Engineering Geology, 9 (1975) 303--326

© Elsevier Scientific Publishing Company, Amsterdam - - Printed in The Netherlands

Review

ALKALI--AGGREGATE REACTIONS IN CONCRETE

J. E. GILLOTT
Department of Civil Engineering, The University of Calgary, Calgary, Alta. (Canada)
(Received October 3, 1973; revision accepted October 14, 1975)

ABSTRACT

Gillott, J.E., 1975. Alkali--aggregate reactions in concrete. Eng. Geol., 9: 303--326.

Concrete durability is adversely affected b y expansive reactions between cement

alkalies and certain rocks and minerals sometimes used as aggregates. Present trends
towards production of portland cements containing higher alkali contents than formerly
indicate that the problem may become more acute. Recent work shows that the rocks
and minerals involved fall into three groups which leads logically to a three-fold
subdivision o f the reactions termed here: (I) the alkali--silica reaction, (II) the alkali--
carbonate rock reaction, and (III) alkali--silicate reactions. A clearer understanding of the
mechanisms of these reactions has practical implications particularly because o f the light
thrown on the criteria for recognition o f potentially expansive rocks and minerals in
aggregate source materials. Appropriate preventive measures prior to concrete placing
make it possible to avoid the worst effects of these reactions. These include use of low-
alkali cement, incorporation of a suitable pozzolan, design to reduce wetting and
beneficiation of aggregate. The effectiveness of these measures varies however, depending
on the mechanism and severity of the reaction.

INTRODUCTION

Alkali--aggregate reactions have recently become a subject of great concern

because of present or proposed increases in the alkali contents of portland
cements. This trend is a by-product of the "energy crisis", economic factors,
n e w technology or legislation aimed at environmental protection. Also there
is increased use of high-strength concrete with mix designs richer in cement
and/or lower water/cement ratios. Use of aggregates of poor quality is
increasingly c o m m o n due to the depletion of readily available good quality
aggregate sources close to urban areas. Hence aggregate-related durability
problems are expected to become of more frequent occurrence. Specifica-
tions for concrete aggregates are provided by standards organizations such
as the American Society for Testing and Materials (ASTM, 1974a, C33).
All alkali--aggregate reactions are principally affected by the mineralogy
and physical state of the aggregate, by the alkali content of the cement and
by the availability of moisture. Important other factors are the proportion
of reactive component (sometimes relative to the proportion of innocuous
304

constituent), temperature, and the presence or absence of pozzolanic mineral

admixtures. As always in durability failure, the extent to which concrete is
damaged depends upon the severity of attack b y other agencies which act in
concert with the initial cause of distress. Other agents of destruction include
freeze-thaw-cycling, temperature-cycling, wet-and-dry-cycling and sea-water
and sulphate attack.
One of the earliest references to expansion caused b y reaction b e t w e e n
aggregate and cement constituents dates back to 1935 and is credited to
Holden of the Virginia Polytechnic Institute (Kammer and Carlson, 1941).
A more comprehensive description of a reaction involving poorly ordered
silica was given somewhat later by Stanton (1940) in California. This work
is c o m m o n l y looked upon as the starting point of detailed investigations in
this field. An extensive literature to do with the alkali-silica reaction developed
from the time of the initial discovery up to about 1960. Poor concrete
durability due at least in some measure to this cause was recognized from
many parts of the United States, and in other countries such as Australia
(Vivian, 1947) and Denmark (Idorn, 1956). After this period the volume of
work declined b u t detailed studies continued in some laboratories either
because of the individual interests of the workers involved or because of the
special conditions resulting from the geology of the country, as is the case
in Iceland (Gudmundsson, 1971) and Denmark.
Poorly crystallized silica, particularly opaline silica and chert, chalcedony
and acid and intermediate volcanic glasses, were characterized as the
expansive components in the aggregate (ASTM, 1974a, b). The synthesis of
the early work led to the adoption of standard test procedures and a
r e c o m m e n d e d limit for alkali content of portland cement (0.6% equivalent
Na20) when used in combination with deleteriously reactive aggregates
(ASTM, 1974c). As experience increased the main features were identified
which make possible the recognition of the reaction in the post-mortem field
or petrographic examination of concrete and working hypotheses were
proposed concerning the expansive mechanism (Powers and Steinour, 1955).
During the 60s interest was focused upon another variety of alkali--
aggregate reaction which is known as the alkali-carbonate rock reaction.
Certain varieties of argillaceous dolomitic limestone were found to be
alkali-expansive. This reaction was investigated in detail in Canada and the
United States (Highway Res. Record, 1964; Gillott and Swenson, 1969).
Phyllites were associated with concrete expansion in some of the earliest
investigations of alkali--aggregate reaction (Kammer and Carlson, 1941). In
the late 60s and early 70s comprehensive studies of phyllites, greywackes,
argillites and other related rocks were made in Canada. This work has shown
that expansion may be caused b y exfoliation of phyllosilicates and it is now
suggested that the term alkali--silicate reactions be introduced. Such a
classification would prove convenient if, as seems certain, other silicate
minerals are found which react expansively with alkalies.
 305

FIELD EVIDENCEAND LABORATORYTESTS

Durability failure of concrete due to alkali--aggregate reaction can

generally be prevented if, prior to its use in concrete, it is realized that t h e
aggregate is alkali-expansive. Identification can often be made directly by a
petrographer experienced in alkali--aggregate reactions (ASTM, 1974d).
Where doubt exists, further tests are required. When expansive aggregate i s
found, preventive measures which can be adopted include use of low-alkali
cement, incorporation of a suitable pozzolan, design to minimize wetting,
beneficiation or selective quarrying (Smith, 1964).
False economy coupled with the diehard conviction that aggregates are
"inert" results in the required examination and tests frequently being left
undone. Concrete is generally examined in detail only if it is showing signs of
failure; the object is to ascertain cause so that remedial action and future
preventive measures can be taken and sometimes to apportion blame.

