Cement, Slag, Pozzolan, & Silica Fume

Concrete Materials
Cementitious Cement Other Supplementary Cementitious Materials (SCMs)
Pozzolan (Fly Ashes) Slag Silica Fume These SCMs are commonly referred to as Mineral Admixtures

Aggregates Coarse and Fine (Rock & Sand) Chemical Admixtures Water Reducers, Retarders, Accelerators, Air Entrainment, and etc.

Learning Objectives
Develop a basic understanding of: Portland cement Pozzolans (Fly Ash) Ground granulated blast furnace slag

History of Cement
The Greeks and Romans used calcined limestone and later learned to add to the lime and water, - sand and crushed stone or brick and broken tiles.
This was the first concrete in History.
Ref. Properties of Concrete A.M.Neville

Pantheon, Rome A.D. 117 - 125

Early Cement Works

Joseph Aspdin 1824

Leas Chemistry of Cement

Aspdins early cement was nothing more than a hydraulic lime, but in 1824 his patent gave him the use of the term Portland cement

Beehive Kiln
Beehive Kiln 1847-1850
William Aspdin

I.C Johnson 1851

Discovered that clinker or overburnt material substantially increased strength of cement

Leas Chemistry of Cement

Vertical shaft kilns

Riverside California Mexican setters burned limestone to make lime early 19th century

The Rotary Cement Kiln by Kurt Peray

1st. Portland cement, as is known today , in the US was produced by David Saylor at Coplay, PA - 1871, in vertical kilns

Rotary Kiln

1885 England
Frederick Ransome patented rotary kiln
(18 inch X 15 ft)

1900
Thomas Edison takes advantage of the horizontal rotary kiln Cement manufacture changed from a batch process to a continuous process

Portland Cements

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Typical Cement Plant

Four Principle Oxides

Major Components

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Calcium oxide 64% CaO "Lime" C Silicon oxide 22% SiO2 "Silica" S Aluminium oxide 6% Al2O3 "Alumina" A F Iron oxide 3% Fe2O3 "Iron"

Minor components
Na2O, K2O "Alkali" SO3 MgO TiO2 "Sulphur" "Magnesium" "Titanium"

Two Major Raw Materials Components in Hydraulic Cement

Calcareous Component
(providing CaO) limestone marly limestone chalk (generally easy to grind) coral limestone marble lime-sand shell deposits etc

Argillaceous Component
(providing SiO2 Al2O3 & Fe2O3) clay shale calcareous marl marl marly clay tuff, ash phyllite. Slate etc.

Calcium oxide

Silicon oxide

Raw Material Mining & Processing

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Raw Material Proportioning & Blending

Raw Material Proportioning Dust Collector
To Preheater or Kiln

Limestone

Shale

Iron Ore

Sand

Grinding Mill
Blending and Storage Silos Raw Meal Pump

After analysis, the raw materials are proportioned, ground to fine powder, and blended. Some cement plants add water to the material during grinding, then blend and store it as a slurry.

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Two types of Cement Kilns

Wet Process Kiln Mix is a Slurry
(30% - 40% water)

Dry Process Kiln Mix is a Dry Powder

Advantages preheating done outside the kiln cost efficiency shorter kiln length Disadvantage alkalies, sulfur, chlorides tall, sophisticated

Advantages more uniform raw material may already contain moisture Disadvantage higher operating cost

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CPU 301 October 10 -12, 2007

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CPU 301 October 10 -12, 2007

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Low red -- dark read bright red -- orange orange -- yellow light yellow - white

875-1200 F 1500-1650 F 1650-2000 F 2400-2800 F

Voila Clinker!!
C2S (belite) C3S (alite)
Most important clinker constituent that governs strength

C3 A C4AF

Significance of Clinker Minerals for Cement Properties

C3S C2S C3A Alite...Contributes to early and late strength (1-3-5 day - ...)
Increases heat of hydration

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Belite... Contributes to late strength (28 day + ...)

Contributes to very early strength (1 - 3 day) Increases heat of hydration Impairs resistance to sulfate attack

C4AF Little effect (mostly color). (Higher C A, lower C AFgenerally more

3 4

reactive)

Grinding Clinker & Gypsum

Clinker Gypsum Dust Collector

Storage Silos

Kiln

Clinker Cooler

Grinding Cement Mill

Pump

Bulk Loading

Bagging Facility

TurningClinkerintoCement
Clinker Gypsum Dust Collector

Storage Silos

Kiln

Clinker Cooler

Grinding Cement Mill

Pump

Bulk Loading

Bagging Facility

Sulfate for Set Control

Gypsum, or naturally occurring anhydrite Reacts with aluminate phases Dramatically slows down C3A reactions Speeds up very high iron aluminate reactions Proper balance needed for good performance
Slump loss Fast set Slow set Slow strength Gain

