Professional Documents
Culture Documents
Pozzolanic Materials
History and origins Greeks: Addition of naturally occurring materials from volcanic origin to hydraulic limes Romans adopted & extended Greek technology (e.g. Parthenon)
Pozzolanic Materials
Pozzolan
Pozzouli, a town in the Bay of Naples that was the source of a highly prized deposit of ash from Mt. Vesuvius The name pozzolan is now applied to any aluminosilicate materials, of either natural or industrial origin Powder: naturally occurring or to be ground to cement fineness
(Mindess et al 2003)
Rice husk ash (RHA) Palm Oil Fuel Ash (POFA) Abundant sources Much have been studied Little in actual use
WHY?
Pozzolanic Materials
Natural Pozzolans
Volcanic ask etc
By-product materials
Fly ash inorganic, non combustible residue of powdered coal after burning in power plants Silica fume a by-product in the manufacture of Silicon metal and alloys Rice husk ash siliceous residue that remains after the rice husks are burnt under controlled conditions Calcined clay under controlled temperatures (700-900 oC) to produce a highly reactive amorphous aluminosilicate (metakaolin)
Composition
Typical CEM l
20
65
(Mindess et al 2003)
Composition
Crystalline components (identified by X-ray diffraction method)
A good pozzolan should have a high fraction of reactive glassy or amorphous material Most pozzolanic materials contain various quantities of inert crystalline phases Examples
Low-calcium fly ash Class F High-calcium fly ash Class C
(Mindess et al 2003)
Class F ash: quartz, mullite, hematite, magnetite Class C ash: free CaO, anhydrite (CaSO4), C3A, C2S, etc
Composition (contd)
Minor components
Alkali oxides
in situations where pozzolanic materials are used to control AAR, alkali content of the materials should be determined
(BS EN 450-1 Na2O equivalent not to exceed 5.0% by mass) Unburnt carbon (determined by Loss on Ignition)
In SF; 1-2% In FA: 0.5-3% (sometimes as high as 25%) In RHA: 3-8% Concern for air-entrainment Color of concrete
Physical Characteristics
(Mindess et al 2003)
Note: Surface area > 1 m2/g (1000 m2/kg) Air permeability not suitable
silica fume small size packing effect reduce bleeding, reduce the size of capillary pores
(Mindess et al 2003)
fly ash
(Mindess et al 2003)
Pozzolanic Reactions
Principal reaction: amorphous silica reacts with CH from cement hydration CH + S + H C-S-H Composition of C-S-H from pozzolanic reactions
In cases of fly ashes or natural pozzolans: not very different from that formed in regular hydration, C/S is slightly lower generally In cases on silica fume or rice husk ash, C/S is significantly different from that of cement hydration, ~1.0
Kinetics of the reaction is similar to the slow rate of hydration of C2S. Thus, the addition of pozzolan has a similar effect to higher C2S content in cement
Reduce early heat evolution and early strength, but not long-term strength so long as water is available Increase the overall solid volume, reduce the porosity, increase strength and durability
Pozzolanic Reactions
The extent of a pozzolanic reaction can be followed by monitoring over time the decrease in CH derived from hydrating of CEM 1
(Mindess et al 2003)
Slow rate of pozzolanic reaction requires prolonged period of moist curing (particularly for durability of cover concrete) Pozzolanic reaction is more temperature sensitive than regular cement hydration (tropical climate beneficial)
Blended Cements - US
Note: Compare with EN 197-1 specifications
- Setting time
- Strength - Heat
- Sulfate resistance
C24
SiO2
Al2O3 Fe2O3 Na2O K 2O MgO
20(22)
5(6) 3.5(3) 0.1 0.7 0.1 3.1 3.2 300 400
38(35)
11(8) 0.3(0) 0.4 0.8 7.5 2.9-3.0 350 600
50(50) [35]#
28(25) [20]# 10.4(10) [5]# 0.7 2.5 2.0 2.3-2.6 400 - 700
92(90)
0.7(2) 1.2(2) 1.0 1.5 0.2 2.2-2.4 20,000*
Density kg/m3
Fineness m2/kg
(Data from a different source) *Approximate value by nitrogen absorption method #[High Lime pfa]
