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INTRODUCTION
Properties,
Characterisation
and Uses
Notes: * - may exceed 6.0% if Strength Index is acceptable; ** - limit does not apply to slurried products; *** - method defined in Standard; **** -
to be carried out in accordance with ASTM C1069.
Activity Index % - >105 @ 7d* >100 @ 28d** >95 @ 7d** >85 @ 28d**
Notes: * uses accelerated curing process; ** uses standard curing process; # - refer to Notes – Table 1.
In Europe, EN 13263-115 nominates chemical (SiO2 In New Zealand, natural amorphous silica deposits in
content, free Si, free CaO, sulfate, chloride and LOI) the Rotorua district have been commercialised. These
and physical (specific surface area and activity deposits are hosted in hydrothermally altered rhyolitic
index) requirements for ‘silica fume for concrete’. This rocks – Mamuka Ignimbrites and Rotoiti Breccia –
Standard includes a conformity assessment process to estimated to be 60,000 to 200,000 years old. The
ensure the ongoing quality and consistency of the silica deposits have been extensively altered geologically,
fume. with widespread silification17. The product is mined,
ground and blended to achieve a product of high
A comparison of several international Standards quality with consistent physical and chemical
requirements for silica fume shown in Table 2 (page 2). properties. The product has a SiO2 content of 85-90%,
being mainly amorphous silica but containing a small
proportion of crystalline quartz and cristobalite. It has
a bulk density of about 500-600kg.m-3 and an average
AMORPHOUS SILICA PRODUCTION particle size of about 2µm17.
AND PROCESSING
Metakaolin
The wide variety of materials in the ‘amorphous silica’
class necessitates separate consideration of the nature
Metakaolin is a fine, amorphous, alumino-silicate SCM
and extent of processing required for each material
that is made by calcining pure or refined kaolinitic clay
type. As with all raw materials for use in concrete, the
at a temperature of 650-800°C, and then grinding it to
key processing considerations are (a) meeting
a specific surface area of about 700-900m2/kg18
Standards or specification requirements, and (b)
resulting in an average particle size of about 3µm. The
providing a product of consistent quality.
product is a highly reactive SCM.
Silica Fume
Rice Husk Ash
Silica fume is a by-product of the production of silicon
A reactive pozzolanic material is produced when rice
metal or ferro-silicon alloys in electric blast furnaces.
husks are burned under controlled conditions –
In these processes, silica sand (quartz) is fed into the
typically at 500-700°C. The resultant material has a
blast furnace with coke, coal and wood chips. These
SiO2 content of about 80%, and contains both
materials are reacted at temperatures of about 2000°C
amorphous and crystalline silica particles. The
to produce the silicon product, with very fine silica fume
average particle size can be quite high (about 50µm),
being produced as a by-product of the reactions.
but because of the highly porous structure of the
Decades ago, the smoke-like silica fume fines were
product it can have an extremely high surface area (up
released to the atmosphere. In the 1970’s more
to 50-60,000m2/kg), which makes it highly reactive5.
substantial environmental regulations required that the
The need to closely control the burning conditions
fines be collected in fabric filters which allowed the
limits the practicality of producing the product in many
silica fume to be recovered and made available for use
regions, and particularly in under-developed countries.
in the concrete industry16.
Natural Pozzolans
Silica fume as produced is an extremely fine material
and is comprised primarily of high purity (typically
>95%) amorphous silicon dioxide (SiO2). A small There is a wide variety of natural pozzolan materials
proportion of crystalline SiO2 is produced. This varies used throughout the world, with a variety of origins.
dependent on the manufacturer, with reported levels of Many are of volcanic origin and the glassy deposits
from <0.05% to <0.5%. The physical characteristics of may be ‘incoherent’ layers of glassy material or
the product are: compacted materials (known as tuffs) that may have
been chemically altered by later geological activity.
Some sedimentary materials (clays and diatomaceous
Particle Sizing: 95% <1µm
earths) also demonstrate strong pozzolanic behaviour.
