Beruflich Dokumente
Kultur Dokumente
M AY
2011
Technical note
Sulfate-resisting Concrete
Sulfate-resisting
concrete
INTRODUCTION 1 Sulfate exposure conditions
This Technical Note discusses the mechanisms in Australia
of external sulfate attack which include chemical Sulfates may occur naturally in soil and
reactions and the physio-chemical effects on groundwater, in industrial effluents and wastes
concrete. It reports the outcome of a research from chemical and mining industries, as well as in
project conducted by Cement Concrete & sea water. Acid sulfate soils are associated with
Aggregates Australia (CCAA). In this project naturally occurring sediments and soils containing
the performance of Australian concrete mixes, iron sulfides usually found in mangroves, salt
proportioned using sulfate-resisting cements marsh vegetation or tidal areas and low lying parts
(AS3972 TypeSR1) and non sulfate-resisting of coastal floodplains, rivers and creeks.
cements were evaluated in both neutral and acidic Very few cases of aggressive sulfate soil and
sulfate conditions. The results were examined groundwater conditions have been reported in
in relation to the long-term concrete exposure Australia. In certain sections of the Parramatta Rail
data from the USPortland Cement Association Link in the Lane Cove Valley in Sydney, aggressive
(PCA) and the 40-year non-accelerated exposure sulfate and carbon dioxide in groundwater were
programme at the USBureau of Reclamation found; concretes with and without protective
(USBR). Current specifications for sulfate resisting membrane were therefore used to satisfy the
concrete in relevant Australian Standards and 100 years design life. The concrete at the base
some Road Authorities' specifications are of water cooling towers have been found to be
reviewed in the context of CCAA research findings exposed to high sulfate levels in the closed circuit
which are applicable to concrete structures in cooling systems. In the case of cooling towers at
sulfate or acid sulfate soil conditions. Bayswater Power Station in NSW, the concrete
was found2 to show no sign of attack when
inspected after 10 years of service. In the M5 East
Motorway project at Cooks River Crossing near
Kingsford Smith airport in Sydney, sulfate-resisting
concrete was used for the piles and diaphragm matrix. Some cements are more susceptible to
wall constructed in areas where the groundwater magnesium sulfate than sodium sulfate, the key
was found to have very high sulfate contents, mechanism is the replacement of calcium in
possibly caused by effluents from the industrial calcium silicate hydrates that form much of the
areas around the Cooks River. cement matrix. This leads to a loss of the binding
According to the NSW Acid Sulfate Soils properties. Formation of brucite (Mg(OH)2) and
Management Advisory Committee3, acid sulfate magnesium silicate hydrates is an indication of
soils are soils containing highly acidic soil such attack.
horizons or layers resulting from the aeration of The presence of chloride in soil and
soil materials that are rich in iron sulfides. The groundwater may be beneficial since there is
oxidation produces hydrogen ions in excess of considerable evidence, from seawater studies6,7,
the sediment's capacity to neutralise the acidity, that the presence of chloride generally reduces
resulting in soils of pH of 4 or less. The field pH expansion due to sulfate attack. The risk of
of these soils in their undisturbed state is pH 4 corrosion of embedded metals in buried concrete
or more and may be neutral or slightly alkaline. in non-aggressive soil is generally lower than
Organic acids are common in coastal ecosystems in externally exposed concrete. However, high
and can produce acid water and sediment. The chloride concentrations in the ground may
pH of these sediments is usually around 4.55.5. increase the risk of corrosion since chloride
As they do not have the ability to generate ions may permeate the concrete, leading to a
additional acid when exposed to air, they do not depassivation of the metal surface.
exhibit the same kinds of environmental risks that Above the soil or water table level in the soil
are associated with acid sulfate sediments. profile where the concrete surface is exposed to
In New South Wales, acid sulfate soil a wetting and drying condition, the concrete will
conditions have been reported by the Roads and also be subjected to a physio-chemical sulfate
Traffic Authority4 in the Pacific Highway upgrading attack. Folliard and Sandberg8 reported that the
programme, eg at the Chinderah Bypass which physio-chemical process is more prevalent in the
involved the dredging and disposal of potential field, in which concrete is physically, rather than
acid sulfate soil from a site near a major bridge chemically attacked by sodium sulfate. The only
over the Tweed River at Barneys Point. Other reactions involved are within the sodium sulfate-
locations include the floodplains of many rivers water system; the phase changes from a solution
including Clarence River, Clyde River, Hawkesbury to a solid, or from an anhydrous solid, thenardite
River, Hunter River, Macleay River, Manning River, (Na2SO4), to its hydrated form, mirabilite
Myall River, Nambucca River, Richmond River and (Na2SO4.10H2O). The amount of deterioration
Shoalhaven River. In Queensland, acid sulfate is a function of the potential crystallisation
soils have also been found in the coastal regions pressures or the volume increase associated with
including sulfide-bearing source rock and sodic a given mechanism. Any of the mechanisms can
soils which cover 45% of Queensland5. This has potentially produce pressures that are an order
led Queensland Main Roads to draw designers' of magnitude greater than the tensile strengths
attention to detailed analysis of the chemistry of the of the concrete. Further, the same pressures can
soil and groundwater, and the design of concrete be reached by any one of several crystallisation
to withstand these potentially harsh conditions. mechanisms by simply varying the temperature
and concentration of the sulfate solution in the
2 Mechanisms of sulfate attack system. The volume increase could cause severe
The deterioration of concrete exposed to sulfate is deterioration of the concrete but may be partially
the result of the penetration of aggressive agents accommodated in air-entrained concrete.
