Tests on Portland Cement

Dr. Kimberly Kurtis

School of Civil Engineering Georgia Institute of Technology Atlanta, Georgia

Composition
Chemical Name Tricalcium silicate Dicalcium silicate Tricalcium aluminate Tetracalcium aluminoferrite Calcium sulfate dihydrate Chemical Formula 3CaOSiO2 2CaO SiO2 3CaOAl2O3 4CaOAl2O3Fe2O3 CaSO42H2O Shorthand Notation C3S C2S C3A C4AF CSH2 Mass (%) 50 - 70 15 - 30 5 - 10 5 - 15 ~5

Composition
The relative quantities of each of these phases affects: setting time rate of strength development overall strength durability color It is important, then, to know the composition of the cement.

Tests on Portland, Blended & Hydraulic Cements

Chemical Properties Chemical analysis Compound composition Chemical limits Physical Properties Fineness Soundness Consistency Setting time False set and flash set Compressive strength Heat of hydration Loss on ignition Density Bulk density Sulfate expansion

Belite, C2S

Alite, C3S

Width of field = 0.31 mm

http://www.bruker-axs.de

Chemical Analysis
SiO2 Al2O3 Fe2O3 CaO MgO SO3 LOI Na2O K2O TiO2 P2O5 ZnO Mn2O3 Silicon dioxide Aluminum oxide Ferric oxide Calcium oxide Magnesium oxide Sulfur trioxide Loss on ignition Sodium oxide Potassium oxide Titanium dioxide Phosphorus pentoxide Zinc oxide Manganic oxide

ASTM C 114 Standard Test Methods for Chemical Analysis of Hydraulic Cement
Major components Separate determinations Insoluble residue Free calcium oxide CO2 (carbon dioxide) Water-soluble alkali Chloroform soluble organic substances Minor components

Sulfide sulfur

ASTM C114
Oxide Analysis
Oxide %

Oxide CaO SiO2 Al2O3 90 95% Fe2O3 MgO K2O Na2O SO3 CO2 H2O

Shorthand C S A F M K N S C H

Common Name lime silica alumina ferric oxide magnesia alkalis sulfate carbonate water

SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3 LOI

20.6 5.07 2.90 63.9 1.53 0.73 0.15 2.53 1.58

+ other trace elements

Compound Composition

Bogue Composition C3S = 4.07C 7.60S 6.72A 1.43F 2.85S C2S = 2.87S 0.75C3S C3A = 2.65A 1.69F C4AF = 3.04F (Only valid when A/F 0.64)

Bogue Composition: Example

Oxide Analysis
Oxide %

Calculated Phase Composition C3S = 4.07(63.9) 7.60(20.6) 6.72(5.07) 1.43(2.90) - 2.85(2.53) = 58.1

SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3 LOI

20.6 5.07 2.90 63.9 1.53 0.73 0.15 2.53 1.58

C2S = 2.87(20.6) 0.754(58.1) = 15.6 C3A = 2.65(5.07) 1.69(F 2.90) = 8.5 C4AF = 3.04(2.90) = 8.8 Bogue Potential Composition: C3S C2S C3A C4AF 58% 16% 9% 9%

Typical Chemical Composition of Portland Cement

Oxide Analysis
Oxide %

Sodium equivalent, Na2Oe

SiO2 Al2O3 Fe2O3 CaO MgO 20.6 5.07 2.90 63.9 1.53

Na2Oe = Na2O + (0.658 x K2O)

Na2Oe = 0.15 + (0.658 x 0.73) Na2Oe = 0.63%

K2O Na2O
SO3 LOI

0.73 0.15
2.53 1.58

+ other trace elements

Bogue Composition
The Bogue equations are based on the following assumptions: 1) All 4 phases are pure 2) All the F present occurs as C4AF, and the quantities of A = 0.64(%F) and C = 1.40 (%F) are subtracted from the appropriate totals. 3) The remaining Al2O3 is combined as C3A and a further quantity of C = 1.65 (% Al2O3) is subtracted fromt eh total remaining CaO. 4) The SiO2 combines initially with CaO to form C2S giving a provisional C2S figure. The CaO combining with SiO2 = 2.87%(SiO2) is subtracted from the total CaO figure, and the remaining CaO is then combined with a part of the C2S = 4.07(%CaO) to form C3S. As a result, Bogue compositions may be off by as much as 10% compared to XRD-determined compositions.