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Finish Mill

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CPU 301 October 10 -12, 2007

THE RECIPE

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CPU 301 October 10 -12, 2007

Significance of Clinker Minerals for ASTM Cement Types

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Type I - No restrictions regarding clinker minerals Type II - Moderate sulphate resistance

C3A max. 8 %

Type III - High early strength

C3A max. 15 %

Type IV - Low heat of hydration

C3S max. 35 % (alite) C2S min 40% (belite) C3A max. 7 %

Type V - High sulphate resistance

C3A max. 5.0 % C4AF + 2 C3A max. 25 % or C4AF + C2F max. 25 %

MATERIAL CERTIFICATION REPORT

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Bingamon and Sorcic

Typical
Holcim cement meets ASTM C1157 Specification for Type GU and ASTM C150 Specification for Type I cement. While permitted additions may res ult in differing compound calculations, the physical properties of the cement are virtually unchanged.

Material: Portland Cement, Hydraulic Cement Type: I (ASTM C-150), GU (ASTM C-1157) Test Period: Certification General Information

Supplier: Holcim Inc. Source Location: Holcim - Midlothian Texas Plant Address: 1800 Dove Lane Midlothian, TX 76065 - 4435 Telephone: 800-326-1821 Contact: Dobber Bingamon The following information is based on average test data during the test period. The data is typical of cement shipped by Holcim; individual shipments may vary.

Tests Data on ASTM "Standard" Requirements

Chemical
Item SiO2 Al2O3 Fe 2O3 CaO MgO SO3 Ignition Loss Insoluble Residue

ASTM C1157 (Table 1) and ASTM C150 (Tables 1 & 3) Limit Physical
C1157 NA NA NA NA NA NA NA NA C150 NA NA NA NA 6.0 max 3.5 max 3.0 max 0.75 max Result (%) 20.50 5.40 2.4 64.70 0.8 3.30 1.30 0.16 Item Air Content (%) Blaine Fineness (m / kg) Autoclave Expansion % - 325M Seive Comp. Strength 3 Day MPa (psi) Min 7 Day MPa (psi) Min
2

Limit
C1157 NA NA 0.80 max NA C150 12 max 280 min 0.80 max NA Result 8 356.0 0.05 94.0 MPa (psi) 25.4 3,680 32.7 4,740

10.0 (1450) 12.0 (1740) 17.0 (2466) 19.0 (2760)

Potential Compounds C3S C2S C3A C4AF

NA NA NA NA

NA NA NA NA

58.5 14.7 10.25 7.3

Initial Vicat (minutes) Final Vicat Initial Gillmore (Alternative) Final Gillmore (Alternative) Mortar Bar Expansion max%

45-420 max 45-375 max 60 min 600 max -

0.020 max

95 187 121 215 0

Tests Data on ASTM "Optional" Requirements

Chemical
Item

ASTM C1157 (Table 1) and ASTM C150 (Tables 2 & 4) Limit Physical
C1157 C150 Result (%) Item C1157

Limit
C150 Result

Notes
List of Constituents: Portland Cement REPRESENTATIVE OF MIDLOTHIAN PLANT Source: HOLCIM
Typical

Supplementary Cementitious Materials (SCMs)

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From left to right: Fly ash (Class C) Metakaolin (calcined clay) Silica fume Fly ash (Class F) Slag Calcined shale

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Slag Cement (GGBFS)

ASTM C 989 Standard Specification for Ground Granulated Blast-Furnace Slag for Use in Concrete (classified by Strength Activity Index compared to a reference Portland Cement) Grade 80 (SAI @ 28days = 75%) Grade 100 (SAI @ 7days = 75% & 28days = 95%) Grade 120 (SAI @ 7days = 95% & 28days = 115%)

GGBFS is a hydraulic cement

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Blast Furnace Slag (BFS)

Iron ore, coke and limestone
added to the top

Blast furnace

+/-3000 oF

Molten slag and iron

flow from the bottom

Molten Blast Furnace Iron & Slag

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Granulated Blast-Furnace Slag (GBFS)

Molten slag is quenched with a large quantity of water, about a 10:1 ratio Shock of the water vitrifies the slag into a glassy sand like material Slag

Water

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US Steel, Fairfield, AL
GRANULATION TANK STACK

DEWATERING PLANT

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Dewatering Drum

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Dewatering Plant

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Birmingham, AL Slag Grinding Plant

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Ground Granulated Blast-Furnace Slag

Ball Mill

Slag Cement

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Slag - Features and Benefits