Field evidence

Concrete affected by a deleterious alkali--aggregate reaction commonly

develops a characteristic form of cracking often referred to as "pattern
cracking" or "map cracking". Its appearance is the same the world over
(Fig.IA--D) and is similar regardless of the type of alkali--aggregate reaction.
This is because the cracks develop in response to a stress distribution which
arises from differences in the amount of expansion in adjacent parts of the
concrete element. In general, expansion is greatest where moisture is most
readily available.
Expansion of concrete side-walk slabs often leads to extrusion of joint
filler (Fig.lC) and may be accompanied by buckling in these and related
structures. In addition to the more usual evidence of expansion in the
concrete decks of bridges, damage to parts of the steel structures sometimes
occurs (Gibson, 1958). Less obvious, but sometimes more serious, evidence
of expansion is found when machines set in concrete suffer misalignment of
working parts due to differences in rate of growth of neighbouring slabs or
elements. Over a period, observation of survey points set in concrete has
revealed concrete growth in some cases.
Concrete affected by the variety of alkali--aggregate reaction known as
alkali--silica reaction often shows exudations of a watery gel which dries to
a white deposit. Chemical analysis of these exudations or deposits shows
them to be composed mainly of silica and alkali often with varying amounts
of lime. Exudations of this sort are generally absent or insignificant in
concrete affected by the alkali--carbonate rock reaction.
Affected concrete sometimes shows pop-outs above particles of expansive
aggregate though this behaviour is not solely due to alkali--aggregate reaction.
306

Fig. 1. Concrete deterioration due partly or wholly to various types of alkali--aggregate

reaction.

Laboratory tests

Petrographic exam i na t i on of concrete involves study o f fracture surfaces

and thin and polished sections of etched and unet ched surfaces. Core samples
are the most satisfactory since t h e y may be obtained f r o m depths in the
s t r u ctu r e where evidence of alkali--aggregate reaction is n o t masked by ot her
causes o f p o o r durability such as weathering or attack b y surface waters. An
 307

indexed photograph of the core location is useful for future correlation of

field and laboratory observations (Fig.lD).
Studies are made in polarized light at low power on the binocular
microscope and up to the highest optical range, appropriate use being made
of immersion oils of known refractive index. The optical identification of
minerals has been routinely supplemented by X-ray diffraction, differential
thermal analysis and other methods for a number of years and examination
on the scanning electron microscope is becoming increasingly common.
When concrete, affected by alkali--aggregate reaction, is observed
microscopically, cracks may often be seen. The cracks occur within and
adjacent to particles of expansive aggregate but rarely radiate from these
particles. When the concrete is affected by alkali--silica reaction there are
frequently pockets of gel in cracks and voids. Gel is isotropic under the
petrographic microscope but sometimes appears anisotropic due to strain,
partial recrystallization or the presence of small inclusions.
When a fracture surface is examined with a hand lens, particles of affected
aggregate are often seen to be surrounded by rims, though these are better
seen microscopically. Rims are not necessarily an indication of deleterious
reactivity. Reactions between aggregate and cement which cause rim
formation certainly occur without significant expansion of the aggregate.
Saw-cut or polished surfaces of concrete made with limestone aggregate may
be acid etched. Rims which etch more rapidly ("negative" rims; Buck, 1965)
or more slowly ("positive" rims; Bisque and Lemish, 1958) than the remainder
of the aggregate particle are clearly revealed. When gravel aggregates are used
many particles show rims caused by weathering of the gravel, long before
it was used in concrete.
Significant amounts of the microforms of silica, the variety of dolomitic
limestone most commonly associated with the alkali--carbonate rock
reaction, and rocks of the phyllite-greywacke type, are readily identified.
When rocks or minerals of this sort are recognized in concrete, or in material
intended for use as aggregate, tests of dimensional change characteristics
should be carried out. Details of these tests are described in publications by
the American Society for Testing and Materials (ASTM, 1974e, f) and by
similar agencies.
Widely used tests involve measurements of length changes of mortar bars
(ASTM, 1974e) and concrete prisms (Tremper, 1944; Scholer and Gibson,
1948; Davis, 1957, Swenson and Gillott, 1960; Olsen, 1963) held at constant
temperature and high humidity. A related test involves measurement of rock
cylinders continuously immersed in alkali (ASTM, 1974f). There is also a
relatively rapid chemical test (ASTM, 1974g). Results, however, are often
anomalous (Dolar-Mantuani, 1969) and not as reproducible as ordinarily
desirable. Nonetheless, in some situations the test may be useful, particularly
when properly correlated with other procedures such as petrographic
examination (Mielenz, 1958).
Cases are known where aggregates would have been classed as not
deleteriously expansive on the basis of laboratory tests but where field
308

performance of concrete was exceptionally poor. In some instances

subsequent detailed investigations showed conclusively that deleterious
alkali--aggregate reactions were involved. The mechanism and t y p e of reaction,
however, were different from the alkali--silica reaction to which most test
procedures apply. In some reactions the rate of expansion is very slow b u t
continues for a long period and is destructive. In such cases the duration of
dimensional-change tests has to be extended b e y o n d the normal limits, and
test conditions require modification to accelerate the expansive reactions.
Methods by which this has been accomplished include artificial increase in
the alkali content of the mortar bars and concrete prisms, elevation of
conditioning temperature and, in the case of heterogeneous gravel aggregates,
concentration of rock types b y sorting. Carefully selected control specimens
are required when it is necessary to resort to such tactics (Carlson, 1944;
Swenson, 1957; Duncan et al., 1973a, b, c; Gillott and Swenson, 1973).

