The volume stability of modern steelmaking slags

L. M. Juckes

Most processes of steel manufacture necessarily generate the current larger tonnages of a by-product that has
a substantial proportion of slag. Often much of this is many examples of successful usage.
landfilled, and at many plants it will be the main item (by For many steelworks, a significant proportion of
tonnage) that is dumped. This rock-like material can be this slag will be landfilled, and of the materials
used as an aggregate, but the main obstacle to widespread dumped it will often form the largest proportion.
use is concern over the volume stability. The main cause Steelmaking slags form in the same manner as some of
of volume instability is hydration of free lime, although the igneous rocks that make prime aggregates, and
hydration of free magnesia may also contribute in some they have been used in similar fashion. With
cases. There are three key steps to effective use of this increasing pressure in many countries for greater use
abundant secondary aggregate. First, some pretreatment of secondary aggregates, to reduce the extraction of
of the slag is usually necessary (such as weathering). natural materials, steel slags offer a promising and
Second, a test is necessary that reliably predicts the relatively abundant alternative.2 The inhibiting factor
behaviour in use, within a reasonable time. This is is concern over the volume stability of such slags, a
commonly an expansion test. Third, calibration of the factor arising mainly from the presence of free lime
test is necessary so that test results can provide a useful which is an unavoidable feature of slags from some
distinction between material which is suitable and that processes.
which is not; this is normally achieved by linking The focus of this paper is on modern BOS slags and
laboratory tests to road trials. Subject to these three EAF slags, largely from a British or at least Western
steps, steelmaking slag can make a valuable contribution European viewpoint. It refers primarily to the use of
to the need for secondary aggregates. slags in roads, where with suitable precautions they
can be used at all levels (unbound in the lower layers,
The author is at Cliffe House, Great Ayton, North Yorkshire bituminous-bound in the upper courses, and as a
TS9 6EY, UK (E-mail: [email protected]). surface dressing). 3–5 Slag can be used for related
© 2003 IoM Communications Ltd. Published by Maney for applications such as general fill, railway ballast,3,5,6
the Institute of Materials, Minerals and Mining in association armourstone for inland waterways,7 and sewage plant
with AusIMM. Manuscript received 8 July 2003; accepted in filter material.3,5 Much of what follows is also relevant
final form 14 September 2003. to such uses although they often have additional tests
suited to their particular requirements. Steelmaking
Keywords: Steelmaking slags, volume stability, secondary
aggregate slags are not normally used as aggregate for concrete,
although they have occasionally found success in non-
structural applications such as paving slabs and blocks
for breakwaters,8–10 nor for hardcore (fill within
foundations or beneath concrete floor slabs) nowadays11
IMPORTANCE OF STEEL SLAG although there are examples from earlier years where
The major steelmaking processes in Europe are basic they have been documented largely because of problems
oxygen steelmaking (BOS) and electric arc furnace that arose.12,13
(EAF). Both produce about 100 kg slag per tonne of
steel made. There may be scope for some reduction in
this proportion by process improvements, but the
THE NATURE OF STEEL SLAGS
change will not be great and production of such slags Basic oxygen steelmaking slags
is likely to continue well into the future. For instance, Molten iron, or ‘hot metal’, as produced by the blast
a steelmaking route that produces only 30 kg slag per furnace contains certain impurities. Most notable are
tonne of steel has been reported 1 but the further carbon, silicon and phosphorus. Various processes
complexity that it introduces into the process is likely have been devised to remove these, and in particular
to inhibit wider adoption. Moreover, although the the variants of basic oxygen steelmaking (BOS; also
secondary steelmaking slags that are generated are referred to as BOF or basic oxygen furnace). The
smaller in total tonnage, finding good disposal routes main variants have been described by Deo and
for smaller streams of unfamiliar materials may in Boom,14 the most widely used being the Linz-
some cases turn out to be more difficult than utilising Donawitz (LD). The oxygen is injected via a lance,

DOI 10.1179/037195503225003708 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112 C177
Juckes The volume stability of modern steelmaking slags

and initially the carbon, silicon and phosphorus oxidise properties and may be recycled or sold to outside
in preference to the iron. As oxides, these elements can markets, they are too diverse to permit a general
then migrate to the slag or the atmosphere, and the discussion of them as a group here. In most cases, it is
exothermic oxidation reactions provide energy to important that they should be kept separate from any
maintain or raise the temperature of the liquid steel. The BOS slags that may be intended for use as an
‘basic’ refers to the lime-rich slag required to remove the aggregate.
phosphorus effectively, with lime/silica ratios typically
around 3 and also to the basic refractories necessary to Other slags
withstand attack by such slags. The slags commonly Other metallurgical processes generate types such as
described as BOS slags are, strictly speaking, known as blast furnace slags and those from non-ferrous metal
vessel or converter slags to distinguish them from any production. These all have their own distinctive
secondary slags that might arise during the complete compositions, properties and characteristics so it is
processing of each batch of steel. important for the user to be aware of the precise type
involved when slag is utilised. In colloquial English,
Electric arc furnace slags an even wider range of materials including cinders,
In the electric arc furnace (EAF), energy is provided ashes and even colliery waste is sometimes termed
electrically and the feed normally consists of scrap or ‘slag’. The considerations described in this paper are
directly reduced iron; again, there are many variants.14 not appropriate to any of these materials.
There is usually still a need to reduce the phosphorus
content, and thus to use a basic slag, although basicities Plant treatment
tend to be lower than in BOS slags. Consequently, Steel slags are formed at a temperature of about 1600°C,
contents of free lime are lower, and these slags have an and their cooling history will affect properties.
excellent reputation as aggregates for roads, particularly Treatment routines at individual plants may differ in
in the upper, bituminous-bound layers.15,16 The alkalinity detail, but most follow a similar pattern. At BOS plants,
caused by the free lime and the lime-rich phases has the slag is commonly tipped from the vessel into slag
benefits in improving the adhesion of asphalt to the ladles and, depending on ladle size, it might be held
particles and giving a harder end product. 12 there until slag from subsequent batches (‘heats’ or
‘blows’) has been added and the ladle filled. It is then
Open hearth slags tipped into slag pits by which time some or all of the slag
Many of the early studies concerning stability were may have solidified. In earlier times, slag pits could be at
conducted on slags from the open hearth (OH) process, some distance from the plant; more modern layout has
which dominated the industry in the first half of the them close to the furnace to avoid the capital and
20th century. By the 1960s, such plants were being maintenance expense of rolling stock to convey the
replaced by the faster oxygen processes; in Britain, BOS ladles. When each pit is full, it is excavated while another
steelmaking had overtaken OH in tonnage terms by is filled.4 Cooling is often accelerated by spraying with
197217 and within a few more years OH production had water. Similar practice may be followed at EAF plants
ended. There was a similar pattern elsewhere in Western or else the slag may be dumped directly beneath the
Europe. The slags from this process are sufficiently furnace and cleared out in relatively small batches. The
similar to those from BOS and EAF for conclusions different cooling rates (slower in a pit) lead to different
concerning testing, treatment and utilisation to be textures and porosity, and thus often different physical
generally interchangeable. The use of OH slag seems to properties. In both cases, strict discipline is necessary to
have generated a disproportionate number of reports of exclude general rubbish and other steelworks materials
damage to structures (e.g. Crawford and Burn12 and such as refractories and spillages of alloying materials.
Gnaedinger13). While there may be unique aspects of its Although the need for this has been known for many
composition that contributed to this, a major factor years,20 it has usually been seen as an unnecessary
appears to have been the use of untested, and even expense at plants where the slag has not been utilised
unidentified, material in inappropriate situations in an and so the slag pit has often been regarded as a
era when the need for precautions had not yet been fully convenient rubbish disposal facility. In such cases, when
recognised. a market is subsequently found for the slag, it can
require considerable effort to achieve the necessary
Secondary steelmaking slags change in attitudes.
Deo and Boom14 defined secondary steelmaking as Molten slag poured into slag pits near the furnace
the after-treatment of the liquid steel produced in a is often contained by walls or bunds of cooled slag. At
primary steelmaking process; a number of different plants where other varieties of slag (such as secondary
processes may be used. 14,18,19 For convenience in the steelmaking slags) are also produced, it must be
task of considering slag disposal, one may include ensured that the slag used for these bunds is of the
pretreatments such as external desulphurisation under same material. Depending on practice, some or all of
this heading. Some of these processes take place in the the bund material may be recovered with the cooling
ladle and thus the slags may be referred to as ladle slag and so contamination is possible if other types are
slags. Suffice it to say that these processes produce a present.
wide compositional range of slags, in comparatively After cooling there can be a delay varying from
small quantities. Although some of them have useful days to months, during which the slag is exposed to

C178 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112
 Juckes The volume stability of modern steelmaking slags

Table 1 Chemical analyses of typical British BOS slags, 198724

Sample source Total Fe CaO SiO2 MgO Al2O3 P 2O5 Mn Total S CaO/ Free Ca(OH)2 CaCO3 UHFL
SiO2 CaO

Scunthorpe 20·37 43·54 11·99 7·76 0·99 1·15 2·98 0·14 3·63 3·9 1·15 0·34 3·0
Ravenscraig 19·46 44·42 15·19 6·88 1·40 1·01 3·32 0·07 2·92 2·5 0·29 1·25 2·3
Llanwern 24·20 36·45 12·11 4·15 2·22 1·12 4·27 0·10 3·01 5·4 3·00 1·45 3·1
Port Talbot 18·64 45·83 10·74 6·65 2·10 1·19 2·73 0·09 4·27 11·9 6·57 1·66 6·9
Teesside 20·86 41·86 11·92 6·51 3·43 1·47 3·18 0·21 3·51 7·2 0·66 0·77 6·7

