Green Concrete

Evolutionary Cement
An evaluation and suggestion for a sustainable concrete industry

John Anderson CEE, UC Berkeley

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Overview of Green Concrete

Environmental aspects of concrete CO2 in Ordinary Portland Cement Alternative binders Alkali activated cements Calcium sulfoaluminate cements Other alternatives Challenges and opportunities for green cement

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Environmental aspects

CO2 emissions Water use Raw material extraction Responsibility of engineers

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CO2 in Ordinary Portland cement

~50% from the calcination of limestone CaCO3 CaO + CO2 (3CaCO3 + SiO2 Ca3SiO5 + 3CO2)

~40% from fossil fuels to heat kiln (1450 C) alternative fuels- Cement Sustainability Initiative (tires, plastic insulation, paper)

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Alternative binders (1)

Cement compound M (magnesia, periclase) C (calcia, quicklime) C3S (alite) -C3S (belite) C3A (tricalcium aluminate) Raw material used Magnesite Limestone Limestone + silica Limestone + silica Limestone + alumina Quantity of RMCO2* generated (g/g) 1.092 0.785 0.578 0.511 0.489

C4AF (calcium aluminoferrite)

NS (sodium metasilicate) CA (monocalcium aluminate) C4A3S (calcium sulfoaluminate)

As above + iron oxide

Soda + silica Limestone + alumina As above + anhydrite

0.362
0.361 0.279 0.216

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* RMCO2- raw material CO2 FDCO2- fuel derived CO2

Alternative binders (2)

Alkali activated cements Calcium sulfo-aluminate cements

Other options
(calcium sulfate, magnesia, and blended OPC cements)

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Alkali activated cements

Alumino-silicate bonding phase
(alumina rich source material and an alkali silicate solution)

Termed geocements, aluminate cements Source materials can be either pozzolanic or non-pozzolanic
Fly ash, blast furnace slag, metakaolin

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Alkali activated cements

Environmental +
Waste as source material (fly ash, blast furnace slag) Low RMCO2 (except metakaolin)

Environmental High RDCO2 and FDCO2 for alkali activator

Elevated curing temps

Alkali runoff Limited source materials

Low FDCO2 (except metakaolin)

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Alkali activated cements

Fly ash alkali activated
Curing (> 30 C) Activator (10% by mass)

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Alkali activated cements

Fly ash alkali activated
Strength development
7 days

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28 days

Alkali activated cements

Fly ash alkali activated
Compressive strength (MPa)
Activator Curing temperature ( C) Activator/fly ash ratio 0.25 (time of curing) 2h Solution 1 65 85 0.0 9.3 5h 0.0 22.0 24 h 21.2 34.6

Solution 2

65 85

0.0 1.4

0.0 9.4

8.7 23.3

Solution 3

65

4.3

31.7

52.7

85

39.8

48.2

54.5

Solution 4
NaOH 12 M (solution 1), KOH 18 M (solution 2), NaOH + sodium silicate (solution 3), and KOH + potassium silicate (solution 4).

65
85

0.0
7.7

9.5
34.3

38.7
63.0

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Alkali activated cements

Slag alkali activated
Similar advantageous as fly ash Influencing factors
Activator, curing temp, specific surface

Metakaolin alkali activated

Human-made
Thermal decomposition of kaolin

Production decreasing Rapid setting time and high shrinkage

High costs Significant RMCO2 and FDCO2

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Calcium sulfoaluminate cements

Known as sulfoaluminate, ettringite, or belitesulfoaluminate cements High alumina, low energy, high early strength, rapid setting, long-term durability Source material
Limestone, bauxite or alumina clays, and gypsum

Clinker result of calcinated source materials Hydration products

Early strength: ettringite, long-term strength: C-S-H

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Calcium sulfoaluminate cements

Environmental appeal
No elevated curing temperature
Use outside of precast

Reduced limestone used Reduced kiln temperatures (1160-1200 C) Lower grinding energy Gypsum not fired in kiln High sulfur industrial byproducts
Slag, flue gas desulfurisation sludge, low calcium FA

No alkali solution/ alkali runoff

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Calcium sulfoaluminate cements

Strength
Higher long-term strength than OPC Cured at room temp (20C), compression strength of ~80MPa
SAC-calcium sulfoaluminate cement, FAC-ferroaluminate cement, PC-portland cement

CAC-calcium aluminate cement

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Additional alternative binders

Calcium sulfate-based cements
Gypsum based mortars
Hydration of calcium sulfate hemihydrate

Zero RMCO2, low FDCO2 Natural and byproduct source material Durability weakness of gypsum
Use dense gypsum (alabaster) or additives (calcium aluminates)

No corrosion protection
Use fibers

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Additional alternative binders

Magnesia cements
Binding phase- magnesium oxide Family
Sorel, magnesium oxysulfates, magnesia phosphate, magnesia carbonate

CO2 sink Recycling

Calcinate at 1000C, high RMCO2 Possible water durability issues $, unproven properties

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Additional alternative binders

Blended OPC
OPC plus replacement (pozzolan) material
Fly ash, slag, rice husk ash

Initiated by lime Low heat of hydration, improved workability 90% of market needs < 3,000 (20 MPa) 80% of SCMs go to landfill, low-value applc.

Low early strengths Characterization of source material Coal not sustainable product

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Future of green cement

Opportunities
Market system for CO2 PC faces mechanical challenges Low strength/ low risk applications

Challenges
OPC well established Conservative nature of construction/design industry More research

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