Specialty Cements

Dr. Kimberly Kurtis

School of Civil Engineering Georgia Institute of Technology Atlanta, Georgia

Specialty Cements
Portland cements do not always meet every need of the construction industry. Other specialty cements have been developed to meet these needs. Generally much smaller production, limited availability, and increased cost. modified portland cements some particular component has been added to portland cement to provide the desired quality In these cements, the calcium silicates continue to provide the strength, but changes are made to the aluminate and ferrite phases non-portland cements Do not rely on the calcium silicates for strength, but on the hydration of other phases

Todays Cements
Wide range of portland, blended & other hydraulic cements available

Sulfate-resisting cements Low-heat cements Rapid strength gain cements ASR resistant cements Air-entraining cements Blended cements

White or colored cements Masonry cements Mortar cements Expansive cements Rapid setting cements Rapid hardening cements Oil well cements Biogenic cements Calcium-aluminate cements

White or Colored Cements

Fe, Mg give clinker and cement gray color Can produce white cement if F<0.5% in raw materials Burn clean fuels Controlled cooling to retain Fe2+ Use ceramic ball mill

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White or Colored Cements

Fe, Mg give clinker and cement gray color Can produce white cement if F<0.5% in raw materials Add pigments to white cement to achieve desired color:
- red, yellow, brown, black - iron oxides - green - chromium oxide - blue - cobalt blue

White cements are ~3x cost of ordinary portland cement

http://www.ahi-supply.com/speccem.html

Masonry & Mortar Cements

Properties of masonry mortars: Workability Water retentivity Consistent rate of hardening Durability Compressive strength Bond Volume stability Appearance Composition of masonry mortars: Cementitious material Masonry sand Water

Masonry & Mortar Cements

Masonry cement consists of: Portland cement or blended hydraulic cement Hydrated or hydraulic lime Other materials like talc, clay, fly ash, slag, air entrainers ASTM C 91 Standard Specification for Masonry Cement Mortar cement: Similar to masonry cement Lower air content Bond strength requirement ASTM C 1329 Standard Specification for Mortar Cement

Masonry & Mortar Cements

Masonry & Mortar Cements: Type M Type S Type N Mortars: Type M Type S Type N Type O
ASTM C 270 Standard Specification for Mortar for Unit Masonry

ASTM C 91 Standard Specification for Masonry Cement ASTM C 1329 Standard Specification for Mortar Cement

Masonry & Mortar Cements

ASTM C 270 Property Specifications for Laboratory-Prepared Mortars
Mortar Type Minimum 28-day compressive strength, MPa (psi) Minimum water retention, % Maximum air content, % Masonry cement 18 18 20* 20* Mortar cement Or Cement-lime 12 12 14* 14*

M S N O

17.2 (2500) 12.4 (1800) 5.2 (750) 2.4 (350)

75 75 75 75

*2% lower if structural reinforcement is embedded in mortar

Masonry & Mortar Cements

Recommended Guide for Selection of Mortar Type
Building Segment Exterior, above grade: Load bearing Non-load bearing Parapet wall Exterior, at or below grade: Interior: Load bearing Non-load bearing Type N or S N N or S S or M N or S O or N

Masonry & Mortar Cements

ASTM C 270 Proportion Specifications
Mortar type Portland or blended cement M 1 1 S 1 N 1 Parts by volume Masonry or mortar cement type M 1 S 1 N 1 1 1 Hydrated lime or lime putty - 1 Sand

2 to 3 times the total volume of cement plus lime

Masonry & Mortar Cements

Requirements for Masonry and Mortar Cements (ASTM C 91 & C 1329) Fineness Autoclave expansion Time of setting Compressive strength Air content Water retention Bond strength

Masonry & Mortar Cements

Requirements for Mortar Cements (ASTM C 1329)
Property M Compressive strength minimum, MPa (psi) 7 days 28 days 12.4 (1800) 20.0 (2900) 9.0 (1300) 14.5 (2100) 3.4 (500) 6.2 (900) Type of Mortar Cement S N

Air content, volume % Minimum Maximum 8 15 8 15 8 17

Bond strength minimum, MPa (psi) 28 days 0.8 (115) 0.7 (100) 0.5 (70)

Expansive Cements
Ordinary portland cements expand slightly during early hydration, but the effect is far outweighed by the amount of drying shrinkage that occurs early.