COMMON F AC TOR S IN ALL A L K A L I - - A G G R E G A T E REACTIONS

All alkali--aggregate reactions are affected b y a number of c o m m o n

factors. The more important are (a) the t y p e and concentration of alkalies;
(b) moisture; (c) temperature; and (d) pozzolanic additions.

The alkalies

The alkalies found in portland cement are derived chiefly from the
feldspars, micas and clay minerals contained in the limestone and argillaceous
material used as raw material in cement manufacture. Alkalies are normally
driven off to an appreciable extent during firing in the kiln b u t complete
volatilization is inhibited b y sulphates (Martin and Gibson, 1966) which are
derived from the fuel used in firing or from gypsum and, more rarely, from
pyrite in the raw material. Hence alkali sulphates are present in many
cements. Also alkalies form solid solutions proxying for other cations in the
principal minerals found in cement klinker (Fletcher, 1969a, b; Pollitt and
Brown, 1969; Adams, 1973). The alkali sulphates dissolve readily and the
sodium and potassium ions are also liberated from the hydrating cement
minerals themselves. The proportion of the total alkali content which is
soluble, however, varies a good deal between different cements (Galliland and
Bartley, 1950; McCoy and Eshenour, 1969). The alkalies in cement pore
solutions are normally present as hydroxides which account for the high pH
of the system. The h y d r o x y l is derived from lime formed as one of the
hydration products of the calcium silicates. Sulphates are known to be largely
precipitated as gypsum and calcium aluminate sulphates (Fig.2).
Both sodium and potassium hydroxide produce expansion in the alkali--
aggregate reaction and sodium hydroxide has been reported as more
aggressive than potassium hydroxide (Davis, 1958; Swenson and Gillott,
1960). Lithium c o m p o u n d s appear to inhibit expansion in the alkali--silica
reaction (Fig.3A) (McCoy and Caldwell, 1951). When susceptible aggregates
 309

CEMENT RAW
M~TER AL KILN

Feldspars
Micas
} Na+ +
K+ ~,~rVol at i l ize

Clay Minerals ~ - " ~ +SO;- AI kal i Sul phates

[Fu;i \
iGypsumi
\Pyrite/

CEMENT

Alkali Sulphates + HzO' .l, Na+ + K+ + SOC-

Z+
Ca - Silicates +H20 > Ca - Silicate - hydrates + Ca(OHiz'- Ca + OH

SOLIDS .CEMENT PORE SOLUTION

..~ Gypsum(ppt.)
SO,~- + Na+ + K+ + OH"
CaZ+~
+A£S%-~,-"-" Ca - Sulpho - Alumi nate (ppt.)
Ca - Silicate - hydrates
Ca(OH)z

Fig.2. The alkalies in portland cement (schematic}.

are present, the amount of alkalies which are allowable in the cement is
restricted because concentration of alkali affects rate and (frequently) degree
of expansion in all known types of reaction (Fig. 3A--D). In North America
the common limit is 0.6% expressed as equivalent Na20 (ASTM 1974c). ~
Hence differences in reactivity betweeta the alkali cations and differences in
solubility of alkalies between different cements are disregarded. Concrete
made with low-alkali cement and expansive aggregate generally has performed
satisfactorily (Lerch, 1959) although some cases of damage from this
combination have been reported (Hadley, 1968). Alkali contents lower than
0.6% equivalent Na20 have been recommended for some cases (Swenson and
Gillott, 1960).
Portland cement is by far the most important source of alkalies in
concrete, but alkalies sometimes may be derived from the aggregate by
exchange reactions, from alkaline waters or from the mixing water, as when
sea-water is used in this capacity (Gudmundsson, 1971).
Addition of alkali to mix water has been used successfully to accelerate
the mortar-bar and concrete-prism tests (Duncan et al., 1973c). However,
inconsistent and unreliable results have occurred with alkali contents as high
as 2.38% equivalent Na20.

Moisture

Moisture has been shown to be a requirement for expansion in allVarieties

of alkali--aggregatereaction. Field observationsshow that concrete distress
310

ALKALI CONTENT GMS OPAL OPAL SIEVE

2.0 EQUIV No20 GMS ALKALI SIZE (MESH) 0 2
• 107 5 16-50
• 107 5 16-50+1%LICI
• 107 5 < 325 9

1.5 • 046 I0 16-50 Z 015

ALKALI CONTENT TEMP
EQUIV NO20
g • 15 iO0°F (378°C)
• 099 125°F (517°C)
w LO IOOeF (378°C)
• 0.99
5 • 040 IO0°F (37 8°C)
J

0.5 ~ 005

i I
I 2 3 4 0 4 8 12 16
AGE IN MONTHS AGE IN MONTHS
A.EXPANSION OF MORTAR BARS (A.ST.M C 2 2 7 ) B.EXPANSION OF MORTAR BARS (ASTM C227)
CONTAINING MEXICAN OPAL ( l O 0 ° F ; 57.8°C) CONTAINING CHERT FROM NWT CANAOA