Benefits for Hardened Concrete
Higher late term strength (14-> day strength) Increased flexural strength Lighter, brighter color (substitute for white cement) Increased ability to reflect solar heat Reduced permeability and increased durabilit Increased resistance to alkali silica reaction
25% to 70%

Increased sulfate resistance with low alumina slag

40% to 70%

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Slag - Cautions
As cement replacement rates increase, freeze/thaw durability can be reduced (on flat work) Sensitive to cold weather, below 40 0 F (set time and early strength) As levels of unoxidized sulfide sulfur increase, a temporary greening of the hardened concrete may occur

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Pozzolans

ASTM Standard Definition

pozzolan, n., a siliceous or siliceous and aluminous material which in itself possesses little or no cementitious value but which will, in finely divided form and in the presence of moisture, chemically react with calcium hydroxide to form compounds possessing cementitious properties

Fly Ash (a pozzolan)

A by-product produced at coal-fired electric generating power plants Residue (or ash) from the combustion of ground or powdered coalin other words coal ash

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Process Schematic

T= 1800o - 2400oF Coal + Air Coal + Air

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Fly Ash Flow Process

Coal/Sourc e
Coal Pulverizer

Boiler

Electrostatic Precipitation

Fly Ash Silo

Customers

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Coal Flyash
Flyash: A finely divided residue that results as a product from the combustion
of pulverized coal in electric generating power plants. Class C Flyash: Most often comes from the burning of sub-bituminous coal and generally has a calcium oxide content above 20%. Class F Flyash: Most often comes from the burning of bituminous coal and generally has a calcium oxide content of less than 10%.

Class C

Class F

Bituminous coal (F) Subbituminous coal (C )

Older coals - eastern - North America and on the west coast Younger coals - western - North America

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ASTM C 618 (AASHTO M 295) Specification

Classes Class FFly ash with pozzolanic properties Class CFly ash with pozzolanic and cementitious properties

Fly Ash

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Fly Ash
Class C
C ash is cementitious and pozzolanic Class C ash contains higher CaO contents
(8% - 40%)

High lime content, light color

Due lower carbon and iron contents

ASTM C 618
Medium High CaO ( 18 40+% )

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Fly Ash Class F

F ash is pozzolanic Class F ash contains low CaO content
( 1-15% )

Low lime content, dark color

Due to presence of unburned carbon

ASTM C 618
Low CaO ( 2-15% )

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Fly Ash - How does it work?

Fly ash reacts with the cementitious free lime during the cement hydration process to enhance the density of crystal growth and realize concrete strength gain.

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Reactions
Primary cement reaction (fast): C3S (and C2S) + water By product from hydration Pozzolanic reaction (slow): Fly Ash + Calcium Hydroxide = C-S-H gel = = C-S-H gel Calcium Hydroxide

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Fly Ash - Features and Benefits

Significant strength gain at later ages
Slower with Class F compared to Class C

Improved concrete mix workability Reduced permability Increased resistance to alkali-silica reactivity & sulfate conditions with Class F Reduced heat of hydration
Primarily Class F more so than Class C

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Fly Ash - Cautions

Fly ash can affect air entrainment dosages Increase initial set time Lower early strengths

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Other Considerations
Must accommodate specific gravity difference when batching with fly ash and slag
specific gravity of fly ash = 2.2 - 2.8 specific gravity of ggbfs = 2.6 - 2.9 specific gravity of Portland cement = 3.15

Must adequately cure concrete when slow hydration occurs

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Fly Ash - Potential Uses

Primary Applications Concrete Concrete Products

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Silica Fume
(microsilica): pure, amorphous silica with particle size of 0.1-0.2 m, collected during the manufacture of silicon and ferrosilicon alloys

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Specification for Silica Fume

ASTM C 1240
finely divided residue resulting from the production of silicon, ferro-silicon, or other silicon-containing alloys that is carried from the burning surface area of an electric-arc furnace by exhaust gases.

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Silica Fume Basics

Typical amounts used in concrete 5% to 10%
In concrete pipe about 8%

Adds to strength gain Reduces permeability Reduces Alkali Silica Reactivity

Typical Chemistries Comparison

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Portland Slag Class F Class C Silica Chemistry Cement Cement Fly Ash Fly Ash Fume CaO 65 38 5 23 1.6 5 0.5 19 20 0.4 Fe2O3 Al2O3 SiO2 SO3 3 20 2.6 10 36 2.1 17 50 0.3 5 37 1.6 0.4 90 0.4

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Conclusions
Portland cement is a complex material that is manufactured from natural materials Pozzolans and Slags are by-products of manufacturing processes The use of SCMs can benefit concrete by improving the desired engineering properties

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Questions?