Type II Addition Supplementary Cementitious (or cementing) Materials (SCM) for Concrete ground granulated blastfurnace slag (ggbs) fly ash (includes co-combustion, pulverized fuel ash - pfa) condensed silica fume (csf) SCM added to Portland cement (CEM I) which provides calcium hydroxide needed for pozzolanic reaction Stage 1 Reaction PC (CEM I) + water ---------> CSH + CH Stage 2 - Pozzolanic (Secondary) Reaction SCM + CH + water ----------> CSH (CSH = calcium silicate hydrates, CH = calcium hydroxide)
C31
BS EN 450 : 2005 Fly ash for concrete Part 1: Definition, specifications and conformity criteria Part 2: Conformity evaluation
Fly Ash Definition Fly ash fine powder of mainly spherical, glassy particles, derived from burning of pulverised coal, with or without co-combustion materials, which has pozzolanic properties and consists essentially of SiO2 and Al2O3, the content of reactive SiO2 as defined and described in EN 197-1 being at least 25% by mass Fly ash is obtained by electrostatic or mechanical precipitation of dustlike particles from the flue gases of furnaces fired with pulverised coal, with or without co-combustion materials Fly ash may be processed, for example by classification, selection, sieving, drying, blending, grinding or carbon reduction, or by combination of these processes, in adequate production plants. Such processed fly ash may consist of fly ashes from different sources, each conforming to the definition given in this clause. If one or more incoming fly ashes are obtained from co-combustion, then the processed fly ash shall be considered as fly ash from 17 combustion
C32
Durability Requirements
Fly ash conforming to definition in 3.2, fulfilling chemical requirements in 5.2 and physical requirements in 5.3 deemed 22 to satisfy durability requirements
Fly Ash
Currently there is no fly ash being produced in Singapore, but new coal fired electricity power plant may be built in the future Currently fly ash cannot be directly import (classified as a waste) Fly ash may be preblended with CEM I as a blended cement (conforming to EN 177-1 CEM II/A, CEM ll/B ) and can then be imported Other cement types with fly ash and other supplementary cementitious materials, e.g. ggbs, limestone powder, may also be used in preblended cements (CEM IV and CEM V) and can be imported
Durability Requirements
Fly ash conforming to definition in 3.2, fulfilling chemical requirements in 5.2 and physical requirements in 5.3 deemed to satisfy durability requirements The k-value concept (EN 206-1, Subclause 5.2.5.2) permits type ll additions (fly ash and silica fume) to be taken into account by replacing water/cement ratio with water/(cement + k x addition) ratio [Note: BS 8500 (SS 544) provides alternate specific recommendations for different exposure conditions in terms of cement type, minimum cement content and maximum water-cement ratio]
Specification for Supplementary Cementitious Materials GGBS SS EN 15671 : 2008 Ground granulated blast furnace slag for use in concrete, mortar and grout Part 1: Definitions, specifications and conformity criteria Part 2: Conformity evaluation GGBS Definition
C31
Granulated blastfurnace slag vitrified material made by rapid cooling of a slag melt of suitable composition, obtained by smelting iron ore in a blastfurnace, consisting of at least two thirds by mass of glassy slag and possessing hydraulic properties when suitably activated NOTE Rapid cooling includes quenching in water (granulation) and projecting through water and air (pelletisation) Ground granulated blastfurnace slag fine powder made by grinding granulated blastfurnace slag Clause 4 Constituents The main constituent shall be granulated blastfurnace slag as defined. Its chemical composition shall consist of at least two-thirds by mass of the sum of calcium oxide (CaO), magnesium oxide (MgO) and silicon oxide (SiO2). The remainder shall be aluminium oxide (Al2O3) together with small amount of other components. The ratio 24 by mass (CaO + MgO)/(SiO2) shall exceed 1.0.