ALKALI CONTENT TEMP

EQUIV NazO
ALKALI CONTENT TEMP • 119 I$O°F ( 5 4 4 ° C )
EQUIV N(]20 • 119 IO0°F ( 3 7 8 ° C )
• 1.0 IO0°F ( 3 7 8 ° C } • 1.19 7 5 ° F 2 5 % OF CEMENT REPLACED BY
I * 099 75 °F (Z2 8°C) CALCINES SHALE
• 1.0 73°F (228°C) O Z~ X 052 7 3 ° F ( 2 2 8°C)
• 0.71 IO0°F ( 3 7 8 ° C )
-- • 054 IO0°F ( 3 7 8 ° C )

0.15
015

, !
0.1o
~ oJ

0.05
D 0.05 •

°'°~"~l T I f I I I r I
3 6 9 ,2 ,5 ,. 2, 2. 27 ~o o . 8 ,2 ,6
ASE ,N MONTHS A~E ,N MONTHS
C. EXPANSION O F CONCRETE PRISMS AT H I G H D EXPANSION OF CONCRETE PRISMS AT HIGH
RB CONTAINING NOVA SCOTIA GREYWACKE RH CONTAINING DOLOMITtC LIMESTONE
COARSE AGGREGATE COARSE AGGREGATE

Fig. 3. Length change data for various sorts of alkali-expansive aggregate.

is most common in moist locations such as footings, bridge decks, dams and
sidewalks. Mortar-bars made with reactive silica at a low water/cement ratio
do not expand and storage at low R.H. also inhibits expansion o f mortars
containing similar aggregate but made with a normal water/cement ratio
(Vivian, 1947, 1950). Comparable behaviour was found in the case of the
alkali--carbonate rock reaction (Swenson and Gillott, 1960). Subsequent
exposure of these test mortars and concretes to moisture resulted in rapid
expansion in both types of reaction. In some instances, however, a drying
period during test has been followed by a reduced rate of expansion when
comparison is made with non-dried companion samples of similar composition
(GiUott and Swenson, 1973). Proper consideration in structural design of the
significant role played by moisture in expansive alkali--aggregate reactions
 311

may do much to reduce damage to concrete from this cause. For example,
concrete elements may be designed so that ponding of water is reduced or
prevented.

Temperature

Increase of temperature accelerates alkali-aggregate reactions. After first

increasing with rise of temperature, expansion, however, has been reported to
decrease as temperature is raised beyond a certain point (Fig.3D) (Lerch,
1956; Swenson and Gillott, 1960). In the alkali--silica reaction the greatest
expansion has recently been reported to occur at 38°C, a minimum at 10°C
and no significant expansion at 60°C (Gudmundsson, 1973).
Conditioning at higher temperatures has been used as a means of
accelerating expansion in test procedures (Fig.3B, C) and to simulate extreme
climatic conditions better (Gogte, 1973). A reversion has not always been
found though this probably depends on differences in the mechanism of
expansion and on the temperatures employed (Kammer and Carlson, 1941;
Stanton, 1943; Carlson, 1944; Duncan et al., 1973c).

Pozzo~ns
A pozzolan is "a siliceous or siliceous and aluminous material which in
itself possesses little or no cementitious value but will, in finely divided form
and in the presence of moisture, chemically react with calcium hydroxide at
ordinary temperatures to form compounds possessing cementitious
properties" (ASTM, 1974h). Pozzolans have some influence on most
alkali--aggregate reactions and expansion due to alkali--silica reaction may
often be prevented or reduced by replacement of 20--30% of the portland
cement by a suitable pozzolan. Suppression of expansion has been reported
even when waste glass is used as coarse aggregate (Johnston, 1974). The
effectiveness of this method of control, however, varies greatly with the type
of pozzolan and with the type of reaction (Fig.3D). Standard tests of the
effectiveness of pozzolans are available (ASTM, 1974i).
The activity of fine siliceous powders and pozzolans probably is related to
the number and arrangement of hydroxyl groups exposed at the surface of
the individual particles. When calcined, pozzolans often become more active.
It is thought that water is driven off by combination of pairs of hydroxyls
attached to adjacent surface silicon atoms leaving strained silicon oxygen
groups (sfloxane bridge systems) at the surfaces (Hockey, 1965).
Reactivity is also affected by pH. In Ca(OH)2 solutions within the pH
range 5--13 the SiOH groups are acidic and hydrogen ions are replaced by
calcium. In sodium-hydroxide solutions at pH's greater than about 3.5,
hydroxyl ions are adsorbed by the silica because of hydrolysis and the
greater dissociation of the sodium--silica adsorption complex (Greenberg,
1956; Heston et al., 1960).
The cementitious compounds formed in portland cement by reactions with
312

pozzolans are believed to be calcium-silicate hydrates. The crystal chemistry

of these compounds implies that water as well as calcium and hydroxyl are
removed from the pore solutions by combination with the silica from the
pozzolan.
Removal of lime has been suggested as the significant factor in the role of
pozzolans in the suppression of expansion in the alkali--silica reaction
(Mather, 1952). Another view is that the effectiveness of pozzolans in this
regard depends upon a lowering of the hydroxyl concentration to the point
at which the amount of expansive reaction is markedly reduced (Diamond,
in press). Another alternative attributes the suppression of expansion to
reduction in alkali content of the pore solutions by reaction at the large
surface of the pozzolan (Powers and Steinour, 1955). This hypothesis hinges
upon relative concentration and diffusion rates of the cations sodium or
potassium versus calcium. It is suggested that in the presence of sufficient
pozzolan a non-swelling lime--alkali--silica complex forms in the potentially
expansive particle rather than an alkali--silica gel which swells by moisture
uptake. Change in viscosity or nature of the reaction product, decrease in
amount of reaction, decrease in permeability of the cement paste, and change
in solution concentrations so that the gradient no longer favours migration
of water into the potentially expansive aggregate, could all be involved in the
effectiveness of pozzolans in reducing expansion but the correct alternative
or combination is not yet clear.