UHFL, unhydrated free lime.

atmospheric weathering, before the slag is crushed and Of the other components of the hot metal, the
screened. At this stage, it usually contains a substantial phosphorus will be oxidised to P2O5 and enter the slag
amount of metallic iron in lumps or nodules of all sizes. where it is thus usually, though not always, reported as
These will be removed magnetically, the efficiency of the P2O5. In earlier processes, in the first half of the 20th
removal depending on both the de-metalling plant and century, the P2O5 content of many slags in Western
the preceding crushing.21 This metal will then be sold or Europe could be in the order of 12–16% and such slags
recycled to the steel plant or blast furnace (the finer were in considerable demand as fertilisers (which is why
fractions usually containing a substantial proportion of they are now rarely found in old tips). With BOS slags,
slag still adhering to the metal). Examples of individual the content is more commonly around 1–2%.
plant process flows are given by Sahay et al.21 and The carbon in the hot metal escapes as carbon
Bannenberg and Arlt.22 At some plants, the same monoxide; at some plants it may be captured for use
crushing, screening and de-metalling circuit is used both as a fuel gas. Of the manganese which is usually
for the vessel slag and for other materials such as present, a significant proportion will oxidise and enter
secondary steelmaking slags (e.g. processing those the slag. A certain amount of the iron itself will do
materials on one day of each week). Such other likewise, leading to Fe contents typically around 20%.
materials must be assessed and, if their incorporation While such loss of iron reduces the yield, it is an
into the slag would be detrimental to its properties or inherent feature of the process and does lead to some
conformance with specifications, then the shared improvement in dephosphorisation.
facilities must be thoroughly cleaned at each change- With a batch process, and operated to give products
over. (At plants where the process circuit includes units that may differ from batch to batch, a substantial degree
such as screens and hoppers whose construction makes of variability is inevitable and so it is not easy to nominate
them difficult to clean effectively, thorough cleaning typical slag compositions. Juckes24 gave chemical
may be so impractical that it becomes preferable to compositions for BOS slag samples from the five
exclude other materials permanently.) The sized, de- integrated works of British Steel in 1987. These analyses,
metalled slag is then normally stored in heaps to shown in Table 1, were compared with the mineralogy as
weather for a specified minimum period prior to determined by reflected light microscopy as shown in
utilisation, a matter discussed in more detail later. Table 2 and despite the years these compositions should
These successive processes have a mixing effect on a be a reasonable reflection of more recent slags. The
material which is produced in somewhat variable samples were collected directly after de-metalling and
batches, and lead to a more uniform product. were estimated to represent a composite from about 7
days’ production. Other published accounts of chemical
Composition and mineralogy and mineralogical composition (for example Motz and
As noted above, the key feature of BOS slags is their Geiseler,2 Presslinger et al.25 and Proctor et al.26) are
high lime/silica ratio; this is achieved by the addition available covering a wider geographical range.
of lime as a slag-former. This addition may also Fluxing agents have been used to lower the
contain enough magnesia to raise the content in the viscosity of the slag and its liquidus temperature,
slag to 6–8% in order to reduce attack on the vessel facilitating the assimilation of lime and thus
lining, despite an adverse effect on the efficiency of the accelerating the dephosphorisation. Fluorspar is the
dephosphorisation. 23 (Some of the flux may be added most commonly used of these, followed by borates
as uncalcined limestone or dolomite, for a coolant such as colemanite, although many other materials
effect.) The silicon in the hot metal is oxidised to have been tried such as briquetted red mud from
silica, which enters the slag and adjusts the lime/silica aluminium smelting. Microscopic and chemical
ratio. Where the initial silicon content of the hot metal analyses of a group of BOS slags confirmed that those
is low (say 0·2–0·3%), this may not be sufficient to give containing fluorine had less free lime and that it was in
the desired lime/silica ratio when the quantity of lime smaller particles.27 It is now rare for such fluxing agents
necessary for adequate phosphorus removal is added; to be added to the BOS vessel in Britain (although they
in such cases, extra silica may be added, for instance as may be used in secondary steelmaking or the EAF
natural stone or blast furnace slag.23 This may also process). The main arguments against them are the cost
raise the alumina content, which can aid the fluxing of of materials, the increased attack on refractories, and
the additions. In addition, iron ore may be added as a the environmental considerations both during plant
coolant, contributing to the FeO content of the slag.23 operation and subsequent utilisation of the slag product.

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112 C179
Juckes The volume stability of modern steelmaking slags

Table 2 Mineralogical analyses of typical British BOS slags, 198724

Sample source C3S Inverted C3S C2S RO Spinel C 2F Free lime Free MgO Others Hydrated/
carbonated lime

Scunthorpe 11·8 10·2 25·6 24·0 2·0 14·6 8·0 2·4 0·8 0·6
Ravenscraig 0·6 7·4 47·0 22·8 0·6 15·8 4·2 0·8 0 0·8
Llanwern 1·8 9·0 31·2 22·0 4·8 14·2 10·2 0·4 6·0 0·4
Port Talbot 2·6 26·2 16·2 18·6 4·4 11·8 13·4 1·0 5·8 0
Teesside 0 7·4 28·6 14·4 5·2 17·4 15·8 1·0 10·2 0

C3S, tricalcium silicate; inverted C3S, dicalcium silicate formed from the inversion of C3S; C2S, primary dicalcium silicate; RO, FeO
probably including small proportions of other divalent oxides; C2F, calcium ferrites, probably mainly dicalcium ferrite.

Trace element contents of slags from the production in the range 3·1–3·7 g cm–3 for BOS slag, compared with
of carbon steel are normally such that they conform 2·8–3·1 g cm–3 for basalt and 2·6–2·8 g cm–3 for granite.
with relevant leaching tests.9,26 Stainless steel is mainly For some purposes, such as armourstone or aggregate in
produced in arc furnaces and the resulting slags can concrete for sea defences, the extra weight is
contain higher contents of elements such as Ni and Cr. advantageous. In roads, the density leads to a lower
The levels of these, and the extent to which they are ‘spread rate’,5 meaning that more tonnes of aggregate
locked within insoluble phases, would have to be are needed per metre of road (unless the properties of
examined for each example. Specifications exist for the the slag allow a different combination of road layers and
environmental aspects of slags and other aggregates2,26,28 thicknesses that can give the same performance while
but these are not considered here. using less aggregate).15 Failing this, both the tonnage
Goldring and Juckes29 described in detail the that has to be purchased overall and the associated
mineralogy of steelmaking slags, although their transport costs are likely to increase.31
reference is mainly to slags from earlier periods. Table 2
shows that the main components of more modern BOS
slags are typically dicalcium silicate, RO (a mixed oxide, VOLUME STABILITY
mainly FeO), calcium ferrites, tricalcium silicate It has long been known that free lime can hydrate
(inverted or metastable), and a spinel close in expansively and can disrupt fragments of steelmaking
composition to magnetite (Fe3O4). Free lime can in slag;12 to a lesser extent, free magnesia may do likewise
some cases be abundant enough to qualify as a major but more slowly.12 It has even been suggested that free
phase, as can free magnesia. (As pointed out elsewhere,29 magnesia is the main expansive component in
the correct mineral name for the former is simply ‘lime’ weathered OH slags because the free lime will hydrate
but that could be ambiguous. Goldring and Juckes naturally within a fairly short time.13 That does not
preferred the name ‘lime phase’, leaving the term ‘free appear to be the case with modern BOS and EAF
lime’ for the figure determined by chemical analysis. slags, where the free lime is normally regarded as
However, the term ‘free lime’ is widely used and being the predominant factor.
understood by both sellers and users of slag as an Because of the wedging effect that may occur,
aggregate, and so that term will be used here. Similarly, whereby a small nodule of free lime can open up a
the term ‘free magnesia’ is more widely recognised fissure extending across the entire fragment, the
within the industry than the correct mineral name expansion that is observed may be substantially greater
‘periclase’.) The compositions of individual phases have than what might be calculated as the theoretical volume
been reported25,29 although the amount of variation increase in the free lime present if it were all to hydrate.
possible within individual phases is not always certain. (This effect may explain observations which have in
It should be remembered that with micro-analysis some cases been interpreted as implying the presence of
techniques, it is not a true point that is measured but a some other unidentified expansive component, as in
spot with significant area and depth, so that in material Verhasselt and Choquet. 32) This applies mainly to
with a fine crystal size it may extend beyond the individual fragments; however, depending on the
boundaries of the crystal of interest. packing density of the aggregate as a whole, the
The mineralogy of steelmaking slag has similarities to expansion of individual fragments of slag may be partly
that of Portland cement clinker, leading some to speculate or fully accommodated by the interparticle porosity of
that it could have similar cementitious properties; the mass as a whole. Thus, in general, a certain
unfortunately, tests show either poor strength or even amount of expansion may be tolerated in slag used as
failure to set.9,30 The main phases of importance to this an unbound aggregate; the problem is knowing the
paper are free lime and free magnesia, which may hydrate threshold at which the expansion becomes
expansively, and dicalcium silicate and tricalcium silicate, unacceptable for the sake of the volume stability of the
which may also react with water and thus influence the aggregate as a whole in any particular application.
study of the free lime and free magnesia. The different requirements of individual applications
This mineralogy leads to a material that is denser are a major consideration. For instance, this is why
than most other potential aggregates (and more so, if steelmaking slags are very rarely used as aggregates for
metal removal was inefficient), a characteristic that can concrete. The nature of concrete means that there is
affect utilisation. Alexandre et al.8 quoted bulk densities not the porosity to absorb the expansion of some