SG: about 2.2 In the main these materials are glassy, silico-aluminate
Specific Surface Area: 15 – 30m2/g compounds and often with significant porosity. They
Bulk Density: 130 – 430kg.m-3 (as produced) can contain small proportions of crystalline silica as
480 – 720kg.m-3 (densified) well as quite high alkali contents19. The materials can
be mined and milled into fine powders for use in
concrete and related applications. There has been
Silica fume as produced is very light, and to improve its little interest in this class of pozzolans in Australia,
handling characteristics and transportability, it needs to although some work has been done on glassy
be densified by agglomerating the fine particles into
Silica Fume
Property
Rice Husk
Un-Densified Densified Microsilica Metakaolin Natural Pozzolans
Ash
S.G. 2.2 2.2 2.15 – 2.3 2.4 – 2.6 2.1 2.3 – 2.6
Bulk Density
130-430 480-720 500-600 600 500 1000 - 1400
(kg.m-3)
Water Requirement
increased increased increased increased increased increased
Use of Silica fume and Microsilica results in Sulfate Resistance – the use of silica fume concrete
improvements to a range of concrete properties as has been found to be as effective as using Type SR
described below. It has been noted that, because of cements to prevent sulfate attack, and if used in
the high degree of cohesivity found with silica fume combination with fly ash or GGBFS, is even more
mixes, concrete slump targets 25mm to 50mm higher effective than Type SR cements47. The improved
than those used for Portland cement mixes are resistance is likely due to (a) the refined pore structure,
necessary in order to achieve similar levels of and (b) the lower lime content. Testing with Microsilica
compaction38. using ASTM C 101248 showed very significant
improvements in sulfate resistance against a cement-
only control35.
Compressive Strength – test work carried out on
Australian silica fume involving comparisons with silica
fume sourced from Europe showed that (a) the Alkali Silica Reaction (ASR) – one of the first
performance of the materials was similar, regardless of commercial uses of silica fume was for the control of
source, and (b) 28-day concrete strengths for silica ASR in Iceland, where since 1979, all concrete has
fume mixes containing 350kg of cementitious material included about 7% replacement of cement with silica
were 15% higher than a cement-only control (43MPa at fume. This has proved to be a very effective solution49.
28-days) at 5% replacement level; 35% higher than the Silica fume acts in several ways to mitigate ASR – by
control at 10% replacement level; and 40% higher than (a) reacting with, and binding, available alkalis and (b)
the control at 15% replacement level32. At higher reducing water ingress because of lower concrete
cementitious contents the proportional improvement is permeability49. It has been reported that agglomerated
expected to be lower. In a separate study with higher silica fume may act as an initiator of ASR, so care must
cementitious contents and higher strengths, be taken to ensure efficient mixing and complete
improvement of 25% and 35% were noted against a distribution of the silica fume50,51. In New Zealand
control that yielded 56MPa at 28-days34. For where ASR has been problematic, natural mineral
Microsilica, trials demonstrated increases in 28-day materials like diatomite and pumicite were used in the
strength of 15-30% against a cement-only control with 1950’s and 1960’s to mitigate ASR until, in the 1990’s,
Microsilica additions of 7% and 10%35. It has also both Microsilica and meta-kaolin were introduced for
been noted that the modulus of elasticity of concrete ASR mitigation52. A substantial Australian review of
containing silica fume is higher than concrete of similar ASR and its control suggests that 8-10% silica fume is
strength containing cement only39. sufficient to mitigate ASR53.
Drying Shrinkage – differing views appear in the Carbonation – carbonation does not appear to be a
literature regarding the drying shrinkage of concrete significant issue with high strength concretes
containing silica fume. An increase in drying shrinkage containing silica fume, but with lower strength concrete
of about 15% has been reported40, while elsewhere it may be problematic, particularly if there has been
lower and slower drying shrinkage has been noted36. inadequate concrete curing39.
This suggests the need for trials to be carried out if
specific drying shrinkage performance is required as Applications of Other Amorphous Silica
the outcome will be dependent on a variety of factors. Materials
Testing of Microsilica showed that slightly higher drying
shrinkage was observed at 1 year against a cement- Where silica fume, fly ash and GGBFS are not readily
only control41. available, natural pozzolans are used as cement
replacement materials and for concrete durability
Pore Structure – the durability performance of concrete improvement where required. Some of these materials
is determined to a large extent by the pore structure increase concrete water demand. Some materials are
and the consequent permeability of the concrete. used after simply mining and milling them to an
Mercury porosimetry testing carried out on concrete appropriate fineness, while others are subjected to
containing Australian silica fume showed reduced ‘calcination’ – heating (to 500 - 800°C) to activate
levels of total porosity and a reduction in the number of certain (clay) minerals. Activated products like meta-
larger pores – both indicative of reduced kaolin are highly reactive54 and are used in both
permeability32. Other testing confirms the reduction in conventional concrete and in the manufacture of
concrete permeability, at least at up to a 10% cement geopolymer concrete. In Australia, some research has
3. Hewlett, P.C. (Ed.) (1998), “Lea’s 15. European Standard EN 13263-1 (2005),
Chemistry of Cement and Concrete”, “Silica fume for concrete – Part 1: Definition,
Fourth Edition, Butterworth-Heinemann, specifications and conformity criteria”,
ISBN 0 340 56589 6, p. 6. European Committee for Standardisation.