T Y P E I - - A L K A L I - - S I L I C AR E A C T I O N

The rocks and minerals involved in the alkali--silica reaction are the
microforms of silica, the "amorphous" and microcrystalline phases (Sosman,
1965; F15rke, 1967). Those of concern, however, are found in igneous,
metamorphic and sedimentary rocks, thus they originate in both high- and
low-temperature environments.
Glass formation from melts takes place when crystallization is effectively
inhibited. As has been appreciated by artisans from early times, this is
favoured by rapid cooling of high-viscosity liquids. The first requirement,
rapid cooling, is obviously met in volcanic ejecta and the second, high
viscosity, is an inherent property of siliceous melts resulting from the
tendency of silicon--oxygen tetrahedra to form cross-links; viscosity increases
with fall in temperature so the depression of the freezing point which
accompanies increasing impurity in melts leads to formation of liquids of
even higher viscosity. The expansion of volatiles because of the abrupt
decrease in pressure on volcanic eruption favours pore formation and large
internal specific surface area.
Volcanic rocks which most frequently have been identified as expansive
in the alkali--silica reaction are glassy to cryptocrystalline rhyolites, dacites,
latites, and andesites and their tuffs (Mielenz, 1956). Refractive index has
been suggested as useful in identification of potentially deleteriously alkali-
expansive cryptocrystalline and glassy siliceous minerals (Mather, 1948).
 313

Work in Iceland has shown that volcanic glass of basaltic composition, which
in that country is used extensively as aggregate, also produces expansion in
mortar bar tests. Alkali--aggregate reaction and microcracks have been
observed in core specimens of concrete made with this type of aggregate
(Gudmundsson, 1971). Work with synthetic glasses has shown that the
nature of the cations has a marked effect on the expansive behaviour of these
materials when used as aggregate in the mortar-bar test. Siliceousglasses of
sodium and potassium were very expansive even in mortars made with
high-alumina cement and gypsum plasterof very low alkalicontent. O n the
other hand, similarglassescontaining lithium and lead were non-expansive
under similartest conditions (Pike et al.,1960).
The low-temperature siliceousrocks form by sedimentary and by
epigenetic processes. Silicais extracted from sea-water by such organisms as
diatoms, radiolarians,silicoflagellatesand spicular sponges. Under some
conditions the tests of organisms of this sort form deposits such as
diatomaceous earth, but there is a great deal of evidence to show that
diagenetic replacement is involved in the formation of flintand some
silicifiedlimestones. The biogenic silicais "amorphous" or very poorly
crystallizedand in opaline silicais associated with considerable water,
probably both as physically adsorbed H 2 0 and as hydroxyl groups combined
with internaland external silicasurfaces (Segnit et al.,1965). Different
samples of opal give X-ray diffractionpatterns which vary from those
showing only a broad reflectionat about 4 A, to others in which well-marked
peaks occur at spacings which match those of a-cristobaliteand sometimes
quartz. Polytypic intergrowths of tridymite-(ABABAB) and cristobalite-
( A B C A B C ) type layers are believed present in low-temperature cristobalites,
but the mixed-layering is said to be absent in cristobalitesformed above
900°C (Greenwood, 1973).
Electron micrographs of many opals show littledetail other than organic
remains (Fig.4C), but regularly arranged pores can be seen on a fracture
surface of the precious opal from Australia (Fig.4A). Etching reveals spheres
of 1700--3500 A diameter which have an internal structure of smaller
particlesof about 400 A diameter (Fig.4B). (The colour of precious opal
results from the diffraction of light by the regularly arranged and correctly
spaced spheres.) Australian precious opal is considered to have been
precipitated in near-surface cavitiesfrom gels concentrated by evaporation
from siliceoussolutions in groundwater (Jones et al.,1964; Sanders, 1964;
Darmgh et al.,1966; Pollard and Weaver, 1973).
Study of marine sediments has led to the conclusion that with time the
"amorphous" opaline silicaof biogenic origin is dissolved and re-precipitates
as cristobaliteand sometimes as chalcedony. Conversion to chert takes place
by a solid-statetransformation in which microquartz (10--50 ~m) nucleates
and grows at the expense of the cristobalite(Heath and Moberly, 1971 ).
This microquartz (Fig. 4D--F) is the principal component of cherts which
are older than Cretaceous. Chalcedony, a microfibrous variety of quartz
containing water-filledpores is a minor constituent fillingfissuresand cavities
314

Fig.4. Transmission and scanning electron micrographs of fine-grained siliceous rocks.