C180 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112
 Juckes The volume stability of modern steelmaking slags

particles as would happen in, say, an unbound layer of oxidation of FeO to magnetite (Fe3O4). This effect,
a road; any local fractures will propagate more readily common at some works but absent at others, causes fine
and over longer distances in concrete. Moreover, pervasive fracturing that weakens the slag to the extent
deterioration of concrete components (such as parts that it is quite unsuitable for use as an aggregate. Little if
of bridges or buildings) can bring a risk to life whereas anything has been published on the mechanism,
with the deterioration of a road the consequences may although such slags (described in German as zerfallen)
be inconvenience and added expense but rarely are commercially significant. Basic steelmaking slag is
include direct risk to life. However, BOS slag has been sometimes milled and sold as an agricultural liming
tested as a concrete aggregate in blocks for coastal agent, and with this disintegrated slag sufficient natural
defence.8 In this situation, if blocks should deteriorate fines can be screened out at the specified size to
there is no direct danger to life although they would eliminate the expensive grinding process; two product
need to be replaced at some convenient time. During categories based on this material are recognised in
the life of the blocks, the high density of the slag is an Germany.38 This effect does not appear to have been
advantage. recorded in slags from other countries and is not
Other potential breakdown mechanisms do exist but considered further here although it should not be
there is little or no evidence of their affecting steelmaking overlooked when seeking causes for cases of unexpected
slag aggregates. Dicalcium silicate (Ca2SiO4, often weakness or disintegration.
abbreviated to C2S) is a major component in steelmaking Carbonation of the hydroxides of calcium and
slags, and the b-form of this phase can undergo an magnesium is a widespread phenomenon in slags as
expansive phase inversion on cooling through a they weather, and the associated volume increase
temperature of about 400–500°C with disruptive effects (theoretically about 12% for calcium and 15% for
on the surrounding structure (a phenomenon known as magnesium) has led some to regard this as another
‘falling’). As discussed by Juckes,33 this can occur with potentially expansive reaction. 39,40 Examination of
certain blast furnace slags but only on cooling. Some samples, particularly with the optical microscope,
countries have Standards with test methods to guard indicates that carbonate formation is largely as crusts
against the marketing of blast furnace slag weakened by on outer surfaces and sometimes as linings to
this mechanism; in Europe, BS EN1744: Part 134 fractures created during the hydration stage. While
contains such a test. Although many publications of expansion during the carbonation stage cannot be
British origin describe this inversion as capable of ruled out, its contribution seems likely to be negligible
occurring at ambient temperatures, these appear to be compared with that caused by the hydration.
based on a misunderstanding of earlier reports and there The large volume increase in the formation of some
is no sound evidence that such inversion subsequent to hydrated silicate phases has prompted speculation that
cooling has ever been recorded as occurring, let alone such crystalline hydration could also play a role in some
affecting the performance of an aggregate.33 This effect is observed cases of aggregate heave.39 As pointed out in a
unrelated to the question of the volume stability of response to that suggestion, at certain stages some of the
steelmaking slags but it is necessary to draw attention to reaction products become gels that can expand into
it because it appears at times to have been confused with existing voids without causing an overall volume
the expansion caused by the hydration of free lime (e.g. change.41 This view appears to accord better with
Schuur and Broadbent35 and Taylor and Cripps36). observed behaviour; the fact that a reaction involves
Various trace components, including phosphorus increased crystal volume does not lead automatically to
and boron, are known to stabilise the b-form of disruption of the surrounding structure, as is illustrated
dicalcium silicate. Certainly in BOS slags, the by the setting of Portland cement which is based on
phosphorus content appears to be the explanation for similar hydration reactions. (The situation might be
the observed stability of the b-form. Although the different for certain phases that may form in old blast
possibility of dicalcium silicate inversion in BOS slag furnace slags, with their higher sulphur content,42 but
has been specifically mentioned as a reason why such that does not apply to steel slags.)
slags should not be used as aggregate for concrete, 30 Hydration of sulphide phases in blast furnace slag
there is no evidence that this has ever affected BOS can contribute to volume instability when those
slag aggregates and it is not the real reason why slag is phases are present in substantial amounts. 34 The
not normally used in concrete. Even if such sulphur content of EAF and vessel slags is normally
breakdown did occur, it would be observed at the low (see for example Table 1) and so it should not be a
plant before marketing. At certain plants, EAF slags problem with such materials. (It is worth noting that
with a particularly low P content have been observed certain papers may give an erroneous impression of
to break down during cooling as a result of dicalcium sulphur content. A common phase in some steel slags
silicate inversion so frequently as to be a major has been identified as the calcium aluminoferrite
problem. In one case described, stability was restored known as brownmillerite, and this is occasionally mis-
by adding sufficient boron to the molten slag to spelled ‘brown millerite’, e.g. Monaco and Lu.40
stabilise the b-form. 37 The wide range of secondary Millerite is a nickel sulphide and would not be
steel slags also includes varieties which can undergo expected in such slags.)
similar breakdown. Steel slags as excavated from the pit may contain
Another instability mechanism has been reported inclusions of steel ranging from microscopic to metres
from Germany, where it has been attributed to the across. Rusting of this metal within a slag lump can

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112 C181
Juckes The volume stability of modern steelmaking slags

cause fracturing or even disintegration but after de- lining is MgO. An alternative approach, typically seen
metalling in modern plants the remaining metal in Germany, is to take cognisance of the fact that
nodules are normally small and few. Furthermore, MgO in the slag reduces its dephosphorising capacity
such rusting is a relatively rapid reaction and much of and to give this greater priority at the expense of lining
it takes place during weathering so that this potential life. In such operations, the flux is lime and typically
mechanism appears not to have been recorded as the lining is doloma. In either case, the life of the
causing any practical problems to aggregates in use. lining can be extended by slag washing or slag
splashing, where the lining is protected by coating it
Free lime with liquid slag between heats and allowing it to
Free lime in steelmaking slags occurs in various forms, solidify.45 This liquid slag may also be used as a carrier
and different authors have classified these in varying for fine solid slag particles, doloma or crushed
ways.29,43,44 Basically there are three forms: (i) undissolved magnesia brick to enhance the effect.
particles or lumps of the lime that was charged; (ii) lime Free magnesia from both these sources may be seen
precipitated from the melt during cooling; and (iii) free in BOS slags.29,43 Their appearances under the
lime exsolved from tricalcium silicate (Ca3SiO5, often microscope are different, with that from doloma flux
abbreviated to C3S) when it dissociates to dicalcium being finer and intimately mixed with lime or lime-
silicate. rich phases. Although both types of free magnesia
The free lime of unassimilated origin is widely may subsequently hydrate expansively, observation
regarded as the most likely to cause damaging suggests that damaging expansion is more associated
expansion. Certainly, it is the only form that can occur with that originating from refractory sources.
in large nodules, say several millimetres or more Free MgO forms solid solutions with other divalent
across, and these can contribute disproportionately to oxides more readily than free lime does, and
the expansion of the aggregate as a whole. particularly with FeO and MnO. The phase relations
The free lime precipitated from the melt has also of the solid solution MgO–FeO show that at lower
been implicated in expansion. This, however, is rarely temperatures the crystals will be more FeO-rich, and
seen in crystals or crystalline aggregates of more than optical microscopy can easily demonstrate that this is
a few hundred micrometres. When initially formed, it the case for the outer zones of such crystals, the last
normally contains substantial amounts of other parts to form during cooling. Crystals richer in FeO
divalent oxides such as MgO, FeO and MnO although will be less likely to hydrate, and Geiseler et al.46 have
these will to some extent be exsolved on cooling. What studied this effect. They established various contents
remains will have a stabilising effect; Inoue and Suito 27 of FeO and MnO at which mix-crystals were stable
found that about 20% of combined FeO and MnO depending on hydration conditions, including the
made free lime unreactive to ethylene glycol and it extreme conditions of autoclave treatment, and
seems likely that resistance to hydration rises similarly, suggested that any crystals with more than 40% MgO
although not necessarily with the same thresholds. might be capable of hydration reactions. Such crystals,
Tricalcium silicate is only stable above a temperature with up to 60% FeO, could well be identified by a
of about 1250°C, although it often survives metastably microscopist as RO phase rather than as free
during cooling to ambient temperatures and for an magnesia. However, their evidence makes it clear that
apparently unlimited time beyond that. In other cases, in many cases such crystals, although mainly of a
it inverts to a mass of polycrystalline dicalcium silicate composition capable of hydrating, will be protected
that retains the characteristic outline of the coarse from reaction by a more inert jacket with a lower
euhedral crystals of tricalcium silicate. This dicalcium MgO content.
silicate can only be formed by the exsolution of free
lime, which forms fine vermiform inclusions. These will Hydration processes
presumably be free of impurities such as FeO and The nature of the hydration reactions of free lime and
MnO, and thus inherently more prone to hydration. free magnesia are crucial to understanding their
However, they are small and normally completely behaviour in use. In particular, Ramachandran et al.47
enclosed within the mass of dicalcium silicate which have demonstrated that the hydration of free lime by
will shield them from outside moisture. Thus although water vapour is more expansive than hydration by
these inclusions can amount to a significant proportion liquid water, apparently because the hydroxide is all
of the free lime present in a slag, their contribution to formed at the original site of the free lime whereas
the expansion during hydration appears to be small if with water there is some solution and transport,
not negligible. distributing the hydroxide formation and its effect
over a larger volume.
Free magnesia The behaviour of slag can be observed by chemical
Magnesia in steelmaking slags arises from two main analysis of samples taken at regular intervals as it
sources, fluxes and the refractory linings of the vessel, weathers under outdoor conditions. In a climate with
and their relative contributions depend to some extent regular rainfall, a clear pattern can be recognised.
on practice. In some cases, with British BOS plants Initially, over a period of weeks, some free lime
providing examples, the emphasis is on prolonging the hydrates to form Ca(OH)2. This tends to be the free
life of the vessel lining. The flux is then largely doloma lime that is easily accessible to moisture, in other
(calcined dolomite, effectively CaO·MgO) and the words at the surfaces of pieces or beside fissures, and