4. Hewlett, P.C. (Ed.) (1998), “Lea’s 16. Silica Fume Association (2005), “Silica fume
Chemistry of Cement and Concrete”, user’s manual”, Federal Highway
Fourth Edition, Butterworth-Heinemann, Administration, Report No. FHWA-IF-05-016,
ISBN 0 340 56589 6, p. 472. April 2005, p.5.
5. Neville, A.M., 4th Edition (1995), “Properties 17. Microsilica New Zealand, (accessed
of concrete”, ISBN 0 582 23070 5, Longman November 2017), “General guide to
Group Limited, England 1995, p. 82. Microsilica”,
www.goldenbay.co.nz/products/microsilica-
6. Elkem, “Guidance for the specification of 600
silica fume”, C1-05 General Information,
18. Neville, A.M., 4th Edition (1995), “Properties
Elkem Materials, www.concrete.elkem.com,
of concrete”, ISBN 0 582 23070 5, Longman
November 2005.
Group Limited, England 1995, p. 84.
7. Hewlett, P.C. (Ed.) (1998), “Lea’s
Chemistry of Cement and Concrete”, 19. Hewlett, P.C. (Ed.) (1998), “Lea’s
Fourth Edition, Butterworth-Heinemann, Chemistry of Cement and Concrete”,
ISBN 0 340 56589 6, p. 679. Fourth Edition, Butterworth-Heinemann,
ISBN 0 340 56589 6, pp. 472 - 480.
8. Burnett, I.D., (1990), “The development of
silica fume concrete in Melbourne, 20. Vessalas, K. et al, (2008), “Pitchstone fines
Australia”, Concrete for the Nineties, pozzolanic activity assessment as partial
International conference on the use of fly Portland cement (PC) replacement”, J.
ash, slag, silica fume and other siliceous Australian Ceramic Society, 44(1), 2008, pp.
7 – 12.
materials in concrete, Leura, Australia,
Sept. 1990, ISBN 0 909375 38 0 21. Tuladhar, R. et al, (2013), “Durability of
concrete with pitchstone fines as a partial
9. Standards Council of Canada, Standard cement replacement”, Proceedings –
CAN/CSA-A23.5-M86, “Supplementary Concrete Institute of Australia Biennial
Cementing Materials”, 1 July, 1986. Conference, Concrete 2013, Gold Coast,
Australia.
10. Standards Australia, Australian Standard
3582.3 (2016), “Supplementary cementitious 22. ASTM C 1169 (2014), “Test method for
materials, Part 3: Amorphous silica”, SAI specific surface area of alumina or quartz by
Global, ISBN 978 1 76035 398 8. nitrogen adsorption”, ASTM International,
West Conshohocken, PA United States,
11. Standards Australia, Australian Standard www.astm.org
3582.3 (2002), “Supplementary cementitious
materials for use with Portland and blended 23. Standards Australia, Australian Standard
cement, Part 3: Amorphous silica”, SAI 3583.6 – 1995 (R2016), “Determination of
Global, ISBN 0 7337 4929 1. relative water requirement and relative
strength”, SAI Global, ISBN 0 7262 9373 3
12. Standards Australia, Australian Standard
3582.3 (1994), “Supplementary cementitious 24. ASTM C 311 / 311M-17 (2017), “Standard
materials for use with Portland cement, Part test methods for sampling and testing fly ash
3: Silica fume”, SAI Global, ISBN 0 7262 or natural pozzolans for use in Portland
8999 X. cement concrete”, ASTM International, West
Conshohocken, PA United States,
www.astm.org
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Australia for its use.