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o123ernational RILEM TC 186-ISA Workshop on Internal Sulfate Attack and Delayed Ettringite Formation (4-6 September 2002, Villars, Switzerland)
K. Scrivener 1 and J. P. Skalny 2
(1) Laboratory of Construction Materials, EPFL, Lausanne, CH- 1015, Switzerland (2) Materials Service Life, USA
Received: 29 March 2005

ABSTRACT
A RILEM technical committee on Internal Sulfate Attack (TC 186-ISA) was established in 1996. In the ensuing years considerable research was carried out, which helped to clarify the scientific knowledge surrounding this form of degradation. A Seminar was organised in September 2002 to bring together the leading researchers in the field to debate the state of the advances made in this area. All known active researchers in the area were invited and most were able to attend. The workshop was organised with sessions designed to address the key questions related to Delayed Ettringite Formation (DEF) and Internal Sulfate Attack. In each session one or more invited presentations and several shorter presentations were made by leading researchers to summarise experimental findings and present their views. These presentations were followed by extensive discussion, at the end of which a summary was made of the main points of agreement and of areas where questions remained open. This report gives these discussion summaries as the current consensus view on this subject. 1359-5997 9 2005 RILEM. All rights reserved.

Une commission technique de la RILEM sur 1"attaque interne des sulfates (TC 186-ISA)fat erdde en t 996. Au eours des anndes qui ont suivi, d'importants travaux de recherche sont OtOmen~s en vue d'aider h elarifier la eonnaissance scientifique entourant cette forme de dOgradation. Un sOminaire fut organis~ en septembre 2002 afin que les prineipaux experts du domaine puissent discuter ensemble et faire ~tat de l' avancOe de leurs reeherehes sur ce sujet. Tous les grands chercheurs spOcialistes du domaine furent invitOs et la plupart put assister au sOminaire. Celui-ci fut divisd en sessions visant h aborder les questions li~es 3 la formation retardOe de l'ettringite (DEF) et g~ l'attaque interne des sulfates. Chaque session comportait une ou plusieurs prOsentations invitdes et plusieurs interventions plus courtes, faites par les experts pour r~sumer leurs rOsultats exp~rimentawc et exposer leurs points de vue. Ces prOsentations Otaient suivies par de longues discussions, gt la fin desquelles dtait fait un compterendu, rdsumant les principaux points d'aceord et les domaines olt des questions restaient en suspens. Dans ce rapport sont regroupOs les rOsum~s de ces discussions, r~sultats du consensus actuel sur ce thkme.

R StJM ;

The phenomenon o f external sulfate attack o f concrete has been known for a long time. At the end o f the 19th century MichaElis observed white deposits in concrete exposed to sea-water, which he called the c e m e n t bacillus. Later this phase was recognised to be ettringite. In external sulfate attack, sulfate entering the concrete from the

environment reacts with calcium aluminate monosulfate in the cement paste to give ettringite, which can lead to expansion. In field conditions degradation may also involve loss o f strength through leaching o f calcium. There is an extensive literature on the subject. Internal sulfate attack is analogous to this external sulfate attack except that there is no influx o f sulfate from

Editorial Note Created in 1996, the R I L E M Technical Committee 186-ISA "Internal Sulfate Attack' was chaired by Dr. Jan Skalny. The author o f this paper, Prof. Karen Scrivener, was the Secretary of RILEM TC 186-ISA. Following the Workshop in Villars, Switzerland, the RILEM TC 186-ISA was closed at the end o f 2003. EPFL (Switzerland) is a RILEM Titular Member. Karen Scrivener is a RILEM Senior Member. She is the Convener o f RILEM Cluster D, "Durability and Deterioration Mechanisms' and she participates in RILEM TCs 197-NCM 'Nanotechnology in construction materials' and PAE 'Performance of cement-based materials in aggressive aqueous environments '. Dr. Jan P. Skalny is a RILEMSenior Member.