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 Juckes The volume stability of modern steelmaking slags

Table 3 Test results for slag samples from the sub-base of a intended to monitor the reactions of the free lime
road panel50 originally present in the slag and so it is possible that
the total of original free lime, if back-calculated, could
Unhydrated Ca(OH)2 CaCO3 Expansion*
free lime (%)
appear to be increasing. In fact this will rarely be
observed because the heterogeneous nature of the slag
As laid 5·8 0·8 1·1 6·9 will normally give rise to significant differences
9 months 5·3 0·8 1·0 ND
17 months 5·1 1·3 2·7 5·9
between analyses of samples even from the same batch
23 months 4·9 2·0 7·0 2·7 and these will obscure other small effects. It may,
36 months 5·1 1·0 8·8 2·1 however, be the explanation for the large rise with time
ND, not determined.
in the CaCO3 values in Table 3 despite the relatively
* Sample held in a climatic cabinet at 80°C and 90% relative small fall in the values for unhydrated free lime.
humidity for 14 days. These hydration reactions appear to make a
significant contribution to the skid resistance of
steelmaking slag.30 While regular wear by traffic tends
in particular the larger nodules. Then, over a period of to polish aggregate surfaces, reducing their skid
months, this hydroxide converts to calcium carbonate resistance, in the case of slag the surface reaction of
by reaction with carbon dioxide in the air. Meanwhile, water-reactive phases on a microscopic scale can
moisture penetrates more deeply but more slowly restore a degree of roughness within hours under
(intermittently assisted by fractures that develop as a moist conditions without causing noticeable loss of
result of earlier hydration) and so hydration reactions road material. A study in 1972 attributed the effect to
continue though at a decreasing rate. Eventually these reaction by a CaO–FeO solid solution; 30 more recent
reactions reach an equilibrium, where hydroxide is observations suggest that the more abundant
being converted to carbonate at the same rate at which dicalcium silicate behaves similarly.
it is being formed. The carbonation reactions can, over time, bind
Extensive testing has revealed that although particles to some extent. Normally this is only
weathering of slag leads to a fall in the content of free significant, or at least noticed as being significant, at the
lime, the value to which it tends asymptotically is surface of stockpiles where fine material can be bound
substantially above zero; the same may be true of into a solid mass. Using more extreme conditions
results from accelerated expansion tests.48 This is (carbon dioxide passed over samples of finely ground
because of the survival of some of the free lime deep slag), Suzuki et al.51 concluded that the carbonation of
within slag lumps, where it is protected from hydration the dicalcium silicate (and even more so, the associated
over a much longer time-scale than the free lime close formation of silicate hydrates) contributed more to the
to or at the surface. In large slag heaps or dumps, this strength increase than the carbonation of the free lime
effect may be more pronounced than in purposely- although in most cases the relative contributions from
constructed weathering piles. Subsequent breakage, these three effects will be difficult to separate. The effect
whether from crushing to produce certain product on slag in normal use is probably small although in
sizes or simply from vigorous handling, can expose Germany for certain aggregate applications it is seen as
this internal lime to surface influences so that further sufficiently important to place them in a separate
weathering will lead to another fall in free lime category with specifications selected to reflect the
content towards a new and lower limit. Expansion binding effect; such a category will probably be included
values may rise briefly, and fall again as weathering in the European Standard currently being drafted.28
proceeds. This can affect slag aggregate: in an example The hydration of MgO is commonly assumed to
from Pennsylvania, material recovered from a slag follow a similar pattern to free lime but on a longer
dump 30 years old and used as fill subsequently time-scale.12 In earlier years, broken magnesia bricks
showed disruptive expansion which continued for have been used as road material with apparent success
some years.49 although the behaviour of more modern bricks does
A small but significant complicating factor arises not seem to permit this now. Isolated observations
from the dicalcium silicate that is normally present in suggest that local sources of heat, such as a buried
substantial quantities, often making up more than steam duct in one case, may lead to considerably
50% of the slag (and presumably, on a lesser scale, the enhanced or accelerated hydration and expansion of
tricalcium silicate). This reacts slowly with water, to such material.
yield silicate hydrates in reactions comparable with Accelerated expansion tests are normally con-
those in the hardening of Portland cement but on a ducted using tap water or demineralised water. In the
longer time-scale because of the much larger grain field, the water may contain salts either dissolved from
size. These hydrates have a lower lime:silica ratio than nearby aggregates or soils, or from external sources
dicalcium silicate, and so a second product of the such as salt applied to roads during freezing weather.
reaction is calcium hydroxide. With time this too will Some tests for aggregates may involve solutions of
convert to carbonate, and again a form of equilibrium salts such as magnesium sulphate. 52 A series of
may be established where the calcium hydroxide is expansion tests in a climatic cabinet24 indicated that
consumed by carbonation at a rate matching its both NaCl and MgSO4 caused a small reduction in the
formation. This hydroxide and carbonate originating final expansion value for a BOS slag sample. The most
from the dicalcium silicate will be detected by analyses striking result from these tests was the observation, by

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Juckes The volume stability of modern steelmaking slags

optical microscopy, that free magnesia was extensively properly used, gave a volumetrically stable road over many
attacked by the MgSO4 solution, the end product years.2,58 Clearly, the material can not only be used, but it
apparently being Mg(OH) 2. No other samples in this can show excellent performance in some properties.2,9,30
series showed any signs of reaction of the free
magnesia on the time-scale involved (14 days). One
inference from this is that some cases of apparently ROUTE TO SUCCESSFUL UTILISATION
differing behaviour by free magnesia in slags in the Steelmaking slags have desirable properties such as
ground may be a result of differences in groundwater good strength and skid resistance,20,30,31 and in some
composition. regions they are the most easily available aggregate
(where transport costs would make alternative
Relevance for utilisation materials substantially more expensive). What steps
Failures of steel slag aggregates and the structures are needed to ensure the safe use of such slags?
containing them are well known (in part because failures Basically, three factors are necessary. First, the slag
are more likely to be reported than successes) and normally needs treatment to reduce the amount of
examples include OH slag beneath buildings,12,13 BOS expansion that can occur. Second, the behaviour of
slag in roads53 and unspecified ‘steel slag’ beneath the material, which will be influenced both by the
buildings.54 However, an examination of such reports original nature and by any treatment, needs a suitable
shows that in almost all cases no quality control had method to assess it. Finally, limits need to be set that
been exercised in the application of the slag; in fact, in link the results from the test to performance in use.
some cases it may not have been realised that steel slag These factors are discussed below and the techniques
had been allowed to mix in with the blast furnace slag12 described range from those in widespread use to
or foundry sand55 that was the intended material. This proposals that have not been adopted or have been
pattern is confirmed by those who have made detailed used but abandoned. Some have been described
studies of such failures.56 Furthermore, in Britain and widely so that the references quoted should be seen as
Western Europe at least, examples are less frequent from examples and not a full listing of the literature on that
recent years when the potential problem has become topic. In other cases, they may have been presented or
more widely known (particularly for hardcore beneath discussed verbally at events such as conferences or
buildings). meetings of standards committees, or they may have
One solution would be to avoid all use of steel slag (a been seen during works visits. In such cases, there may
policy which has been advocated for more critical be no published descriptions, or at least none easily
applications such as hardcore11 and rigid bound layers).53 located. Test methods will be considered first, as they
While complete exclusion of a material will undoubtedly tend to be clearly documented and less prone to
eliminate all failures, it may also exclude much successful change and variation.
use and is thus not compatible with the aim of optimal It should be noted that no industrial process can be
use of resources. If the same principle were applied to such that one can guarantee that failures will never
every other construction material that had suffered occur. One can only minimise failures to the extent
failures, the world would be deprived of many useful that their occurrence will be sufficiently unlikely or
products, including for instance concrete made with sufficiently innocuous that it can be neglected for the
Portland cement. A more constructive approach is to sake of the application in question.
seek a way that still permits successful utilisation while
avoiding or preventing failures.
If past failures are to a substantial extent attributable EXISTING AND EARLIER
to the uncontrolled use of materials inappropriate for the SPECIFICATIONS
specific application, it is a situation that would give rise Specifications have been prepared or proposed by
to failures with many other products too. Thus it is various bodies to protect against the use in roads of
necessary to consider how such failures can be steel slag whose volume instability can be sufficient to
minimised or eliminated by appropriate techniques and compromise the performance and life-span of the
controls, linked to the particular application. Initial road. The main approaches are free-lime content,
guidance on this subject can be found by an examination accelerated expansion tests, and breakdown during
of successful applications of steelmaking slags. immersion or boiling. Another method, reported in
In Britain, much BOS slag has gone unsold although 1969,12 involved forming small bars from Portland
sales of BOS slag from Scunthorpe steelworks in cement and the slag (presumably finely crushed).
Lincolnshire for roads averaged about 200 kt year–1 over After curing, they were tested in an autoclave and then
the last decade of the 20th century. Published details of any expansion or breakage was noted. While the
successful use tend to be more general than those on authors saw this as a useful rapid test, it does not seem
failures, and they do not always distinguish between BOS to have been used subsequently.
and EAF slags. In 1999, one company reported that it had In many cases these tests have been devised, and
produced over 30 Mt of steel slag roadstone in Britain often used extensively, without any link to
since 1892, and that its world-wide operations were then performance in use; the mere fact that some expansion
selling more than 9 Mt annually into various or breakdown can be seen has been taken as a sign
applications.57 In Germany, the construction and that they are effective. However, if the reactions
monitoring of test roads has demonstrated that steel slag, occurring in the test are greatly different from those