Expansive Cements

Expansive Cements
Expansive cements expand during the early setting period Can be used as: Shrinkage compensating cements - induce a small (25-100psi) self-stress in restrained members to offset drying shrinkage and avoid cracking Chemically prestressing or self-stressing cements - induce a larger self-stress (500-1000psi) for prestressing precast elements

Shrinkage compensating concrete at Love Airport taxiways

Expansive Cements
Expansive cements are generally a blend of portland cement or calcium aluminate cement and some expansive component ASTM Type K - Blend of Type II or V portland cement and the calcium sulfoaluminate Kleinite (C4A3S) C4A3S + 6C + 8CS + 96H --> 3(C3A3CSH32) or 3(C6AS3H32) Amount of Kleinite depends on degree of desired expansion (850% by mass) Ettringite produced by this reaction is believed to produce the expansion - colloidal ettringite - topochemical growth Typically good sulfate resistance

Expansive Cements
ASTM Type M - Blend of portland cement, calcium aluminate cement, and calcium sulfate CA + 3CS + 2CH+ 30H --> C6AS3H32 Precast units made with solids in the ratio 66:20:14 ASTM Type S - Portland cements with high C3A content (~20%) and suitable amounts of gypsum Difficult to control setting Rapid slump loss Sulfate durability problems

Expansive Cements: Influence of Curing Conditions

Expansive Cements: Influence of Curing Conditions

It is desirable for the ettringite to form after setting, rather than in plastic concrete, to maximize expansion.

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Rapid Setting and Hardening Cements

Type III cements harden rapidly, but may not set quickly enough for some applications, such as repair.

Rapid setting and rapid hardening cements include: Calcium sulfoaluminate cements Calcium fluoroaluminate cements

fc>1000psi at 1 hour

Rapid Setting and Hardening Cements

Calcium sulfoaluminate (or very high early strength) cements Typically contain more C4A3S than Type K cement C4A3S is formed during clinkering (rather than used as an addition, added after grinding) CS is added to feedstock or during grinding Contain little C3S and much C2S Contain little C, which is believed to produce non-expansive ettringite with better strength

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Rapid Setting and Hardening Cements

Calcium fluoroaluminate or regulated-set cements C3A is replaced by C11A7CaF2 (20-25%) C11A7CaF2 can be produced in kiln or added during grinding C11A7CaF2 reacts even more vigorously than C3A Use very soluble additives, such as citric acid and/or sodium sulfate, to control reaction rate Setting can be controlled to occur 2-40 min. Initial strength due to C11A7CaF2 hydration; later strength due to C3S

Other Rapid Setting/Hardening Cements

High iron cements (HIC) Use a combination of C4A3S and C4AF to produce ettringite Finely ground cements Type III cements ground to high fineness (700-900 m2/kg) May contain chemical accelerators as well Mixtures of Type I cement and gypsum Magnesium phosphate cements Mixtures of calcium aluminate and portland cement Use of 20-80% calcium aluminate cement in a blend can produce an almost instantaneous set Early strength will be very high, but late strength will be low

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Oil Well Cements

Make up 5% of portland cement used in US Not used for structural concrete

Oil well cement slurries are used to: protect casing from damage from surrounding water give strength prevent fluid migration

Oil Well Cements

Extreme conditions exist: slurry must be flowable for hours and then set rapidly slurry may be pumped thousands of meters below the surface slurry may be exposed to high temperatures (100-250C) at the bottom of the well (up to 300C) slurry may be exposed exposed to high pressure (>20,000 psi)