1359-5997 9 2005 RILEM. All rights reserved. doi: 10.1617/14111

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secondary ettringite in the cracks formed by these deterioration processes? 9 Can the formation of ettringite in pre-existing cracks lead to the lengthening and/or widening of these cracks? Can the deposition of ettringite in air-voids jeopardise the resistance of the concrete to frost damage? The workshop was organised with sessions designed to address these key questions. In each session one or more invited presentations and several shorter presentations were made by leading researchers to summarise experimental findings and present their views. These presentations were followed by extensive discussion, and at the end of each discussion session a summary was made of the main points of agreement and of areas where questions remained open. This report gives these discussion summaries as the current consensus view on this subject. A fuller account of the discussions and written versions of the presentations can be found in the published proceedings [1]. 1: S U L F A T E S I N P O R T L A N D CEMENT CLINKER AND CEMENT, TYPES, CONTROL, REACTIVITY
T h e m e

the environment. Two forms of internal sulfate attack (ISA) have long been known: 9 ISA due to contamination of the aggregates by sulfates (The rise in the use of recycled building materials as aggregate makes this an increasingly important issue) 9 ISA due to over sulfation of the cement The amount of sulfate needed to induce expansion depends on the composition of the clinker, but is generally above 5 or 6% SO3 by weight of cement. A second important feature is that in these forms of ISA the expansion occurs fairly rapidly, within about 6 months. Both of the above cases of ISA are addressed by standards and norms which limit the amount of sulfate in aggregates and cement to prevent their occurrence. This workshop deals with a third form of ISA, which has only come to attention relatively recently. This form of ISA has been observed in concretes (and mortars) which have experienced elevated temperatures during curing, either through the external application of heat as in steam curing, or from internal temperature rise due to the heat evolved during hydration. This form of ISA is widely known as Delayed Ettringite Formation or DEF. Despite its general use, this term can be misleading as it has long been known that in concretes exposed to moisture, ettringite will recrystallise harmlessly into pores, voids and previously existing cracks. This phenomenon is more usually referred to as secondary ettringite formation. Furthermore, it has also been observed that in concretes which have been heat cured ettringite may form at late ages (delayed formation) without any detrimental effect on the concrete. A RILEM technical committee (TC 186-ISA) was established in 1996. At that time the subject was highly politicised because the role of DEF was a critical element in litigation concerning damaged concrete. In the ensuing years considerable research was carried out, which helped to clarify the scientific knowledge surrounding this form of degradation. A Seminar was organised in September 2002 to bring together the leading researchers in the field to debate the state of the advances made in this area. All known active researchers in the area were invited and most were able to attend. Some of those who were not able to attend, submitted contributions which are included in the Proceedings [ 1]. In particular, the seminar aimed to establish the extent to which the following questions could be answered: 9 Does the DEF form of ISA occur only in concretes which have experienced temperatures in excess of some threshold temperature (around 70~ Can it also occur in concretes which have been maintained at ambient temperatures? 9 What parameters in the cement and concrete influence the likelihood of expansion after exposure to elevated temperatures during curing? 9 Can high sulfate contents originating in the clinker (rather than added during grinding) induce this form of ISA even in the absence of elevated temperatures? 9 How prevalent is this form of ISA in the field? How may it be identified in the field concrete given the confusion of other forms of degradation - frost damage or alkali silica reaction, coupled with the formation of

The origin of sulfate in clinker is the impurities in the raw materials and fuel. According to the ratio of alkalis to sulfur, sulfates are found as either as alkali sulfates (K2SO4 and calcium langbenite (KCa2(SO4)3)) or anhydrite. General schemes exist to predict the distribution from the clinker composition but remain to be validated. For the alkali/sulfate ratios normally found in clinker anhydrite is very rarely present. The alkali sulfate phases are rapidly soluble. - Anhydrite is more slowly soluble but still disappears in a matter of a few days. - Anhydrite present in clinker reacts in the same way as natural anhydrite often present in calcium sulfate added during grinding. Some sulfate is present in solid solution in the clinker phases, mainly belite. - The total amount dissolved is around 0.5%. The amount of sulfate dissolved in the belite is limited by the appearance of anhydrite in the clinker [2]. Sulfate dissolved in clinker phases is balanced by dissolved aluminate such that late reacting sulfate would not be in sufficient excess to form ettringite. - Overall, sulfates in clinker can be considered to have broadly the same impact on cement hydration and delayed ettringite formation as sulfate added during grinding. There was broad agreement with these points. However, for very high clinker sulfate contents, well outside the range of those found in commercial clinkers, there remained a question of whether sulfate phases could be encapsulated by other clinker phases such as belite, and as such not available for reaction until late ages.
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Theme