C184 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112
 Juckes The volume stability of modern steelmaking slags

that will occur in the field, the test may not even rank developing between the different subsamples of the
a group of slags in the correct order. ASTM D 4792- same material.
95 describes an expansion test but shows rare honesty The eluant or solvent must be carefully selected to
in advising readers that: ‘Test values have not been ensure complete solution of the free lime present while
correlated with field performance, and values not reacting at all with the other lime-rich (and often
obtained do not necessarily indicate expansion that highly-reactive) phases such as tricalcium silicate and
may occur in service conditions’.59 This warning dicalcium silicate that are often present. In fact, it
should be applied to any test unless it is known that it appears that all currently used eluants will also extract
is linked with adequate road trials. Moreover, any Ca(OH)2 present (which is not a problem for the
commercial laboratories and even government bodies immediate analysis of slags sampled from the vessel
may have their own reasons when they advocate but is important in most other cases). Indeed, some of
multiple testing or recommend methods in which they the development of these methods was aimed at
have a near-monopoly. determination of the hydroxide. Thus to obtain a true
value for unreacted free lime in a sample that might
Analysis of free-lime content have undergone hydration, it is necessary to determine
In earlier years, specifications for the use of BOS slag the Ca(OH)2 content separately, usually by a thermal
were often simply limits on the free-lime content. method, and to subtract its equivalent. To prevent
Geiseler reported in 1994 that in Germany 7% for slag certain lime silicates and aluminates from being
used in unbound road construction and 4% for bound extracted and thus contributing to the analysis, the
use were found to be suitable limits;10 in 2001, the free- reagents for the extraction must be completely water-
lime content was still being monitored.2 Elsewhere, other free and must be protected from atmospheric moisture
limits have been proposed such as 4·5%32 or 5%.60 during storage. The method specified in the European
In practice, this has not proved to be a reliable Standard for the chemical analysis of cement requires
indicator of subsequent performance, for several reasons. the water content of the eluant to be determined (a
Most importantly, other factors such as the size and maximum of 0·5% is permitted); 61 perhaps this should
nature of the free-lime grains exert a major effect; one be done in other applications too. Equally, it is
study found that similar initial free-lime contents led to essential to ensure that equipment is absolutely dry
linear expansions varying by factors of 2–3 or even before the analysis is carried out.62
more.53 Another problem is that chemical analysis of free Probably the most commonly used eluant is ethylene
lime can show poor reproducibility between laboratories. glycol (1,2-ethanediol; e.g. BSI34,61), in some cases
For these reasons, free-lime contents are not specified in diluted with an alcohol;63 an alternative is ethyl
European standards. However, it was considered during acetoacetate (butanoic acid, 2-acetyl-3-oxo-, ethyl-ester)
the early stages of certain drafts and the test methods diluted with an alcohol.34,63 Glycerol (also known as
that were selected to support these specifications are still glycerin or 1,2,3-propanetriol) diluted with an alcohol is
described in BS EN1744.34 used63 for free lime in cement but has not featured in
Although the free-lime content is not a reliable more recently proposed methods for slags. An aqueous
indicator of the long-term volume stability of a sucrose solution 64 has been used for samples such as
particular batch of aggregate, it does still have some quicklime but would not be suitable for slags as they
wider uses. Examples are comparing changes in slag contain soluble calcium silicates. With some eluants, an
composition over time at one plant or assessing the accelerator may be added such as strontium nitrate63 or
likelihood of success when transferring a treatment barium chloride.65 Some proposed routines require
routine from one plant to another. Thus the analytical other distinctive features, such as preliminary heating of
techniques available are still of relevance to the utilisation samples to 540°C, raised extraction temperatures, or
of BOS slag. repeated extractions to achieve complete solution.65
With chemical methods, the main obstacle in Determination of the calcium extracted is commonly
analysing free lime is avoiding the inclusion in the done by titration although instrumental methods such as
analysis of other lime-bearing phases. Thus the atomic absorption have been used, and also precipitation
analysis is usually performed in two stages, the first as sulphate or oxalate.65 Titration may be against
being the extraction of the free lime with a suitable acid34,61,63 or complexometric, against an aqueous
solvent followed by filtration. Thereafter, analysis of solution of EDTA (ethylene diamine tetra acetic acid
the Ca content of the solvent can be done by a range disodium salt);34 a solution of ammonium acetate in
of established methods. There is a problem in that ethanol has also been specified.63 It should not be
standard materials are difficult to retain for any length overlooked that other oxides such as FeO and MnO may
of time without being changed by hydration and also be extracted and may interfere with the titration.
carbonation reactions. Samples can be spiked with They may also colour the solution to the extent that
known amounts of freshly-calcined free lime to during titration the colour of the indicator is largely
provide a calibration curve, but it is questionable masked.
whether this will behave identically to the impure free There appears to be little to choose between the
lime in slag when extracted. Exchanges of samples can different methods in common use (apart from the
help to reveal any major differences between necessity of complying with whatever standards are
laboratories or to confirm general agreement, but locally applicable). Müller and Fix compared eluants
analysis must be prompt to avoid real differences and found both glycol and ethyl acetoacetate to be

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112 C185
Juckes The volume stability of modern steelmaking slags

suitable although they preferred the former because of determination of the CaO extracted. This method is
the greater solubility of free lime in it, and thus the also described in BS EN 1744:1.34
more rapid achievement of complete solution. 66 They X-ray diffraction analysis (XRD) yields results in the
noted that both eluants could react with lime-rich form of a trace with one or more peaks representing
silicates although this was inhibited by having some each crystalline phase present; the peak height can give
lime in solution; thus they recommended the addition an indication of the total content of that phase (in the
of a known quantity of lime to the eluant at the start absence of overlaps with peaks from other phases).
unless it was known that the sample contained at least Peak heights can be measured accurately, but whether
2% free lime. (They also investigated a solution of this constitutes a reliable analysis method depends on
glucose in water and found solution of silicates whether other factors (such as influence on peak height
excessive even when lime was added as an inhibitor.) of other components, sample preparation, and so on)
Pressler et al.65 compared ethyl acetoacetate extractions can be safely ignored or else corrected. If they can, such
with glycerol–alcohol, looking in particular at the a method will give true results for free lime and also
possibility of reaction with hydrated silicates. They calcium hydroxide and calcium carbonate. This method
concluded that both could react with certain hydrated was proposed for cement by Bartl and Pekarek,68 and
silicates but that ethyl acetoacetate was less affected. has been used for slag69 in Belgium. Those who
Their preferred method used that eluant followed by developed the method described its precision as
anhydrous titration with perchloric acid dissolved in satisfactory 62 although others have generally regarded it
isobutyl alcohol, a combination often referred to as the as of low precision (e.g. Crawford and Burn41). It would
Franke method (although the original method of be expected that modern equipment will improve this.
Franke used titration against hydrochloric acid). The Microscopy can reveal the phases present, including
literature shows examples of various combinations, and free lime, and these can be quantified using standard
of the glycol methods the European Standard covering petrographic techniques such as point counting. Apart
slag specifies titration against EDTA34 while that for from the requirement for an experienced microscopist,
cement specifies hydrochloric acid;61 Inoue and Suito 27 there are problems both in reliably identifying and
used glycol followed by atomic absorption. Among counting phases present as very fine crystals; distin-
those preferring ethyl acetoacetate, the alternative guishing calcium hydroxide from the oxide can also be
European method for slag has titration against difficult. These considerations are probably among the
hydrochloric acid34 whereas the ASTM method for reasons for the differences between the free lime figures
cement stipulates perchloric acid.63 The glycerol–alcohol determined chemically (Table 1) and microscopically
method is rarely specified although one example uses a (Table 2) on the same samples.
glycerol–ethanol eluant followed by titration against
ammonium acetate for cement.63 Analysis of calcium hydroxide
The values given in Table 4 show that experienced Current extraction methods detect both free lime and
laboratories can get reasonably similar results (although calcium hydroxide. To obtain a true figure for free
well below the reproducibility considered acceptable for lime, it is necessary to determine the calcium
other determinations). 50 However, other exercises have hydroxide content so that it can be subtracted. There
shown even wider spreads between laboratories and the does not appear to be any suitable chemical method
conclusion is probably that any of the combinations although several thermal methods are available which
above can give good results when rigorously performed are based on the characteristic temperature at which
but that very close attention to detail is required with all calcium hydroxide dissociates. Within the British steel
of them or errors can easily arise. industry, in earlier years differential thermal analysis was
A conductimetric method has been described, used although as more modern equipment became
using ethylene glycol, where the solution is monitored available differential scanning calorimetry proved more
in a specially designed vessel during extraction so as to accurate. These depend on the endothermic reaction as
give a result as soon as extraction is complete, said to the calcium hydroxide dissociates; Inoue and Suito27
be 10–15 min. 62,67 Other oxides will also be extracted used thermal gravimetry to monitor the change in mass
by the glycol but they are said not to interfere with the as the water was driven off. An alternative approach is to