 315

in cherts. Granular and spongy surface textures in chert have been related to
impurity content and rate of precipitation of silica (Folk and Weaver, 1950;
Oldershaw, 1968; Folk and Pittman, 1971; Greer, 1972).
A study of a considerable number of cherts from the viewpoint of their
expansivity with cement alkalies led Kneller and co-workers (1968) to
conclude that a correlation exists between expansivity and micropore
structure. Variations in internal porosity were linked to the extent of
recrystallization and weathering. Somewhat similar ideas have been expressed
by other workers (Niemeyer, 1973). Cherts, however, sometimes produce
unexpectedly high expansions. The microstructure of chert from Missouri
and of novaculite from Arkansas, for example, may be compared with that
of the chert from Banff, Alberta (Fig.4D--F). The Missouri and Arkansas
specimens shown in the micrographs were obtained from the same samples
as those which were tested by Mielenz et ah (1947) in a mortar-bar test and
in which they registered high expansions. The Banff cherts similarly tested,
albeit in a different laboratory, showed only low expansions. Though the
crystallite size of the Missouri and Arkansas material is small the appearance,
on the basis of comparison with the Banff and other cherts, would suggest
only a low expansion--producing potential. Even more remarkable are the
cases of alkali--aggregate reaction involving coarsely crystalline quartz
(Mielenz, 1958, p.25), quartzites (Buck and Mather, 1969; Duncan et al.,
1973a, b, c), granites and chamockites (Gogte, 1973). Hence, while a
correlation between microstructure and expansivity is to be anticipated, the
relationship is evidently complex. Poorly crystallized siliceous rocks are often
etched rapidly on exposure to alkali (Fig.6A, B, p. 318). Solubility of
amorphous silica is affected by the local radius of curvature of the silica
surface, by the number of internally trapped SiOH groups, small amounts of
adsorbed A1 and Fe (Iler, 1973) and other factors such as internal stress and
it seems probable that parameters such as these also affect expansivity in the
alkali--silica reaction.
Extent of expansion often depends upon the proportion and particle size
of a given variety of reactive silica (Stanton, 1940; McConnell et al., 1947;
Vivian, 1951; Bredsdorff et al., 1966). A m o u n t of expansion at a fixed time
plotted against proportion of expansive siliceous aggregate of fixed size
shows a maximum which is often sharp when opal is the expansive component
(Fig.5), but which may be broader for less reactive minerals and rocks. The
term "pessimum" is used to describe the proportion of reactive aggregate
which produces the maximum expansion. This proportion, however, appears
to depend upon the alkali content of the cement (Fig.5) as well as on the
type and particle size of the aggregate and it may be affected by other factors.
When reactive silica is sufficiently finely ground it has been reported to lose
its expansion-producing capability (Fig.3A) (Vivian, 1951) and it functions
as a satisfactory pozzolan (Bennett and Vivian, 1955). Recently it has been
shown, however, that opal from the Faroe Islands will produce expansion
when ground to pass the No.300 sieve and used in appropriate proportions
(Diamond and Thaulow, 1974).
316

1.4 - ALKALI CONTENT OPAL SIEVE SIZE

EQUIV No20 (MESH)
• 1.07 16-50
L2 H

, 16 - 5 0

z I0
o
6o
z
~ 08
n
x
w

a: 0.6
w
Z
d 0.4

0.2

5 I0 15 20 25 30 35
GMS O P A L / G M S ALKALI

Fig.5. Expansion of mortar bars (ASTM C227) containing Mexican opal at age of 3
months (100°F; 37.8°C).

Expansion due to alkali--silica reaction has been suppressed by addition

of a b o u t 1% of the weight of cement of soluble salts of lithium and barium
(Fig.3A) (McCoy and Caldwell, 1951; Hansen, 1960). Silica glasses contain-
ing lithium and lead, unlike those containing sodium and potassium, have
been found to be non-expansive in the mortar-bar test (Pike et ai.,1960).
These findings generally have been attributed to the lower solubility of
lithium silicates in comparison to those of sodium and potassium (Shmidt,
1960). Soluble lithium silicates are known (Mellor, 1947) and lithium-
stabilized colloidal silicas have been described (Iler, 1973). Also lithium has
the lowest ionic mobility and the largest hydration in solution of the alkali
metal ions (Sneed and Brasted, 1957, p.36).
The mechanism of expansion involves moisture uptake by the siliceous
aggregate which leads to an increase in volume. When the pressure exceeds
the tensile strength, the concrete or mortar will crack. It once was thought
that the water imbibition was due to osmosis, the cement paste acting as a
semi-permeable membrane separating an alkali--silica gel from water of pore
solutions in the cement (Hansen, 1944). Experiments showed that cement
paste will indeed function as a semi-permeable membrane (Verbeck and
Gramlich, 1955) b u t it was also found that expansion due to alkali--silica
reaction had sometimes continued even after extensive cracking had rendered
the cement useless as a barrier b e t w e e n fluid phases. The more m o d e m view
is that although the mechanism is related to osmosis, a semi-permeable
membrane probably is n o t required. Expansion results from swelling pressures
generated while the silica is still solid, though it frequently is converted to a
liquid at some stage of the reaction, owing to decrease in viscosity (Vail,
1952; Iler, 1973). The moisture migration takes place in response to a
 317

gradient in the relative vapour pressure and is accompanied by a lowering in

the partial free-energy of the water (Powers and Steinour, 1955). Attempts
to extend this theory to account for other features of the reaction on the
basis of diffusion rates of alkali versus calcium ions have won less general
acceptance (Diamond, in press). The concrete takes up water from its
external surroundings to replenish the self-dessication losses caused by
water movements within the material. Hence concrete in a dry environment
is generally not subject to durability failure from alkali--silica reaction.