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2: B A S I C S O F E T T R I N G I T E STABILITY

- As a pure phase ettringite does not decompose until about

114 ~ It may lose two of its 32 water molecules below this temperature, but this is reversible. - At low relative humidities partial reversible water loss may occur, but such low relative humidities are unlikely to occur in cementitious systems (even those heat cured) under normal conditions. - The existence of ettringite in cementitious systems is determined by the thermodynamics of the partition of aluminate and sulfate between, ettringite, AFro phases, C-S-H, hydrogamet and the solution. This system has not been fully characterised. - Elevated temperatures favour the formation of calciumalumino-mono sulfate (AFro) relative to ettringite. - T h e presence of alkalis in the system increase the solubility of ettringite and this influence on solubility is greater at higher temperatures.
Theme - It 3: C A S E

- Questions remain as to the relative lengths of time during which supersaturation is maintained; during which ettringite crystals can form on a submicroscopic or microscopic scale; and the timescale over which macroscopic expansion occurs. - Generally there is a lack of detailed understanding of the link between chemical changes and mechanical effects. 5: P A R A M E T E R S AFFECTING EXPANSION AFTER EXPOSURE TO ELEVATED TEMPERATURES - There was general agreement that there was unlikely to be a simple universal relationship between expansion after heat curing and parameters of cement composition. - Little study had been made of physical factors such as pore structure and saturation, which are probably related to DEF damage after heat curing. - I n addition to maximum temperature achieved, other curing parameters are important, but have been much less studied. o Very short precuring times (less than about 4 hours) favour thermal cracking, which increases vulnerability to DEF damage. o Curing at ambient temperatures for significant periods can remove the risk of DEF for concrete subject to short periods at high temperatures. o Concretes cured for very long periods at high temperature may not expand on subsequent moist storage, probably due to the incorporation of aluminate and sulfate in hydrogamet. - The presence of other active damage mechanisms (e.g. alkali silica reaction) may promote DEF - Additions of fly ash and slag additions may be effective in avoiding the risk of DEF.
Theme 6: C R A C K S AND AIRVOIDS Theme

STUDIES OF DEF

was unanimously agreed that there was no substantiated evidence for the occurrence of DEF related damage in concretes that had not experienced elevated temperatures. It had been impossible to produce such expansion in the laboratory even in extensively precracked specimens subject to wetting drying cycles [3]. Field cases, where the occurrence of DEF related expansion had been claimed, could not be substantiated; either due to the questionability of the DEF diagnosis or to lack of information on the early thermal history of the concrete, or both. - T h e diagnosis of DEF related damage can only be confirmed by observations at several levels. The following must be confirmed: o Evidence of macroscopic of expansion of the structural element. o Overall levels of sulfate in the concrete lie within standard limits. o Microscopic evidence of gaps occurring around aggregate, which are generalised throughout the structure. - T h e simple presence of ettringite in cracks IS NOT diagnostic of DEF related damage. - The incidence of field cases is low.
Theme 4: M E C H A N I S M S OF EXPANSION

- Considerable experimental and thermodynamic evidence exists to support the view that expansion related to delayed ettringite formation is caused by the growth pressure of the formation of submicroscopic ettringite crystals throughout the paste. This leads to a generalized expansion of the paste and the formation of gaps around the aggregate particles. - Nevertheless there is not unanimity on this view. Some researchers believe that the nucleation and growth of ettringite in cracks and at aggregate interfaces plays a significant role in expansion