Table 4 Comparative tests on three slags by three laboratories50

Testing laboratory German slag Belgian slag British slag

Expansion Free lime Expansion Free lime Expansion Free lime

% % % % % %

FEhS, Germanya 0·8 3·7 3·0 12·1 6·0 7·8

CRM, Belgiumb 1·1 4·5 4·7 10·9 12·6 7·6
British Steel, UKc 1·4 3·2 1·7 11·1 2·0 7·2

All three tests use a compacted sample in a cylindrical mould.

a
Mould has permeable base, steam passed through sample for 24 h, mould walls held at 120°C.
b
Immersion of sample in water at 80°C, for 20 days.
c
Sample held in a climatic cabinet at 80°C and 90% relative humidity for 14 days.
Free-lime contents given are as analysed, in other words including lime present as Ca(OH)2.

C186 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112
 Juckes The volume stability of modern steelmaking slags

heat the sample while sweeping it with inert gas and to Extensive tests would be needed to establish
analyse the content of water vapour in the gas that leaves whether this is correct although if there were a specific
the sample chamber during specified temperature test for free magnesia the question would lose much of
intervals; results based on this method have been reported its relevance. This thus points to one area where there
by the German slag institute Forschungsgemeinschaft is a clear need for further work to improve the current
Eisenhüttenschlacken.58 European Standard: the development of a reliable
These methods can normally provide simultaneously technique for the accurate and precise determination
a determination of the content of calcium carbonate, a of the content of free magnesia.
useful figure when the weathering progress of slag is The qualification that the method must be accurate
being followed. and precise is important. The content of free magnesia
has been estimated by use of the XRD technique, as
Analysis of free magnesia content for free lime,70 although this method has usually been
The principles for analysis of free magnesia are the regarded as semi-quantitative at best. However, more
same as for free lime: selective extraction, followed by modern equipment might yet prove to offer the best
analysis of the MgO in the liquid after filtering. method available for this determination. The principle
However, unlike CaO, MgO can form a continuous will be affected by solid solution of other oxides, and
solid solution series with the FeO that is abundantly although this is not insuperable it must be taken into
present in most slags, and thus the problem of mix- account.
crystals is more significant. There appears to be no
widely accepted method capable of achieving a Expansion testing
sufficiently selective extraction. Lea70 reported a Ideally, if a steel slag is used as an unbound or bound
method for use with cement, where extraction is by a aggregate, one wishes to assess the extent of any
solution of ammonium nitrate in anhydrous alcohol expansion that later might occur over a period
and glycerol. Juckes47 described trials with a method extending to a number of years at least. One also
using an aqueous solution of potassium dichromate to wishes to do this within a time-span that is convenient
extract the free magnesia in LD slags; potassium to the delivery and emplacement of such an aggregate.
oxalate was added to suppress the extraction of Ca In fact, it is simple to accelerate the hydration process,
from phases such as free lime. Despite some and thus the expansion, in part by ensuring free
encouraging results, extraction that was thorough but availability of water in liquid or vapour form but
selective could only be achieved under very specific much more effectively by raising the temperature. This
conditions. There was no guarantee that the same can be enhanced by also raising the pressure during
conditions would apply to other samples, and so the test. At some point, however, one must question
although the method may provide a starting point for whether the test is revealing the same reactions and
future work it cannot be regarded as robust. mechanisms that occur when the process occurs over a
This subject has a practical effect on slag testing, in time-scale of years or whether the accelerated
that expansion of steel slags in the European test reactions might be so different that they no longer give
method of BS EN1744-134 is regarded as likely to be a useful guide to long-term behaviour in, say, a road
affected by the free magnesia if it is present in situation.
substantial amount. Ideally, this slower reaction would As noted earlier, some expansion of fragments can
be covered by conducting the test for a longer period be accommodated by the porosity within the
when the sample contains more than a certain amount aggregate; consequently, the stage at which the entire
of free magnesia; the problem is knowing the actual aggregate begins to expand is also controlled by
content of free magnesia. In the absence of a reliable test porosity and packing. Thus in the development of a
method, the Standard uses total MgO content as an suitable test, the degree of compaction needs to be
indicator of the probable content of free MgO. Thus selected carefully and specified precisely.
samples with less than 5% total MgO are tested for 24 h, The many variations possible mean that the same
and those with 5% or more are tested for 168 h. This will slag sample will give different results under different
clearly have a major effect on the throughput of a testing tests. Table 4 illustrates this, showing results obtained
laboratory, and on the cost of the test. when three different slags were tested using three
It is arguable that the figure for total MgO content different test methods; 50 it can be seen that each gives
might in some cases actually correlate negatively with very different results for the same slag. In the most
free MgO and the expansion that it might cause. This extreme example, values of 2·0%, 6·0% and 12·6% were
could be the case if it is true that only the free obtained for the same material. It also shows that the
magnesia that is derived from refractories causes highest expansion was not found in the sample with the
sufficient expansion to be of concern. High values of highest content of free lime (although the values have
total MgO are usually the result of higher additions of not been corrected for any Ca(OH)2 present).
MgO-rich flux, which inhibits the attack on the vessel This illustrates the extremely important point that
lining and so should lower the content of the free an expansion value of, say, 5% in some expansion test
magnesia type that is most expansive. The MgO in the does not mean that a road containing this aggregate
flux would also tend to assimilate more readily and so will eventually expand by a factor of 5%. It may be
it would not in itself cause the free magnesia content less, it may even be more, and it could well be zero, but
to rise greatly. the actual figure will depend on such factors as the

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112 C187
Juckes The volume stability of modern steelmaking slags

grading, compaction and so on for both test and road. needed with the interpretation of the results; the
Juckes24 reported on samples drilled from a road panel application of limits intended for samples consisting
with a 250 mm thick sub-base of BOS slag screened at only of slag is unlikely to be appropriate. It is even
–40 mm from a heap that had weathered naturally for possible that addition of inert material could in some
6 months; the results are summarised in Table 3. cases spuriously increase the measured expansion, by
Because of the relatively small sizes of the drilled occupying voids which would otherwise accommodate
samples compared with the particle size, the scatter on some of the particle expansion. The current European
the chemical analyses partly obscures the trends, Standard method specifies the sample grading, listing
although the expansion value clearly falls with time. the weights to be used from each of the different size
Throughout this period and the subsequent decade fractions.34 A number of aspects of this test will
the road showed no signs of failure or distortion, require consideration when the Standard comes up for
despite the fact that weathering had neither reduced its 5-yearly review, and one of the most important will
the free-lime content nor the measured expansion surely be an agreed and reliable way of testing
value to zero. materials that lack one or more of the size categories
This means that it is not possible to set a figure, in listed in the test method.
isolation, as an expansion value that should not be A compromise is necessary in specifying sample
exceeded. The appropriate limiting value for any size. With a material that often contains a substantial
particular application will depend upon the test used proportion of relatively coarse material, an
and can only be determined by a comparison of unmanageably large sample might be required to
different levels of test results with performance under ensure good representativity. This can be to some
true road conditions. It also assumes that the results extent counteracted by testing two or more such
from the test are known to correlate with performance samples and averaging the result; an example is the
in the field, something that can only be ascertained by current European Standard method which specifies
suitable test programmes including road panels. It duplicate tests with a sample weight of 4·5 kg each.34
would be wrong to assume that any laboratory routine In fact, sample size is often specified by the volume of
that produces measurable and accelerated expansion the vessel used, and most tests have been devised using
will automatically correlate with road performance; if some vessel already available for an existing test such
the conditions selected produce different reactions as Proctor compaction or the California Bearing
and mechanisms, then the results could be virtually Ratio (CBR). (It should be noted, though, that the
unrelated. Indeed, it would not have been a great exact dimensions of even these vary from country to
surprise if the three test methods giving the results in country and time to time.)
Table 4 had ranked the three slags in different orders, In all the proposed tests, the vessel appears to be
bearing in mind that each operated on a different cylindrical; no exceptions have been noted. This
principle (immersion, percolation of dry steam, and constrains lateral expansion so that a measurement of
high humidity below boiling point). linear expansion is the equivalent of volume expansion.
Additionally, some have argued that different tests It has been shown that application of a weight or
are required to assess slag for use in different surcharge on the upper surface can cause a reduction of
applications, such as an unbound aggregate and a the measured value, possibly reflecting a reduction that
component of a bituminous mix. In European would occur in the field as a result of the weight of the
Standard BS EN 1744 the same steam test (originally overlying road layers.71 Presumably this occurs by
developed for unbound aggregates) is specified for the directing a greater proportion of the expansion into the
aggregate to be used in both applications.34 In this, remaining porosity within the compacted aggregate.
steam at 100°C is passed through a compacted sample Even where such a surcharge is not specified, the
in a cylindrical mould that has heated walls to prevent necessary components may have the same effect (a metal
condensation. Earlier, for slag to be used in bituminous plate is often placed over the upper surface of the
mixes, some have used expansion tests of slag compacted slag, partly to counteract any asymmetrical
compacted with bitumen, immersed in water, in one expansion). As an example, the European Standard test
example at a lower temperature of 40°C for 42 days.44 specifies use of a loading weight such that total mass on
Sample grading requires a major policy decision. A the slag surface is 6 kg.34
specified grading gives an element of consistency to Probably the most important decision in selecting a
the tests but may seem inappropriate for materials test method involves the form of the water to be
where the proposed use would be in a significantly present during the test: should it be as a liquid or
different grading. (It is important not to crush or vapour? Bearing in mind that they can produce
grind the sample to yield any missing sizes, as this different modes of hydration, and thus expansion,47 it
would expose fresh particles of free lime and alter the is important to consider first the nature of the water
behaviour of the sample. This consideration also that will affect the material if it is used in a road.
means that a large sample, probably at least 10 kg, will While no single test can simulate all possible
be necessary for testing or else coarse samples will situations, the most probable scenario (in temperate
have unacceptable heterogeneity.) In some cases, such climates, at least) is that liquid water will rarely if ever
as single-size or gap-graded aggregates, the addition be present to the extent of saturation, although it will
of an inert component in the missing sizes may rarely be so dry that the effect of water vapour is
provide a solution. In this case, however, care is negligible. Thus, the most likely situation is that water