Bogue

XRD

Chemical Limits
ASTM C 150 Portland Cement - Chemical Requirements
Cement Type I SiO2, min. % Al2O3, max. % Fe2O3, max. % MgO, max. % SO3, max. % C3A 8% C3A > 8% LOI, max. % Insoluble residue, max. % 6.0 3.0 3.5 3.0 0.75 II 20.0 6.0 6.0 6.0 3.0 n/a 3.0 0.75 III 6.0 3.5 4.5 3.0 0.75 IV 6.5 6.0 2.3 n/a 2.5 0.75 V 6.0 3.0 n/a 3.0 0.75

Chemical Limits
ASTM C 150 Portland Cement - Chemical Requirements
Cement Type I C3S, max. % C2S, min. % C3A, max. % C4AF + 2 C3A, max. % II 8 III 15 IV 35 25 7 V 5 25

Chemical Limits
ASTM C 150 Portland Cement Optional Chemical Requirements
Cement Type I C3A, max. % C3A, max. % C33 + C3A, max. % Na2Oe, max. % 0.60 II 58 0.60 III 8 5 0.60 IV 0.60 V 0.60

Chemical Limits
ASTM C 595 Blended Cement - Chemical Requirements Cement Type I(SM), I(SM)A, IS, IS-A S, SA I(PM), I(PM)-A, P, PA, IP, IP-A 6.0 4.0 5.0 -

MgO, max. % Sulfur reported as SO3, max. % Sulfide sulfur (S), max. % Insoluble residue, max. % LOI, max. % Water-soluble alkali, max. %
*Only

3.0 2.0 1.0 3.0 -

4.0 2.0 1.0 4.0 0.03*

required when cement is specified to be nonstaining to limestone

Fineness
Fineness of cement is also important; it affects: rate of hydration rate of setting rate of hardening durability (ASR) rate of carbonation during storage cost rate of gypsum addition bleeding

Fineness
However, later strength is not directly affected.

Neville, Fig. 1.5

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Fineness
Approx. 95% 45 microns Average diameter ~ 15 microns Those retained on the No 200 sieve (75 microns) will never hydrate completely Those retained on the No 325 sieve (45 microns) will be difficult to hydrate completely Type III >> Type I, II, V > Type IV

Fineness is generally described as the specific surface of the cement, which is the surface area expressed in m2/kg

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Lea and Nurse Air Permeability Relates flow of fluid (air) through a bed of granular material (cement) to the specific surface area of that granular material By knowing cement, a bed 10mm thick with porosity of 4.75% is made; air is passed through at constant velocity; pressure drop is measured. Sw= 14 [(3Ah1)/(KLh2)]0.5 (1-)

Blaine Air Permeability

With the Lea Nurse method, air passes through the bed at a constant rate In the Blaine test, a known volume of air passes at a constant pressure through the bed The rate of flow decreases steadily The time for flow to occur is measured for a given apparatus and a standard porosity of 5% (0.500). Sw = K2t0.5

Blaine Air Permeability (ASTM C 204)

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Wagner Turbidimeter
Uses a photoelectric cell to measure light passing through cement particles suspended in kerosene Test is based on Stokes Law that states that a sphere will obtain a constant velocity under the action of gravity Allows calculation of particlesize distribution (psd)

Wagner Turbidimeter (ASTM C 115)

Blaine, in general, is 1.8X Wagner

Laser Particle Size Analyzer

Laser particle size analyzer Particle-size distribution (psd)

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Cement Fineness

ASTM C 430 Sample washed over 45-m (# 325) sieve Used in production Limits for pozzolans and slag (ASTM C 595)

Cement Fineness
Requirements for Type I, II, IV & V (No requirements for Type III) Air Permeability Turbidimeter Minimum, m2/kg ASTM C 150 & AASHTO M 85 280 400 350-380 Type I 450-600 Type III No limits for blended cement (ASTM C 595) or hydraulic cements (ASTM C 1157) but values must be reported on mill test reports 160 220