- Ettringite growth in cracks or air voids will not generate expansive forces to damage normal strength concrete. - Furthermore in concretes which have never experienced elevated temperatures the conditions of supersaturation needed to produce expansive pressures will not arise. - I n badly damaged concrete, with very low tensile strength, it may be possible for the growth of ettringite in cracks to contribute to the development of high strains. - The in-filling of airvoids by ettringite will not impair the frost resistance of a properly air entrained concrete. - For a concrete which is poorly air entrained and which has a high enough w/c ratio to become saturated, the infilling of remaining air voids by ettringite may be a contributory factor to frost damage.
Theme 7: H O W TO AVOID DEF

- Blanket limits on temperature or cement composition impose restrictions which are difficult to justify to precast producers with long established reliable practices outside these limits.

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- M o r e workable guideline might contain alternative solutions for intermediate temperature ranges (ACI), or performance based tests or both. - The establishment of a reliable performance based test was made difficult by the lack of field cases and by the difficulties of finding good methods to accelerate the expansion process due to lack of knowledge on the mechanism of expansion.

There is limited evidence showing that the use of selected pozzolanic materials or ground granulated blastfurnace slag may reduce the risk of damage due to the expansion.

8.2 Mechanisms
Although much progress had been made on understanding the mechanism of expansion due to delayed ettringite formation, several details remain unclear: The absence of ettringite after heat curing is not a result of the decomposition of pure ettringite, but a consequence of the redistribution of aluminate and sulfate in other phases - C-S-H, AFm phase, hydrogarnet. The thermodynamic stability and solid solution range of the two later are not well known and this is an obstacle to a more complete understanding of the system as a whole. Alkalis are known to increase the solubility of ettringite and this is probably the main explanation for their role in increasing the susceptibility of concretes to expansion from DEF. However, their effect on other phases is unclear. Furthermore, the mechanism whereby leaching of alkalis appears to facilitate expansion is not well understood.
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T h e m e 8: W H A T H A V E W E L E A R N E D F R O M THIS C O N F E R E N C E ?
In his presentation Skalny reviewed the points of agreement and controversy regarding the subject of DEF and the progress which had been made in this workshop. The discussion focussed on three areas:
Definitions Mechanisms Practical measures
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8.1 Definitions
The consensus of the workshop was that the form of damage, widely referred to as "delayed ettringite f o r m a t i o n " - DEF is in fact a form of internal sulfate attack induced by exposure to heat. Therefore it should be more correctly known as "Heat Induced Internal Sulfate A t t a c k " . Nevertheless it was acknowledged that the term DEF was now in widespread use and was unlikely to be discontinued. The presence of ettringite recrystallised in pores or cracks is a common feature of mature concretes and not indicative of damage. Furthermore it has been extensively observed that the formation of ettringite in a delayed manner - i.e. in set and hardened concrete- was not necessarily damaging. It was felt important that any definitions published by organisations such as ACI should indicate that the mere presence of ettringite within cracks of a concrete could not be taken as diagnostic of internal sulfate attack. The following definition was agreed: Heat-Induced Internal Sulfate Attack - is sulfate attack induced without intrusion of sulfate into the concrete from external sources. The usual early generation of ettringite in concrete cured at ambient temperature is postponed as a result of exposure to excessive temperature during early stages of curing (i.e. > 70~ either as a result of heat curing or selfheating or both. The delayed development of ettringite can, under certain, but not unequivocal circumstances, lead to expansion of the concrete; the likelihood is greater for concretes using highly-reactive, primarily high-alkali cements. In concretes which have undergone such expansion, deposits of ettringite in gaps surrounding some aggregates and in paste cracks are produced during subsequent exposure to moisture in service. The mere presence of ettringite in cracks cannot be regarded as diagnostic, as cracks caused by other degradation mechanisms (e.g., freezing-thawing, ASR) will also become filled with ettringite.