C188 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112
 Juckes The volume stability of modern steelmaking slags

vapour will be the main agent, although particle regarded as a reliable indicator of performance, and
surfaces may quite often be damp. Moreover, the for suitable thresholds to be established.
hydration that occurs when the agent is vapour will be The duration of a test needs to be such that the
more expansive and it is this possibility that is of more results indicate clearly the final or maximum value, even
concern. This suggests that the best compromise if they might not yet have reached it. In some cases, the
would be a test with water present as vapour. asymptotic approach to the final value suggests that it
Temperature cycling, to cause intermittent surface can be estimated long before it is effectively attained.
dampness, might improve the simulation. Cyclical However, Verhasselt and Choquet32 give examples to
expansion tests are not common, probably because of show that the expansion can occur in irregular steps
the more complex controls that would be necessary, rather than in a smooth curve with time. (This would
although a test routine specified in Japan72 uses presumably be smoothed out by using larger test
continuous immersion and varying temperature, with samples, but with coarse material up to 20–30 mm one
10 cycles of 6 h at 80°C and 18 h during which it would need unmanageably large samples to eliminate all
reverts to ambient. effects of heterogeneity.) Thus a time needs to be
Most tests are designed for ambient pressure; in specified at which all parties in a transaction can agree
Britain, at least, the statutory restrictions on the use of that the test has ended. While long periods (of the order
pressure vessels do not prohibit the use of higher of 100 days) may be useful for the general study of the
pressures but are a strong disincentive. Higher mechanisms and reactions involved, for commercial use
pressures allow liquid water to be present at higher a test is required that will give a result within a few days
temperatures, and for this reason tests have been at most.
proposed or tried using pressure cookers or In cases where a moist sample is used (for instance,
autoclaves.2,44,73,74 Three basic types of pressure vessel to facilitate compaction) the recording of expansion
are easily available commercially, and attention has should begin immediately or else part of the early
largely been directed to these. Autoclaves for phase, when most of the expansion occurs, may be
sterilisation of medical equipment normally operate at missed even if the temperature is still at ambient.
pressures of 1–2 atmospheres (100–200 kPa) above Alternatively, any permitted delay should be clearly
ambient, giving a boiling point for water of around specified. An example is ASTM D 4792-95 which
120–134°C. Domestic pressure cookers tend to lack specifies a delay of 30 min before recording of the
precise calibration but operate in the lower end of the expansion begins, to allow any thermal expansion of
same range. In contrast, autoclave testing of cement is the apparatus to stabilise.59
normally carried out at a pressure of 20 atmospheres While by no means comprehensive, Table 5
(2000 kPa).75 Published accounts of autoclave testing summarises the characteristics of some of the tests that
of slags can use either of these two very different have been described in the literature or encountered by
regimes, and this should be taken into account if the industry.
autoclave testing of slag is being considered or if
published results from such tests are being used. Also, Boiling and immersion tests
some accounts report pressures in absolute terms If a sample of BOS slag contains free lime, placing
while others quote the pressure above ambient which fragments in a container of water and boiling them
will thus be 100 kPa lower. usually leads to some degree of breakdown. The
One study of the behaviour of slag under pressures simplicity of such a test and the low cost of the
ranging from ~300–4500 kPa found the reactions to equipment required make it a tempting candidate as a
be unchanged throughout this pressure range.74 On standard method. However, the primary aim in devising
this basis, the authors recommended that autoclave a test is not simplicity but accurate and reliable
testing at any pressure that gave a measurable degree differentiation between good and bad; between material
of hydration would be useful for assessing the that can be used for a certain purpose and that which
expansion potential of LD slags. Others have cannot.
considered autoclave tests to be too severe an There does not appear to be any published
environment, 76 and elsewhere after a series of tests at information linking results from boiling tests to
2100 kPa and 215°C it was concluded from X-ray aggregate performance in roads, although such a test
examination that different reactions were occurring is extensively used for armourstone in The
and so the method was abandoned. 2 Subsequent Netherlands and Belgium where it is regarded as a
experience suggests that testing at pressure leads to good predictor of performance. In this application,
exaggerated disintegration of particles; this is aggregate (typically in the size range 25–100 mm) is
confirmed by the data of Okamoto et al.74 and so applied to the banks and beds of rivers and canals to
caution is required with the use of such results. One protect them from erosion. 2,7 (Slag is not used for the
possibility is that even when actual reactions remain much larger rock slabs, also termed armourstone, that
the same, the physical mechanisms are not the same at are used for coastal protection.) The density of BOS
different pressures. slag, higher than that of most natural aggregates,
It is reported that pressure cookers are currently offers an advantage in that it better resists being swept
used in Canada,3,5 although little seems to have been away by the flow. In such a situation, the behaviour
published on this. It would require careful comparison might indeed be best monitored by a test involving
with field performance before such results could be continuous immersion 9 although that is not normally

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112 C189
Juckes The volume stability of modern steelmaking slags

Table 5 Examples of expansion tests proposed for steel slag aggregate (in all cases the vessel is cylindrical and linear expansion
is measured)

Source Vessel size Sample Sample Compaction Temp Moisture Duration

(nearest cm)* grading mass (°C)

Crawford & D 5, H 10 NS By volume NS 100 100% RH ; ~50 days

Burn (1969)12 wet at base

Crawford & D 5, H 10 NS By volume NS 15 ~90% RH ~150 days

Burn (1969)12

Emery (1974)76 D 10, H 11 Actual By volume ‘Standard 82.2 Immersion ~7 days

(Proctor) Proctor’ (180±3ºF)

Piret et al. Apparently D 15, NS By volume NS 80 Immersion ~10 days

(1988)71 H 17 (‘Proctor
modified’)

Juckes (1988)50 D 15, H 13 (CBR) 60% 5–20 mm, By volume BS1377:197577 80 90% RH 14 days
40% –5 mm

JIS A 5015– D 15, H NS 7 size classes By volume Ramming 80 ± 3 for Immersion 10 days
199272 specified, routine 6 h each day;
max 31.5 mm specified otherwise
ambient

ASTM D D 15, H 18 as in If +19 mm fraction By volume As in ASTM 70 ± 3 Immersion; 7 days (but

4792–95 ASTM D188378 > 10%, then +75 mm as in ASTM D188378 surcharge first 30 min
(1995)59 discarded and the D188378 of 4·54 kg not
–75 +19 mm fraction applied measured)
replaced by equal
amount of –19
+4.75 mm

BS EN D 21, H 10 Fuller parabola; 4.5 kg Vibrating Boiling Steam; 24 h or

1744:199834 weights listed; table, or any point; vessel surcharge 7 days
max 22 mm equivalent walls held of 6 kg (depending
method at 120 ± 10 applied on MgO
content)

*Dimensions approximate, not always given in original description. See references for more precise details.
H, height; D, internal diameter; NS, not specified; RH relative humidity; Max, maximum.

