COMPOSITE CEMENTS

Use of Supplementary Cementations Material (SCM) + Limestone

-RBSJakarta, 27 Juni 2013

Introduction & History

Composite/Blended cement is an old component of concrete mixtures. Pozzolanic cement was standardised in Italy in 1929. Blast-furnace slag cements were produced in Germany, France, Luxembourg and Belgium for more than a century. Cements containing fly ash appeared in France in 1950. However, the importance of mineral additions has notoriously rose in the last decades due to cement industry requirements, as well as the need of longer service life for concrete structures. The use of mineral additions in cement production implies a reduction in consumption of fossil fuel, mineral natural resources and the gas emissions that contribute to the green-house effect.

Consequently, partial replacement of Portland clinker is a feasible solution from an economic, ecological and technical point of view.
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Technical Descriptions
Cement mixtures containing ordinary portland cement (OPC) and at least one Supplementary Cementitious Material (SCM) are called blended cements. Binary cements contain OPC and one SCM, e.g. blended cements containing 85% OPC and 15% Class C fly ash. Ternary cements contain OPC and two SCMs, e.g. blended cements containing OPC, 15% Class C fly ash and and 20%, 25%, or 35% slag.

Potential Benefits of Blended Cements

Support sustainable cement development policy. Improved concrete workability. Lower risk of thermal cracking. Improved concrete durability and long-term strength. Reduced overall concrete cost.

Range of Applications
Composite cements for general applications (clinker replacement 10-30%)
Special concrete applications Mass construction Hydraulic construction Industrial construction (Chemical attack, heat attack) (Ultra) high performance concrete (example: M2C Obourg Origny using 80% slag) Self Compacting Concrete Special binders Road binders Soil stabilisation Sealing walls Etc.

Supplementary Cementitious Material (SCM)

Most common and widely used is Fly Ash
Ready-to-use product Clinker replacement around 20% (max. 55% EN 197-1)

Slags produced in blast furnaces, steel converters, nonferrous industries, or municipal waste incinerators.
Milling/granulation is generally required Once milling plant installed easy to produce composite cement Clinker replacement around 35% (max. 95% En 197-1

Rice Husk Ash (RHA) Pozzolans

Natural (volcanic ashes, sediments, etc.) By-product/waste (burned clays, dusts e.g. Cement Kiln Dust, silica fume)
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Global Fly Ash & Slag Production (in million ton/year)

Global volumes: FA+S in Cement : 603 mio t/y FA+S in Aggregates: 257 mio t/y Cement Production : 1500 mio t/y Granulated Blast Furnace Slag 113 Seaborne Slag Trading

(6)
72 Non-granulated Blast Furnace Slag Steel Slag

Fly Ash

490
120

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Bottom Ash

Introduction of SCM in cement industry

Natural SCM e.g. Pozzolans, CKD
SCM Sourcing SCM Cements SCM Direct Supply

Fly Ash Raw material from quarry Clinker production Cement mill Concrete producers

Granulated blast furnace slag (GBFS)

Air-cooled blast furnace slag (ACBFS) Slag mill
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Characteristics
Blended cements either blended or interground at cement plants are generally more uniform and produce better results than blended concrete mixtures combined at the concrete mixer. Concrete performance varies with the source and proportion of cementitious materials used.
Fly ash can function as a water-reducing agent in cement mixtures. As a result, ternary cement concrete can achieve the same flowability as OPC concrete. Fly ash replacement in binary cements generally increases paste/concrete set time when compared with OPC concrete. Slag replacement in ternary cements can either increase or decrease the set time, depending on the type of clinker used when compared with binary cement concrete.
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Initial Set Times

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Effect of SCM on Strength

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Pozzolanic Materials

Criteria of Using Pozzolanic Materials

1. Quarry information Geographic location Legal situation Geologic history and set-up Exact sampling location
2. Moisture

Between 2% and 5%

3. Mineralogical composition Low degree of rock heterogeneity Small particle sizes (< 150 mm) High porosity (> 20%) High amount of vitreous phases Low amount of minerals (except zeolites) No clays and xenoclasts 4. Chemical composition High sum of SiO2+Al2O3+Fe2O3 (> 70%) High amount of reactive SiO2 (> 25%) Low LOI (< 10%) Low amount of SO3 (< 1%) Low amount of Cl (< 0.1%)

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Testing the Reactivity of Pozzolans (According to EN 196-5)

Materials with pozzolanic properties contain glassy silica and alumina that will, in the presence of water and free lime, react with the calcium in the lime to produce calcium silicate hydrates (cementitious compounds).