moisture content
a b
Annex A
1.0 %
Requirements are given by mass of the ground granulated blastfurnace slag Ground granulated blastfurnace slag may contain more than 0.10 % chloride but in that case the maximum chloride content, as a value not to be exceeded, shall be stated on the packages of the documents (see Clause 6)
25
Physical Requirements
Fineness (EN 196-6) Specific surface not less than 275 m2/kg Requirements when combined with test cement Initial setting time (EN 196-3) Combination (by mass) of 50% ggbs with 50% test cement shall not be more than twice as long as that of test cement on its own Activity index (EN 196-1) Ratio (in %) of compressive strength of combination (by mass) of 50% ggbs with 50% test cement to the compressive strength if test cement on its own with water : combination ratio and water : cement ratio both at 0,50 Activity index: at 7 days and at 28 days shall be not less than 45% and 70% respectively
26
Test Cement
The test cement shall conform to EN 197-1 and shall be selected by the ground granulated blastfurnace slag manufacturer, subject to the following restrictions: - CEM I, of strength class 42,5 or higher; - Blaine fineness shall be at least 300 m2/kg; - tricalcium aluminate shall be between 6% and 12%; - alkali (Na2O equivalent) content shall be between 0.5% and 1,2% (same requirements as test cement for fly ash)
Durability Requirements
GGBs conforming to SS EN 15167-1: 2008 is deemed to satisfy durability requirements, provided that other requirement for durability of concrete in relevant standards and/or regulations valid in the place of use are fulfilled. The k-value concept (EN 206-1, Subclause 5.2.5.2) covers only type ll additions (fly ash and silica fume) without any provision for GGBS in a similar manner (see SS 544-1: 2009 for guidance) 27
Evaluation of conformity
Initial type testing and factory production control shall be carried out according to relevant clauses in EN 15167-2 Conformity shall be continually evaluated on the basis of testing of spot samples for properties using test methods and minimum testing frequency for autocontrol testing by manufacturer as specified in Table 2 Statistical criterion: percentile Pk of 10% for required characteristic value or an allowable probability of acceptance CR (consumers risk) of 5% Conformity shall be verified either by variables or by attributes, as described in 8.22 and 8.2.3 and as specified in Table 2 The control period shall be 12 months for the routine situation.
Table 2 Properties, test methods and minimum testing frequencies for the autocontrol testing by the manufacturer or his agent and the statistical assessment procedure Minimum testing frequency: Routine situation and Initial period for a new GGBS Statistical assessment procedure: Inspection by Variable or by Attributes for indicated chemical and physical properties [Use of combination without producers certified conformity data may need to verify conformity by user pre-blended cement preferred]
Slag Hydration
GGBFS reacts slowly with water, strength development too slow Activation of slag by
Soluble sodium salts, NaOH, Na2CO3, NaSiO3 Ca(OH)2
The rate of hydration of activated slag is similar to that of C2S, as is the heat of hydration
Specification for Supplementary Cementitious Materials Silica Fume BS EN 13263 : 2005 Silica Fume for concrete Part 1: Definition, requirements and conformity criteria Part 2: Conformity evaluation Definitions
Silica fume (condensed silica fume, microsilica) very fine particles of amorphous silicon oxide collected as a by-product of the smelting process used to produce silicon metal and ferro-silicon alloys Silica fume slurry homogeneous, pH regulated liquid suspension of silica fume in water, typically with a dry content of 50% by mass, corresponding to about 700 kg of silica fume per m3 of slurry Densified silica fume silica fume that has been treated to increase the bulk density by particle agglomeration, the bulk density typically being above 500 kg/m3 Undensified silica fume silica fume taken directly from the collection filter, the bulk density typically being in the range 150 kg/m3 to 350 kg/m3 30
A48
Chemical Requirements
Silicon dioxide (EN 196-2) SiO2 : not less than 85% by mass Elemental silicon (ISO 9286) Si : not less than 0,4% by mass Free calcium oxide (EN 451-1) CaO : not greater than 1,0% Sulfate (EN 196-2) SO3 : not greater than 2,0% by mass Total content of alkalis (EN 196-2) Na2O equivalent : to be declared Chloride (EN 196-2) Cl : not greater than 0,3% by mass, if > 1,0% by mass, upper limit for characteristic value to be declared by manufacturer Loss on ignition (EN 196-2) by using ignition time of 1 hour, not greater than 4,0% by mass
31
Physical Requirements