8.3 Practical measures

It was now felt that the emphasis should be placed on education and finding practical measures to avoid problems of DEF. However, work on mechanisms should continue, as progress in this area may be needed to establish the validity of accelerated tests. It was felt that the workshop had made progress in bringing together knowledge on the scientific aspects of DEF expansion. However, this was of limited use to those faced with the need to avoid problems of DEF expansion in practice. The discussion of Theme 7 (How to avoid DEF in practice) highlighted the differing view points on whether a blanket maximum temperature was the only solution or whether it was possible to go above this temperature for certain compositions or after carrying out a performancebased test. Following this workshop the Technical Committee 186ISA was closed at the end of 2003.

REFERENCES
[1] RILEM PRO 35, 'International RILEM TC 186-ISA on Internal Sulfate Attack and Delayed Ettringite Formation' (Eds. K. Scrivener and J. Skalny) Proceedings (RILEM publications, Bagneux, France, 2002) (ISBN: 2-912143-44-6). Herfort, D., 'Distribution of sulfate in Portland cement clinker', pp. 18-27 in [1]. Collepardi, M. and Ogoumagh Olagot, J.J,. 'The influence of sulfate content in clinker or cement and curing temperature on DEF-related expansion', pp. 212-228 in [1].

[2] [3]

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Annex:

LIST OF PARTICIPANTS

BARBARULO, R6mi CAPMAS, Alain CASTELLOTE, Marta COLLEPARDI, Mario CORAZZA, Fabio DEJA, Jan DIENEMANN, Wolfgang DROLL, Klaus ESCADEILLAS, Gilles GALLUCCI, Emmanuel GHORAB, Hanaa GLASSER, Fred HEINZ, Detlef HERFORT, Duncan HOOTON, Doug JOHANSEN, Vagn KELHAM, Stephen KURDOWSKI, Wiestaw LUDWIG, Udo MARSHALL, Mel MATHUR, Prakash MENENDEZ, Esp6ranza MORANVILLE, Micheline OLEK, Jan PAVOINE, Alexandre POUPARDIN, Val6rie RONNING, Terje ROSANI, Diego ROUGEAU, Patrick SAMSON, Eric SCHERER, George SCRIVENER, Karen SKALNY, Jan STARK, Jochen SYLLA, Heinz-Martin TAYLOR, Hal THOMAS, Michael VICHOT, Ang61ique VIEIRA, Silvia WIEKER, Wolfgang

CEA Saclay, France ATILH, France Instituto Eduardo Torroja (CSIC), Spain Politecnico di Milano, Italy CTG Italcementi Group, Italy Polska Cement LTD, Poland Heidelberg Cement Technology Center, Germany DyckerhoffZementGmbH, Germany INSA Universit6 Paul Sabatier, France EPFL-LMC, Switzerland Helwan University, Eygpt University of Aberdeen Technische Universit~itMtinchen (TUM), Germany Aalborg Portland A/S, Denmark University of Toronto, Canada Construction Technology Laboratories, Inc., USA Lafarge Cement UK, UK University of Mining and Metallurgy, Kracow, Poland Institut flit Gesteinshuttenkunde, RWTH Aachen, Germany Mel C. Marshall Industrial Consultants Inc., Canada EPFL-LMC, Switzerland Instituto Eduardo Torroja (CSIC), Spain Ecole Normale Sup6rieure Cachan, France Purdue University, USA LCPC - Laboratoire Central Ponts & Chauss6es, France Lafarge LCR, France Norcem AS, Norway Holcim Group Support Ltd, Switzerland CERIB, France University of Laval, Canada University of Princeton, USA EPFL-LMC, Switzerland Materials Service Life, USA F.A. Finger-lnstitut fiir Baustoffkunde, Germany Forschungsinstitut der Zementindustrie e.V., Germany Consultant, UK University of New Brunswick, Canada ATILH, France Holcim Group Support Ltd, Switzerland WITEGA GmbH, Germany