Maximum, m2/kg AASHTO M 85 Typical values, m2/kg

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Soundness

Soundness

- ability of hardened paste to maintain volume after setting

Unsoundness (abnormal expansion) caused by hard-burned CaO or MgO

CaO + H 2O Ca (OH ) 2 MgO + H 2O Mg (OH ) 2

ASTM C 151 Standard Test Method for Autoclave Expansion of Portland Cement Expansion for all portland, blended & hydraulic cements

0.80%

Consistency
Consistency of Cement Paste Penetration of 10 1 mm of Vicat plunger ASTM C 187 Standard Test Method for Normal Consistency of Hydraulic Cement

Consistency of Mortar Flow table ASTM C 1437 Standard Test Method for Flow of Hydraulic Mortar

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Setting Time

Initial Set

Time from moment water is added until the paste ceases to be fluid and plastic Time from moment water is added for the paste to acquire a certain degree of hardness

Final Set

Setting Time: Standard Test

Vicat Needle ASTM C 191 Standard Test Method for Time of Setting of Hydraulic Cement by Vicat Needle Initial set occurs when needle penetrates - after 30s - 25 mm (1 inch) into paste Final set occurs when there is no visible penetration

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Setting Time: Field Measurements

Concrete penetrometer, measures resistance to penetration in sieved mortar samples Pocket penetrometers

Setting Time: Standard Test

Gillmore Needles ASTM C 266 Standard Test Method for Time of Setting of Hydraulic-Cement Paste by Gillmore Needles Setting determined as time when paste resists indentation by needles

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Setting Time
Vicat Needle ASTM C 150 Portland Cement Initial Set, not less than (h:min) Final Set, not more than (h:min) ASTM C 595 Blended Cement Initial Set, not less than (h:min) Final Set, not more than (h:min) ASTM C 1157 Hydraulic Cement Initial Set, not less than (h:min) Final Set, not more than (h:min) 0:45 7:00 0:45 7:00 0:45 6:15 1:00 10:00 Gillmore Needles

Setting Time

Type I Type II Type III Type IV Type V 0 100 200 300 400 Initial Final

Time of Set (Minutes) - Vicat Method

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False Set and Flash Set

Early Stiffening False Set Loss of plasticity shortly after mixing little heat Due to hemihydrate (plaster) in cement hydrating to gypsum Workability restored by additional mixing

False Set and Flash Set

Early Stiffening False Set Loss of plasticity shortly after mixing little heat Due to hemihydrate (Plaster) in cement hydrating to Gypsum Workability restored by additional mixing

Flash Set

Rapid & early loss of workability significant heat Due to rapid reaction of aluminates when insufficient sulfate present Workability cannot be restored

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Compressive Strength

ASTM C 109 Standard Test Method for Compressive Strength of Hydraulic Cement Mortars. 50-mm (2-inch) mortar cubes Sand:Cement = 2.75:1 Water/Cement = 0.485 for portland cement (0.460 for air-entraining portland cement) Sufficient water for flow 110 5 for blended (ASTM C 595) and hydraulic (ASTM C 1157) cements

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Compressive Strength
ASTM C 150 Standard Specification for Portland Cement
Minimum Strength Requirements, MPa (psi) Age I 1 day 3 days 7 days 28 days 12.0 (1740) 19.0 (2760) II 10.0 (1450) 17.0 (2470) Cement Type III 12.0 (1740) 24.0 (3480) IV 7.0 (1020) 17.0 (2470) V 8.0 (1160) 15.0 (2180) 21.0 (3050)

Lower strengths permitted for air-entraining cements (Types IA, IIA & IIIA) and when heat of hydration option is specified for Type II cement

Compressive Strength
ASTM C 595 Standard Specification for Blended Hydraulic Cements
Minimum Strength Requirements, MPa (psi) Age I(SM), IS, I(PM), IP 3 days 7 days 28 days 13.0 (1890) 20.0 (2900) 25.0 (362) Cement Type IS(MS), IP(MS) 11.0 (1600) 18.0 (2610) 25.0 (3620) S 5.0 (720) 11.0 (1600) P 11.0 (1600) 21.0 (3140)