Specific surface (ISO 9277) by nitrogen absorption, not less than 15,0 m2/g, (15 000 m2/kg) nor more than 35,0 m2/g (35 000 m2/kg) Dry mass content in slurry dry mass content shall not deviate from value declared by supplier by more than 2% by mass of slurry when determined by drying a representative sample of at least 5 g of slurry in a well ventilated oven at (105 5) OC to constant mass Activity index (compressive strength from mortar bars EN 196-1) ratio (in %) of compressive strength prepared with 80% test cement plus 10% silica fume per mass of total binder to that prepared with 100% test cement, when test at the same age and at least 100% when tested at a mortar age of 28 days
32
Conformity Criteria
Autocontrol testing based on testing spot samples by manufacturer for properties, test methods and minimum testing frequencies as specified in Table 1 of EN 13261-1:2005 Conformity criteria for physical and chemical properties and evaluation procedure based on spot samples and statistical conformity criteria on the same basis as for fly ash, either using inspection by variables or inspection by attributes [Silica fume in powder or slurry form, product likely to be certified] [Note: Conformity control for fly ash follows similar approaches as for ggbs and silica fume see EN 450-1 and EN 15671 for details]
Test cement
Selected brand of Portland cement of type CEM I, strength class 42,5 or higher, conforming to EN 197-1 to be used for carrying the tests needed to evaluate conformity to the requirement of 5.3.3 in EN 13263-1:2005
Test cement is selected by the silica fume manufacturer and is further characterised by its fineness and contents of tricalcium aluminate and alkalis as follows: Fineness (Blaine): 300 m2/kg to 400 m2/kg (EN 196-6) Tricalcium aluminate: 8% to 12% (EN 196-2) Alkalis (Na2O equivalent): 0,6% to 1,2% (EN 196-2)
The requirements of test cement for silica fume is not identical to that for fly ash and GGBS (both with same requirements)
34
Note: Test cement for silica fume meets requirements for testing fly ash and GGBS [single test cement for all three preferred] Cements used as test cements are for conformity testing of additions and may not be of the same chemical and physical properties as that to be used in a project. Initial testing of designed concrete is necessary, unless the particular concrete has been certified or demonstrated to meet the requirements for the project from inspection records by an accredited Certification Body (by SAC in Singapore)
35
Workability
Improve cohesiveness Fly ash and silica fume are particularly beneficial due to their spherical shape
Effects on Microstructure
Increase C-S-H & reduce CH leads to more homogenous microstructure (CH contributes mainly high pH) Improve pore structure, reduce overall porosity & pore size
(Mindess et al 2003)
(Mindess et al 2003)
Effect on Durability
Used extensively for improving the durability of concrete Improvements in durability result from the reduction in CH, changes in pore structure, and reduction in w/c
Increase sulfate resistance Control alkali-aggregate reaction Reduce chloride diffusion Reduce leaching and efflorescence
EN 206-1 5.2.5.2 k-value concept: Type II additions to be taken into account by replacing: water/cement ratio with water/(cement + k x addition) ratio in minimum cement content for durability requirements BS 8500 (SS 544) for deemed to satisfied approach for different exposure conditions provides specific minimum cement content and maximum water/cement ratio directly in relation to specific types of cement (i.e. inclusive of k-value concept)
Linear expansion of concrete exposed to standard ASTM tests for sulphate attack or alkali-aggregate reaction (More details in topic on aggregates)
(Mindess et al 2003)
BS EN 1008: 2002 Mixing water for concrete Specification for sampling, testing and assessing the suitability of water, including water recovered from processes in the concrete industry, as mixing water for concrete
The new standard replaces BS 3148: 1980 and provides more specific requirements and test methods including water recovered from processes in the concrete industry
Water recovered from processes in the concrete industry shall conform to the requirements of Annex A (normative)
Clause A.4 Requirements provides additional requirements to those set out in Clause 4 Requirements for all types of water
500
1 000
4 500
6.1.3
100
Annex B (informative) Testing scheme for mixing water for concrete (see EN 1008: 2002 for details)
BS-EN
197-1: 2000 (SS EN 197-1: 2008) CEM I Portland cement 197-1: 2000 (SS EN 197-1: 2008) CEM II Portland comp. cement CEM III blastfurnace cement CEM IV pozzolanic cement CEM V composite cement
C 618 Spec for coal fly ash 450-1: 2005 Fly ash for concrete and raw or calcined natural Definition, spec, and conformity pozzolans for use in concrete criteria C 989 Spec for GGBFS for use in concrete and mortars 15167-1: 2006 (SS EN 15167: 2008) Ground granulated blast furnace slag for use in concrete, mortars, and grouts 13263-1: 2005 (SS EN 13263: 2008) Silica fume for concrete
Admixtures C 494 Spec for chemical admixtures C 1017 Spec for chemical admixtures for flowing concrete Water C 94 Spec for Readymixed concrete calls for test on setting time and 7day strength of mortar
BS EN 1008: 2002 Mixing water for concrete (including water recovered from processes in the concrete industry, as mixing water for concrete