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Metallurgical Slag

Metallurgical Slags
Metallurgical slags are disposed as waste from the ferromanganese and ferro-manganesesilicon alloys manufacturing plants and in the smelting of non-ferrous metals such as lead, zinc and copper. The slags are found in two types, i.e. granulated and air-cooled (lumpy). They find little use unlike blast furnace slags from steel plant, although in Canada, some steel alloy slags are being used as an additive in cement raw materials

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Characterisation of raw materials

It can be chemically classified as the high MnO slag contains 33% MnO and the low MnO slag has 15% MnO. The specific gravity: 3.20 g/cm3 , whereas there was a variation in the bulk density, with low MnO slag having 1.73 g/cm3 and high MnO slag having 2.05 g/cm3. High silica (39%) in the low MnO slag indicates the possibility of a partial replacement for cement.

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Physical Properties and Compressive Strength

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FLY ASH

490 million ton produced in 2002 worldwide

Fly Ash
Fly ash is defined in Cement and Concrete Terminology (ACI Committee 116) as "the finely divided residue resulting from the combustion of ground or powdered coal, which is transported from the firebox through the boiler by flue gases." Fly Ash primarily contains a silico-alumino material capable of reacting with calcium hydroxide at room temperature to form compounds having cementitious properties Fly ash is commonly known as a by-product of coal-fired power plants. The characteristics of a fly ash depend on the nature of the coal used and the type of operating furnace Fly ash to be used in blended cement must meet the requirements of ASTM C618

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ASTM standard for blended cement

ASTM has introduces performance standard for blended cement, C 1157. ASTM C595(1) defines two blended cement products in which fly ash has been added: 1) Portland-pozzolan cement (Type IP), containing 15 to 40 % pozzolan or 2) Pozzolan modified Portland cement (Type I-PM) containing less than 15 % pozzolan.

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Global Fly Ash Production (in million ton/year)

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Fly ash classification according ASTM C 618

Class F, referred to low-calcium fly ash, usually produced by burning anthracite or bituminous coal. Class C, usually produced by burning sub-bituminous coal or lignite. Both types of fly ash are pozzolanic and contain a substantial amorphous phase. The difference between Class F and Class C fly ash is the amount of calcium and the silica, alumina, and iron content. In Class F fly ash, total calcium typically ranges from 1 to 12 %, mostly in the form of calcium hydroxide, calcium sulfate, and glassy components in combination with silica and alumina. In contrast, Class C fly ash may have calcium oxide contents as high as 30 to 40%. Another difference between Class F and Class C is that the amount of alkalis (combined sodium and potassium) and sulfates (SO4) are generally higher in the Class C fly ashes than in the Class F fly ashes. It is important to stress that not all fly ashes are able to meet ASTM C618 requirements and that could be acceptable for applications other than concrete. The American Concrete Institute (ACI) recommends that Class F fly ash replace from 15 to 25 % of the Portland cement and Class C fly ash replace from 20 to 35 %
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Quality of fly ash according to JIS-A 6201

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Physical Properties of Fly Ash

Fly ash consists of fine, powdery particles that are predominantly spherical in shape, either solid or hollow, and mostly glassy (amorphous) in nature. The specific gravity of fly ash usually ranges from 2.1 to 3.0, while its specific surface area (measured by the Blaine air permeability method) may range from 170 to 1000 m2/kg. The carbonaceous material in fly ash is composed of angular particles. The particle size distribution of most bituminous coal fly ashes is generally less than a 0.075 mm or No. 200 sieve.