TYPE II -- A L K A L I - - C A R B O N A T E - R O C K REACTION

Well-lithified carbonate rocks generally make excellent concrete aggregates.

Reaction between dolomitic-limestone coarse aggregate and cement alkalies
that caused expansion and cracking of concrete in the presence of moisture
was first described clearly during the early 1960s (Swenson and Gillott,
1960; Hadley, 1961; Newlon and Sherwood, 1962). It since has been
concluded that potentially expansive rocks probably occur in most
geographic areas where there are limestones and some of these alkali-reactive
aggregates may be expected to be sufficiently sound to pass physical
acceptance tests.
The alkali-expansive rocks are typically grey, very fine grained, dense and
of close texture in hand sample. In thin section under the petrographic
microscope, dolomite may be seen as isolated well-formed rhombic euhedra
(~50 ~m) sometimes containing regularly arranged inclusions. The matrix is
very fine grained and consists of calcite (~3--5 ~m), clay and other detrital
minerals (Gillott, 1963a). The scanning electron microscope discloses that
the clay may be preferentially distributed close to the dolomites. This may
be because the phyllosilicates 8 as dolomite nucleators or because crystal
growth of the carbonate tends to expel the clay as an impurity. The dolomite
is commonly of the metastable variety which contains more CaCO3 than the
ideal 50 mole percent. In the calcite the Ca is sometimes partially replaced
by Mg in amounts which vary from a fraction of a mole percent up to
several mole percent. Illite and chlorite are the clay minerals which most
frequently have been reported.
A few years after the initial discovery of the problem, two laboratories
found independently, and at about the same time, that a "dedolomitization
reaction" takes place (Swenson and Gillott, 1960; Hadley, 1961). Alkalies
attack fine dolomite and the solid products are calcite and hexagonal plates
of brucite which sometimes show sectors and internal structure (Fig.6E, F);
alkali-carbonate also is thought to be formed in solution. These findings
have been amply confirmed. In addition, other workers reported that they
found hydrated carbonates in dried rock powders separated by filtration
from alkaline solutions (Sherwood and Newlon, 1964). Complex magnesium-
carbonate hydroxides of the hydrotalcite-sjogrenite group of minerals also
were reported on the surface of rock prisms soaked in alkali (Walker, 1967).
None of these findings, though significant, seemed to account directly for
 318

ALKALi •

F ~ . 6 . Scanning electron micrographs of alkali-expansive rocks before and after treatment

with 2M NaOH.
 319

expansion of the concrete or rock prisms immersed in alkali. On the one

hand, the calculated volume of the solid products of the dedolomitization
reaction is less than that of the dolomite which is replaced. On the other
hand, the hydrated carbonates evidently form only when evaporation causes
the salt concentration in solution to rise to levels which all the evidence
indicates are not reached in expanding concrete. Furthermore, concrete
stops expanding under the conditions of drying which are required for
crystallization of hydrated double salts. The distribution and amounts of
complex double salts also seem too small to account for the observed large
expansions.
Most workers considered that the mechanism of expansion had eluded
satisfactory explanation. It seemed to the author, however, that there were
certain particularly significant facts in the information available at that stage.
These were:
(1) the small size of the crystals in the rock and its close texture;
(2) the presence of clay; and
(3) the dedolomitization reaction.
This feeling appeared justified since most expansive rocks had a similar
composition and fabric and it seemed unlikely that the dedolomitization
reaction was purely incidental. Conversely, one or other of these parameters
was absent when non-expansive limestones were investigated. Later extensive
research has in general supported these conclusions.
Various forms of dilatometers were used to measure expansion of
powdered material (Gillott, 1963b). X-ray diffraction and differential
thermal analysis used in conjunction showed that the rate of dedolomitization
corresponded fairly closely to the rate of expansion of powdered rock.
However, analyses also showed that dedolomitization took place at a similar
rate on similar treatment of powdered mixtures which failed to expand. Many
different powdered mixtures were tried. For example, powdered protodolo-
mite and calcite of the same particle size range as in powdered expansive rock
were mixed in the correct proportions with the acid-insoluble fraction
separated from expansive rock. Dedolomitization, but no expansion,
occurred when alkali was introduced. Thus it became evident that dedolomi-
tization itself could not account for the difference between expansive and
non-expansive materials. As was expected, the rate of dedolomitization was
faster for fine-grained powders than for coarser ones. It was also found that
the amount by which powdered rock expanded depended on its particle size
distribution. Contrary to expectation, however, more finely ground rock
expanded less than coarser rock powders. This seemed to contradict the
supposition that dedolomitization was in some way responsible for expansion
and was the cause of careful re-examination of the evidence. Since coarsely
powdered rock showed large expansions, very finely powdered rock smaller
expansions, and mixtures of the pure components no expansion at all, it
finally became clear that the fabric of the rock must play a key role in the
expansive mechanism (Gillott, 1964).
Microcracks can sometimes be induced by thermal shock and rock wafers
320

treated in this way develop a capacity for expansion on exposure to moisture

similar to that which they normally display when soaked in alkali. Conversely,
when placed in alkali, the thermally shocked wafers show no expansion
b e y o n d that which they achieve on first exposure to moisture (Swenson and
Gillott, 1967).
Pore solutions in the sediment at the time of deposition are expelled
during lithification and minerals gradually lose their adsorbed moisture. The
rock develops a tight fabric and so mineral surfaces subsequently remain dry.
The role of the dedolomitization reaction is to open channels through which
moisture and solutions enter the rock where surface hydration and sorption
leads to moisture imbibition and the generation of swelling pressure. The
conclusion is that the moisture intake by the clay and other fine constituents
causes the expansion of the rock.