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Oil Well Cements

Eight classes: Class A - general use, like Type I Class B - sulfate resistant, like Type II Class C - rapid hardening, like Type III Classes D, E, F - sulfate resistant with set modifying admixtures; Class E can be used in hotter conditions than Class D, and Class F hotter still Classes G and H - sulfate resistant with stringent thickening times; Class H is more coarsely ground Class J - withdrawn, was a C2S-based cement with silica flour (finely ground quartz) In US, Type H is most common Outside US, Type G is most common

Oil Well Cements

In addition, there are 3 grades: O - ordinary MSR - moderate sulfate resistant HSR - high sulfate resistant Class A - only grade O Class B - only MSR, HSR Class C - O, MSR, HSR Class D, E, F - only MSR, HSR Class G, H - only MSR, HSR

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Oil Well Cements

Oil Well Cements: Temperature Effects

High temperatures during oil well applications can influence slurry properties and chemistry: Many retarders and water reducers decompose at T > 150C Cement hydration, particularly of C2S and C4AF phases, is accelerated at ~70-90C Changes in C-S-H structure and strength can result >100C, C-S-H --> -C2SH (crystalline, low fc, high permeability) >200C, -C2SH --> C6S2H3 (Jaffeite, similar properties) Silica flour is added to prevent strength retrogression initially form C5S6H4 (tobermorite) >150C C5S6H4 --> C6S6H + C2S3H2 (xonotlite and gyrolite) > 250C residual tobermorite and gyrolite form truscottite > 400C truscottite and xonotlite decompose

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Biogenic Cements
Rice hull ash (RHA) is most common source of biogenic silica for cement manufacture Rice hulls are an abundant by-product in many developing countries Contain cellulose, lignin, and hemicellulose, but are also 10-20% silica by mass Rodrigues et al. have produced -C2S from biogenic silica at relatively low temperatures (650-800oC) Cements are typically doped with barium or manganese to increase reactivity.

1m

unhydrated

6% Ba2+ -C2S

Calcium Aluminate Cements

Calcium aluminate cements or high alumina cements (HAC) or ciment fondu rely on hydration of calcium aluminate phases, rather than calcium silicates. Composed of: alumina ~40% lime ~40% ferric or ferrous oxides ~15% fused silica ~5% small amounts of titanium dioxide, silica, and magnesia Common applications are for refractory brick and where sulfate resistance is needed

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Calcium Aluminate Cements

Raw materials are bauxite and limestone Composition varies (iron rich vs. iron poor) Monocalcium aluminate (CA) is principal phase

Calcium Aluminate Cements: Hydration

<10C --> CAH10 10-30C --> C2AH8 + AH3 >30C --> C3AH6 +2AH3

CA + H

no CH

In addition, xC12A7 + yH --> zC2AH8 C12A7 sets within a few minutes, but CA sets more slowly; CAC with higher C:A sets more rapidly Generally, setting time is comparable to portland cement However, strength gain is RAPID, achieving 80% ultimate fc at 24 hours 24 hour strengths for CAC are similar to 7 day strengths for PC Total heat evolved is similar to PC, but rate is 3x as fast Excellent sulfate resistance

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Calcium Aluminate Cements: Conversion

With these great properties why isnt CAC more widely used?!? CONVERSION Both of the primary hydration products are metastable at both normal and elevated temperatures. In the presence of moisture, 3CAH10 --> C3AH6 +2AH3 + 18H 3C2AH8 --> 2C3AH6 + AH3 + 9H The original hydration products have a lower density than the conversion products Thus, conversion leads to increased porosity and hence reduced strength and impermeability

Calcium Aluminate Cements: Conversion

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Calcium Aluminate Cements: Conversion

Higher temperatures, higher concentrations of lime, and greater alkalinity all promote conversion.

Calcium Aluminate Cements: Conversion

Some have suggested that post-conversion strength of CAC concrete with w/c<0.40 may be adequate for some structural applications. Current French recommendations require maximum w/c of 0.40 and minimum cement content of 400kg/m3.

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Calcium Aluminate Cements: Conversion

Small variations in w/c can significantly affect strength after conversion

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