into the concrete and their chemical reaction
with the cement matrix. The three main reactions 3 Physical and chemical resistance
involved are: of concrete
Ettringite formation conversion of hydrated Both the physical resistance of concrete to the
calcium aluminate to calcium sulphoaluminate, penetration and capillary-induced migration of
Gypsum formation conversion of the calcium aggressive agents and the chemical resistance
hydroxide to calcium sulfate, and of the concrete to the deleterious reactions
Decalcification decomposition of the described above are important attributes of
hydrated calcium silicates. sulfateresisting concrete. Thus factors influencing
These chemical reactions can lead to the permeability and surface porosity of the
expansion and cracking of concrete, and/or concrete and the chemical resistance of cement
the loss of strength and elastic properties of are prime performance parameters of concrete
concrete. The form and extent of damage to exposed to sulfate attack.
concrete will depend on the sulfate concentration, The physical resistance of concrete is
the type of cations (eg sodium or magnesium) traditionally achieved by specifying mix design
in the sulfate solution, the pH of the solution parameters such as maximum watercement
and the microstructure of the hardened cement ratio and minimum cement content, while the
EXPANSION (microstrains)
EXPANSION (microstrains)
1000 1000 1000
0 0 0
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
DAYS IMMERSED DAYS IMMERSED DAYS IMMERSED
EXPANSION (microstrains)
EXPANSION (microstrains)
1000 1000 1000
0 0 0
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
DAYS IMMERSED DAYS IMMERSED DAYS IMMERSED
0 100 100 100 100 100 100 100 100 100 100
514 126 126 129 164 129 161 125 131 116 116
776 134 135 125 159 131 158 124 132 115 115
939 128 130 121 152 145 158 116 126 112 105
1240 118 123 122 161 136 159 117 130 111 101
S1 S2 S3
Exposure 0.4 0.5 0.65 0.4 0.5 0.65 0.4 0.5 0.65
period (days) S1A S1B S1C S2A S2B S2C S3A S3B S3C
0 100 100 100 100 100 100 100 100 100 100
514 125 130 136 151 146 158 117 137 125 123
776 120 116 141 153 136 151 109 128 118 109
939 120 122 138 151 135 146 113 129 115 106
1240 123 127 136 163 131 149 111 136 115 108
S1 S2 S3
Exposure 0.4 0.5 0.65 0.4 0.5 0.65 0.4 0.5 0.65
period (days) S1A S1B S1C S2A S2B S2C S3A S3B S3C
The conditions of the concrete cylinders after 3-years exposure were quite varied with most retaining their integrity but
some were badly cracked especially around the top edges. See Plate 3 showing contrast in colour of cylinders after
3-year exposure.
The US Bureau of Reclamation (USBR) water-cement ratios of 0.4 and 0.5. This clearly
nonaccelerated sulfate testing programme, on showed the integrity of the concrete and its
concrete cylinders partially submerged in 2.1% mechanical resistance to sulfate attack.
or 21,000 ppm sodium sulfate solution at ambient
temperature, showed concrete with w/c ratio of 4.2 Performance of partly buried concrete
0.45 and lower to be intact even after 40-year While most buried concrete elements such as
exposure period15. The Bureau defined failure piles and footings are likely to be kept moist
when expansion reached 0.5% or 5000 microstrain. throughout their service life, parts of some of them
The results also showed the importance of (eg the top of footings and pile caps) may be
permeability and cement composition for concrete exposed to periodic wetting and drying conditions.
with w/c exceeding 0.45. USBR results support The PCA study confirmed that the exposure to
the validity of current service life performance alternate immersion and atmospheric drying in
specification. the sodium sulfate-rich soil was a more severe
It can be observed from Tables 1 and 2 exposure condition than continuous immersion
that the compressive strength of the concrete in the same solution. Attention must therefore
increased well above the 28 day strength in the be given to the sulfate resistance of concrete
first 12 years of immersion, followed by a gradual under such exposure conditions. Stark14 found
reduction in strengths. After three-year exposure a consistently improved trend in the rating of the
in both neutral and acidic sodium sulfate solutions, surface deterioration of concrete with increased
the strengths remained at or above the 28-day cement content irrespective of the type of cement.