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Physical Properties of Fly Ash (contd)

The color of fly ash can vary from tan to gray to black, depending on the amount of unburned carbon in the ash. The lighter the color, the lower the carbon content. Lignite or subbituminous fly ashes are usually light in color, indicating relatively low amounts of carbon as well as the presence of some lime or calcium. Bituminous fly ashes are usually some shade of gray, with the lighter shades of gray generally indicating a higher quality of ash. Subbituminous coal fly ashes are are generally slightly coarser than bituminous coal fly ashes.

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Chemical composition of fly ash of different coal types (% w/w)

Component FA Bituminous FA Subbituminous FA Lignite

SiO2
Al2O3 Fe2O3 CaO MgO SO3 Na2O

20-60
5-35 10-40 1-12 0-5 0-4 0-4

40-60
20-30 4-10 5-30 1-6 0-2 0-2

15-45
10-25 4-15 15-40 3-10 0-10 0-6

K2O
LOI

0-3
0-15

0-4
0-3

0-4
0-5
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Fly Ash Fineness

Fineness is the primary physical characteristic of fly ash that relates to pozzolanic activity. As the fineness increases, the pozzolanic activity can be expected to increase. Current specifications include a requirement for the maximum allowable percentage retained on a 0.045 mm (No. 325) sieve when wet sieved. ASTM C618 specifies a maximum of 34 % retained on a 0.045 mm (No. 325) sieve. Fineness can also be assessed by methods that estimate specific surface area, such as the Blaine air permeability test commonly used for Portland cement.
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Fly ash Treatment

Fly ash must be in a dry form when used as a mineral admixture. Fly ash quality must be closely monitored when the material is used in blended cement. Fineness, loss on ignition, and chemical content are the most important characteristics of fly ash affecting its use in concrete. Fly ash must also have sufficient pozzolanic reactivity and must be of consistent quality.

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Fly Ash Storage

Fly ash is typically stored dry in silos, from which it can be used or disposed of in a dry or wet form. Water can be added to the fly ash to allow for stockpiling or landfilling in a conditioned form (approximately 15 to 30 % moisture), or for disposal by sluicing into settling ponds or lagoons in a wet form. Approximately 75 % of the fly ash produced is handled in a dry or moisture-conditioned form, making it much easier to recover and use. The main advantage to the conditioning of fly ash is the reduction of blowing or dusting during truck transport and outdoor storage.

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Fly Ash Quality Control

Fly ash used in concrete should be as consistent and uniform as possible. Fly ash to be used in concrete should be monitored by a quality assurance/quality control (QA/QC) program that complies with the recommended procedures in ASTM C311. These procedures establish standards for methods of sampling and frequency of performing tests for fineness, loss on ignition (LOI), specific gravity, and pozzolanic activity such that the consistency of a fly ash source can be certified. ASTM C618 specifies a maximum allowable moisture content of 3.0 %. Due to concern of air-entraiment, many users specify a maximum LOI value that does not exceed 3 or 4 percent, even though the ASTM criteria is a maximum LOI content of 6 %.

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Quality-compromised fly ash

To Ensure the quality of fly ash being used, the following sources of fly ash should be avoided:
Ash from a reserve powerplant. Ash from plants burning different coals or blends of coal. Ash from plants burning other fuels (wood chips, tires, trash) blended with coal. Ash from plants using oil as a supplementary fuel. Ash from plants using precipitator additives, such as ammonia. Ash from start-up or shut-down phases of operation. Ash from plants not operating at a "steady state." Ash that is handled and stored using a wet system.

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TRASS

Mineral Composition & Oxides

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Mineral Composition & Oxides

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Effect on Strength (case study)

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LIMESTONE

Introduction & History

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Grinding of Limestone Cement

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Effect of Limestone

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Effect of Limestone

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Effect of Limestone

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Effect of Limestone

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Effect of Limestone

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Effect of Limestone

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THANK YOU

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