING PROCESS IN KILN

• Clinker Formation (~1400C) by dissolution &

• TYPICAL ROTARY CEMENT

Gypsum affects the solubility of aluminate

CHEMICAL COMPOSITION OF CEMENT

ROLE OF MAIN COMPONENTS OF

ACTUAL HYDRATION MECHANISM

– After reaching a saturation concentration, compounds Solid-state

• “SHEAF OF WHEAT” HYDRATES ARE FORMING ON THE CEMENT

ROLE OF MAIN COMPONENTS OF

Extremely Important !!!

CEMENT HYDRATION & CHEMICAL

REACTIVITY OF CEMENT COMPOUNDS

VOIDS IN HYDRATED CEMENT

(C-S-H layer space)

VOIDS IN HYDRATED CEMENT

STRENGTH VS. PERMEABILITY

• IN GENERAL, EACH 1% OF AIR

DIMENSIONAL RANGE OF SOLID AND

SETTING AND HARDENING

• DRYING: LOOSING WATER = EVAPORATION

OTHER FACTORS AFFECTING

• INCREASED CEMENT FINENESS

• WATER TO CEMENT RATIO

ASTM PORTLAND CEMENTS

• TYPE I: GENERAL PURPOSE

TYPES OF PORTLAND CEMENTS

I General purpose 45-55 20-30 8-12 6-10 370

II General purpose with moderate 40-50 25-35 5-7 6-10 370

IV Low heat of hydration 28-35 40-49 5-6 10-12 380

V High sulfate resistance 45-50 25-35 0-4 10-20 380

TYPES OF PORTLAND CEMENTS

Decreasing C3S + C3A

• BLENDED PORTLAND CEMENT

OTHER HYDRAULIC CEMENTS

• MODIFIED PORTLAND CEMENT