TYPE III -- ALKALI--SILICATE REACTIONS

Phyllites were among the first rocks to be associated with expansive

alkali--aggregate reaction. Since then, related rocks -- greywackes and
argillites -- have been found to be involved (Duncan et al., 1973a, b, c;
Gillott and Swenson, 1973). These rocks c o m m o n l y contain quartz, feldspars,
rock fragments, phyllosilicates and sometimes carbonates and other accessory
constituents. Expansible phyllosilicates are sometimes present in the clay size
or coarser size range.
The quartz is c o m m o n l y fine-grained and strained. Because of this evidence
of relatively high specific surface area and disorder in the crystal structure, it
has been postulated that the quartz may be alkali-reactive. Hence the rocks
may expand b y a similar mechanism to that proposed for the alkali--silica
reaction when minerals such as chert or opal are present. This may be so, b u t
studies of the greywackes, phyllites and argillites from Nova Scotia provided
clear evidence that in those rocks the phyllosilicates are at least partly
responsible for expansion in the alkali--aggregate reaction.
X-ray diffraction and scanning electron microscopy were used to assess
the effect of alkali and h o t water on powdered rock and rock wafers. R o c k
surfaces were photographed on the scanning electron microscope before and
after the rock had been immersed in alkali or water (Gillott, 1970). Likewise,
X-ray diffractograms were recorded from rock wafers before and after
soaking in alkali or water for increasing periods of time.
The scanning electron micrographs~showedthat certain phyllosilicates
exfoliate after alkali treatment (l~g.6C, D). Also the X-ray diffractograms
showed a shift in the position of a peak from about 10 £ to a b o u t 12.6 £
after treatment of the rock wafers in alkali. There was no corresponding
shift in peak position after similar soaking of wafers in h o t water, even after
immersion for more than one year and although the samples were held at
high humidity while the diffractograms were recorded. The peak positions
and response of the material to other pre-treatments did n o t correspond
exactly to those of vermiculite.
 321

The phyllosilicate was linked by size with brown porphyroblasts which in

optical thin section showed marked pleochroism and which looked like biotite
sometimes partly altered to chlorite. It is not known whether biotite
exfoliates after alkali treatment and it would be interesting to investigate
this possibility. It seemed more probable, however, that the mineral was
related to vermiculite. Several authors have described clay minerals in which
there are interlayer precipitates which partially fix the basal spacing (Gillott,
1968, p.205). Possibly there are similar interlayer precipitates in the brown
pleochroic mineral. Removal of the interlayer precipitates by alkali would
make it possible for the mineral to exfoliate and account for the changes
observed by scanning electron microscopy and X-ray diffraction. Water intake
accompanying the exfoliation would generate swelling pressure and it was
concluded that these processes were largely responsible for the alkali-induced
expansion of the rock (Gillott et al., 1973).
The difference in mechanism no doubt accounts for the differences in
behaviour of this variety of alkali--aggregate reaction from those observed in
the other main categories. Other expansible phyllosilicates may contribute
to expansion. In general such silicates are readily detected by X-ray
diffraction methods. It should be made clear that not all layer-structure
silicates exfoliate when soaked in alkali but some of those present in the
greywackes, phyllites and argillites in Nova Scotia do so and hence similar
minerals may well be found to give similar results elsewhere.
It seems probable that other silicates will be found which react with alkali.
For example, Mather (1973) expressed the strong suspicion that plagioclase
feldspar was alkali-reactive in concrete highway bridges in Georgia. Studies
of subgreywackes from the Northwest Territories, Canada (Gillott and
Swenson, 1973) have shown that minerals other than layer-structure silicates
are corroded by alkali, though it is not known to what extent these reactions
are involved in the mechanism of expansion in that case.
Evidently expansion due to alkali-attack upon rock can result from new
and previously unsuspected mechanisms. So it is proposed that such cases be
placed in a new category termed alkali--silicate reactions.

CONCLUSIONS

(1) The poor durability of concrete which can result from alkali--aggregate
reactions is a problem expected to become more common and more severe
because of present trends in concrete practice and in cement manufacture.
(2) Absence of some of the features associated with alkali--silica reaction
does not imply that alkali--aggregate reaction may be excluded as a cause
of poor durability of concrete. There is more than one expansive mechanism.
(3) Alkali--aggregate reactions may be subdivided into three categories
termed the alkali--silica reaction, the alkali--carbonate-rock reaction, and
alkali--silicate reactions.
(4) An understanding of the mechanisms of these reactions helps in the
identification of potentially expansive rocks and minerals. It may also lead
322

to a better understanding of appropriate remedial action.

(5) It is important to carry o u t the necessary tests and analyses when
assessing the suitability of rocks and gravels for use as concrete aggregates.
(6) Tests for alkali-expansivity include: examination by a petrographer
with experience of alkali--aggregate reactions; measurement of dimensional
change characteristics of mortar bars, concrete prisms, or rock cylinders.
(7) Limits in dimensional-change tests require careful consideration. Some
aggregates which pass accepted tests cause p o o r durability of concrete.
(8) Dimensional-change tests sometimes have to be accelerated.

ACKNOWLEDGEMENTS

I wish to thank Dr. J. W. Costerton, Howard Johnson and Bob Fitch for
assistance. Financial support is acknowledged from The University of Calgary,
the Defence Research Board, and the National Research Council of Canada.

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