strength level for Type SR cement concretes with In the PCA's 17 concrete mixtures with a cement
Water permeability
(x1012 m/s) 0.070.28 0.341.70 0.16 1.5 70.3 0.14 0.35 13.4 0.13 0.44 16
Water-to-cement 0.400.41 0.50 0.39 0.50 0.63 0.39 0.5 0.66 0.40 0.50 0.66
and good chemical resistance of the cement Figure 5 Water permeability of the concretes at
matrix to the deleterious sulfate reactions. A w/cof 0.4, 0.5 and 0.65
performance specification based on water
permeability of the concrete has been proposed 4000
RAPID SULFATE PERMEABILITY (coulomb)
2011
sulfate ions. Good physical resistance of the Concrete, ACI31805, American Concrete Institute.
concrete is directly related to the water-cement ratio 10 Building Research Establishment. Concrete in
and the cement content. Good chemical resistance aggressive ground, BRESpecial Digest 1:2005.
is related to the resistance of the cement matrix to 11 Sirivivatnanon V and Khatri R P 'Performance
the deleterious sulfate reactions. Based Specification for Sulphate Resisting
Sulfate-resisting concrete can be achieved using Concrete,' Proceedings of International
a sufficient quantity of a sulfate-resisting cement Conference on a Vision for the Next Millennium,
(Type SR complying with AS 3972) and a low water edited by R N Swamy, Sheffield, UK, June 1999,
cement ratio to obtain a concrete with low water pp 10971106.
permeability. For fully buried concrete structures in 12 Tumidajski P J and Turc I, A Rapid Test for Sulfate
saturated soils, a sulfate-resisting concrete can be Ingress into Concrete, Cement and Concrete
achieved from Type SR cement at a cement content Research, Vol. 25, No. 5, 1995, pp 924928.
of 335 kg/m3 and a watercement ratio of 0.5. For 13 Verbeck G J 'Field and Laboratory Studies of the
partially buried structures exposed to a wetting Sulphate Resistance of Concrete', Proceeding
and drying condition, the same sulfate-resisting of a symposium in honour of Thorbergur
concrete can be used but with additional protective Thorvaldson, Candana, 1967, 113124.
measure such as the application of an appropriate 14 Stark D C 'Performance of Concrete in Sulfate
sealer to the surface of the exposed concrete. Environments, RD129, Portland Cement
Alternatively, a sulfate-resisting concrete can be Association, (USA), 2002
achieved from Type SR cement at a cement content 15 Monteiro P J M and Kurtis K E, 'Time to failure
of 415 kg/m3 and a watercement ratio of 0.4. The for concrete exposed to severe sulfate attack',
AS3600 specifications for concrete structures in Cement and Concrete Research, Vol. 33, No. 7,
acid sulfate soils, based on minimum compressive 2003 pp 987993.
strength and TypeSR cement, is shown to produce 16 AS3600 Concrete Structures, Standards
adequate sulfate-resisting concrete for the exposure Australia, Sydney, 2009.
condition indicated. Alternatively, performance- 17 AS2159 Piling Design and installation,
based specifications based on TypeSR cement and Standards Australia, Sydney, 1995.
a concrete with a limit on either water permeability or 18 AS3735 Concrete structures for retaining liquids,
rapid sulfate permeability can be used. Standards Australia, Sydney 2001.
19 AS3735 Concrete structures for retaining liquids
7 References Supplement Commentary, Standards Australia,
1 AS3972 General purpose and blended cements. Sydney, 2001.
Standards Australia, Sydney 2010. 20 AS5100 Australian Standard for Bridge Design,
2 Sulphate Attack on Concrete. Fly Ash Technical Standards Australia, Sydney, 2004.
Notes No. 2, Ash Development Association of
Australia, 1995 CCAA OFFICES
3 Acid Sulfate Soils Assessment Guidelines,
SYDNEY: (61 2) 9437 9711
NSW Acid Sulfate Soils Management Advisory BRISBANE: (61 7) 3227 5200
Committee, 1998. MELBOURNE: (61 3) 9825 0200
4 Selim H, Forster G and Chirgwin G 'Concrete PERTH: (61 8) 9389 4452
ADELAIDE: (61 8) 8274 3758
Structures in Acid Sulfate Soils', Proceedings
TASMANIA: (61 3) 6491 1509
of Austroads Bridging the Millennia Conference,
WEBSITE: www.ccaa.com.au
edited by G.J. Chirgwin, Vol. 2, Sydney, 1997,
pp 393409. EMAIL: info@ccaa.com.au
5 Carse A 'The design of concrete road structures Disclaimer: Cement Concrete & Aggregates
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