Lower strengths permitted for air-entraining cements (with suffix A)

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Compressive Strength
ASTM C 1157 Standard Specification for Hydraulic Cement
Minimum Strength Requirements (MPa) Age GU 1 day 3 days 7 days 28 days 10 17 HE 10 17 Cement Type MS 10 17 HS 5 10 17 MH 5 10 LH 5 17

Compressive Strength
ASTM C 1157 Standard Specification for Hydraulic Cement
Minimum Strength Requirements (MPa) Strength Range Minimum Strength, MPa (psi) Maximum Strength, MPa (psi) 5 5 (725) 15 (2175) 10 10 (1450) 20 (2900) 17 17 (2465) 30 (4350) 25 25 (3625) 40 (5800) 35 35 (5075) 60 (8700) 45 45 (6525) -

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Heat of Hydration

Heat evolution in portland cement tested by conduction calorimetry

Heat of Hydration
Heat of Solution Test
ASTM C 186 Standard Test Method for Heat of Hydration of Portland Cement

Conduction Calorimetry

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Heat of Hydration
Moderate Heat of Hydration ASTM C 150 Portland Cement Type II (Option) 290 kJ/kg at 7 days Low Heat of Hydration Type IV 250 kJ/kg at 7 days 290 kJ/kg at 28 days

Heat of Hydration
Moderate Heat of Hydration ASTM C 150 Portland Cement Type II (Option) 290 kJ/kg at 7 days Low Heat of Hydration Type IV 250 kJ/kg at 7 days 290 kJ/kg at 28 days ASTM C 595 Blended Cement Suffix -MH 290 kJ/kg at 7 days 330 kJ/kg at 28 days Suffix -LH 250 kJ/kg at 7 days 290 kJ/kg at 28 days

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Heat of Hydration
Moderate Heat of Hydration ASTM C 150 Portland Cement Type II (Option) 290 kJ/kg at 7 days Low Heat of Hydration Type IV 250 kJ/kg at 7 days 290 kJ/kg at 28 days ASTM C 595 Blended Cement Suffix -MH 290 kJ/kg at 7 days 330 kJ/kg at 28 days ASTM C 1157 Hydraulic Cement Type MH 290 kJ/kg at 7 days Suffix -LH 250 kJ/kg at 7 days 290 kJ/kg at 28 days Type LH 250 kJ/kg at 7 days 290 kJ/kg at 28 days

Loss on Ignition
ASTM C 114 Standard Test Methods for Chemical Analysis of Hydraulic Cement Loss on ignition LOI Sample ignited at 900 to 1000C (1650 to 1830F) High LOI indicates prehydration and/or carbonation Improper or prolonged storage (transportation)

ASTM C 150 Portland Cement ASTM C 595 Blended Cement ASTM C 1157 Hydraulic Cement

LOI 3.0% (2.5% for Type IV) LOI 3.0 5.0% No limit must be reported

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Density
Le Chatelier flask - ASTM C 188 Standard Test Method for Density of Hydraulic Cement Range= 3100 to 3250 kg/m3 Average = 3150 kg/m3 (196 lb/ft3) Not indicator of quality Used for mixture proportioning calculations

Relative density (specific gravity) = 3.15

Helium pycnometer

Bulk Density

Bulk density of cement varies between 830 kg/m3 (52 lb/ft3) and 1650 kg/m3 (103 lb/ft3).

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Sulfate Expansion
ASTM C 452 Standard Test Method for Potential Expansion of Portland-Cement Mortars Exposed to Sulfate Gypsum added to cement to yield 7.0% SO3 (by mass of cement + gypsum) Mortar bars stored in water Length change monitored periodically Only applicable to portland cements

ASTM C 150 Portland Cement

Optional requirement for Type V Sulfate-Resisting Portland Cement Expansion 0.040% at 14 days Limits for C3A, C4AF + 2C3A, SiO2 & Fe2O3 not required

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