the case for roads. This test has been incorporated into their individual histories. In earlier years, however,
the European Standard for armourstone, and requires British Standards did mention the need for weathering
slag fragments to be boiled for 8 h after which the although no period was specified. BS 6543:1985,
fragments are examined for crack formation, and the covering ‘Use of industrial by-products and waste
percentage breakdown or weight loss is calculated.79,80 materials in building and civil engineering’,82 noted
A similar test but with boiling for 36 h is sometimes that hydration of free lime and magnesia could cause
used in testing for ‘sonnenbrand’, a specific type of instability. Thus they advised that ‘steel slags should
breakdown that occurs in some basalts, where exposure be allowed to weather before use in roads. Steel slags
to atmospheric conditions following quarrying leads to should not be used where failures can be caused by the
the development of hairline cracks over a time-scale instability, e.g. as fill under buildings or as aggregate
ranging from months to decades.80,81 Again, the in concrete.’ A more specific standard, BS 594: Part 1:
simplicity and cheapness have on occasion led to its 1992, covering ‘Hot rolled asphalt for roads and other
being proposed as a test for BOS slag in roads, although paved areas’,83 permitted ‘Steel slag, either electric-arc
it seems equally unlikely to simulate conditions in that furnace or basic oxygen slag, which shall be weathered
application. until it is no longer susceptible to falling’ (‘falling’ is a
An immersion test at 60–70°C has been described, 53 term used to describe the disintegration of certain
where the change in particle density was observed over products, although with slags it is more usually
periods ranging from 30 to 56 days. This was only seen restricted to disintegration as a result of the inversion
by the authors as suitable for material finer than 4 mm, of b-dicalcium silicate). An identical requirement
and does not seem to have been adopted by others. appears in BS 4987: Part 1: 1993, covering ‘Coated
macadam for roads and other paved areas’.84
Weathering
European Standard BS EN 1744-134 deliberately does
not include any requirements concerning the LIMITS
weathering of steelmaking slags; those drafting it saw For any test method, calibration is necessary if results
their task as providing tests for materials regardless of are to be any more than an indication. Rigorous road

C190 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112
 Juckes The volume stability of modern steelmaking slags

tests involve panels with lengths of the order of a steelworks dusts, with some success. Building on this
hundred metres or more, preferably without curves, work, a process has been developed and is in commercial
and control panels using standard aggregates are operation2,87,88 whereby silica sand is injected via a lance
necessary in addition to those using the material (thus reducing dust losses) together with oxygen. The
under test. Thus such tests are not only expensive but consequent oxidation of the FeO (and some metallic
it can also be difficult to find suitable locations at the iron) in the slag is exothermic, providing heat to assist the
time when the tests are required. Consequently, few of assimilation of the sand. The resulting higher silica
the test methods described above have been confirmed content of the slag leads to a lower free-lime level. A
in the field. It is fortunate that the steam test specified point not yet fully assessed is the loss of included metal in
by BS EN 1744-1:1998 is linked to a number of road the slag, and its value. This would normally be recovered
tests, and that these do confirm that it is a good magnetically after excavation of the slag pit but that is
indicator of likely performance. 2,9 not possible after its oxidation to FeO.
In Europe, the existence of a European Standard An alternative approach to facilitating assimilation
specifying a test method34 means that choice of tests is is to use a material with a low melting point. Cullet
restricted in that region. Although a buyer and seller are (scrap glass) is a material available on the scale
free to agree any specification between them, for public required, and early tests in Belgium are said to have
tenders a European Standard must be specified or else shown promising results when the cullet was placed in
suppliers can object on the grounds of a barrier to trade. the empty slag ladle and the slag poured over it.
However, the European Standards for aggregates do not Liquid additions will ensure better mixing, and
prescribe the values for any specific application; they Geiseler et al.85,86 experimented with pouring both blast
simply define categories into which products may be furnace slag and BOS slag into the same ladle. Although
classified. The question of which category is appropriate this produced an excellent product, at most plants the
for a particular application is to be decided by the design logistics and scheduling that would be required to bring
engineer guided by personal experience, documented the two materials together in appropriate proportions,
accounts and locally established values. and before either solidifies, have seemed too challenging
for the adoption of such a process.
The free-lime content of slags from individual heats
TREATMENT TO REDUCE EXPANSION varies widely, and so if one could selectively divert those
Process modification with a high content then the average content for the
Clearly one can introduce process changes that will remainder would be significantly lower.2 This requires at
reduce the amount of free lime in the slag but in most least one extra slag pit, more flexibility in the slag
cases they will have adverse effects on the steelmaking handling, and also information on the free-lime content
process. Lower lime:silica ratios (achievable by lower of each batch of slag on a time-scale of well under an
additions of lime or by silica additions) correlate with hour. Methods proposed for this have involved either
lower free lime contents but to the detriment of models based on factors such as flux addition levels,
dephosphorisation of the steel. Longer blowing time is blowing time and chemical composition, 89 or schemes
known to reduce free-lime content, but is accompanied for providing a rapid chemical analysis of free lime.69
by product loss as more molten metal is oxidised and Despite the difficulties, some plants have claimed
enters the slag as FeO. Selection of lime source for rapid success using this principle.69
solution could give an improvement, but only in areas Disintegration of the slag is normally regarded as
where alternative sources are available without undesirable. In a rare paper that saw it as a useful aid
unreasonable cost. Use of solid BOS slag as a flux in to crushing, experiments were described to increase
place of lime gives better assimilation but this recycles the effect.90 At Shanghai No. 5 Steel Works, the LD
phosphorus causing the levels in the steel to rise. In slag was treated by injection of water to slag in a metal
general, the process at most plants is planned on the enclosure while still hot, and this was said to give
philosophy that effective steelmaking is paramount adequate fracturing as a result of the hydration of the
and the slag composition must follow from that. free lime. The EAF slag contained less free lime and so
the slag was not sufficiently broken up. In a series of
Treatment of molten slag tests, the molten slag was poured onto materials in the
Following the view above, the first opportunity to metal container before the water was added. The
modify the slag arises after it has been transferred to materials included lime, wet sand and wet slag, at
the slag ladle. Many have considered this a suitable levels between 0·5% and 4%. The added lime was said
stage for introducing additives that will reduce the free- not to have an adverse effect on the stability of the slag
lime content (and possibly improve other aspects too), after disposal (the application was not given).
although most tests that have been reported show Although the tests were described as successful, 90 the
limited success. With fine additions, dust losses can be cost of materials and handling would probably be
large. With coarse additions, the lumps are immediately prohibitive in most cases. The authors acknowledged
coated by a layer of solidified slag that isolates them the danger of explosions when bringing together
from the melt and thus from any assimilation, molten slag and water but said that the use of damp
preventing the chemical reaction that is desired. materials such as sand obviated this. Nevertheless,
Attempts have been made to obviate these problems. anyone who contemplates replicating such tests
Geiseler et al.85,86 described tests with the injection of should proceed with great care.

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Juckes The volume stability of modern steelmaking slags

Rate of crystallisation was that BOS slag should be weathered for a

In general, more rapid cooling is known to lead to a minimum of 6 months in the ‘as-dug’ form, followed
lower content of free lime. This in turn can be expected by a further 3 months after crushing and screening.
to lead to improved volume stability, and so various This work was associated with road trials, using the
techniques have been proposed to take advantage of the slag as a bituminous-bound wearing course.96
effect. In German trials, improved pit management Work in Belgium71 used five different slags covering
ensured that the slag formed thinner layers and these a range of free lime contents, in heaps up to 6 m high,
were found to solidify more rapidly and to contain and showed comparable results. In some cases with
measurably less free lime. A more extreme treatment, heaps of 6 m, it was found that after a year the
producing what was called ‘instant-chilled steel slag’,91 expansion value for material from the centre had not
uses four stages including thin slag layers on metal plates changed significantly, although that for material
and water-spray cooling to give an aggregate said to be nearer to the surface had fallen substantially. (In
sufficiently stable for use in concrete and with a particle practice, the different zones of the heap will become
size of 30–50 mm. Again, the danger of explosions was mixed during recovery so that an intermediate value
noted, when bringing molten slags and water together, applies overall.) This was attributed to the failure of
but the relatively thin layers of slag were seen as rainwater to penetrate deeply into the heap, especially
preventing this. if an impermeable cap had formed. Air sampled
Blast furnace slag is commonly granulated to through pipes laid into the bases of heaps showed that
produce material with latent cementitious properties, the moisture content of the air in the centre
and comparable plants, both wet and dry, have been corresponded closely with that outside and on some
described for processing steelmaking slags.92,93 occasions there was condensation within the heap,
Although the products from such processes do tend to showing that atmospheric moisture was not being
have low contents of free lime, the glassy granules of excluded. The different degrees of weathering reflect
about 2–5 mm in size do not seem suited for any the fact that moist air is less effective than liquid water
major aggregate application. Sand blasting has been at hydrating free lime. Whether the changes in free
proposed 94 but this is a relatively small market with lime matched the trends for expansion could not be
competitive alternative materials. established because the analysis method used gave
Plants intended to bring molten slag and water only a combined value for free lime and Ca(OH)2.
together need careful design if explosions are to be Other authors have recommended weathering
avoided;95 liquid slag can contain pockets of molten periods, with varying degrees of technical justification.
metal which greatly increase the danger of explosion. Following a series of weathering and road tests,
Andrieux 97 noted that in the Nord Pas de Calais the use
Treatment of cooling slag of BOS slag, air weathered for 6 months, was adopted as
Cooling of the slag in the pit is normally accelerated by a surface dressing. More recently, 6 months has been
spraying with water, and the hydration of free lime reported as the accepted period in Finland where it was
caused by this water will be accelerated by the higher used mainly in the wearing course.98
temperature. Belgian work suggests that a schedule of Although not a standard, a booklet published in
breaking and watering, designed to take fuller Britain by the Building Research Establishment
advantage of this effect, can give an improved product. (BRE)99 will be seen by many as authoritative and it
states that ‘weathering for about a year with the
Treatment of solid slag stockpile being turned over several times is usually
The most widespread treatment method for cooled necessary’. The authors give no technical justification
slag is weathering in heaps in the open, with rain for this requirement, and their only reference on the
providing the moisture to hydrate the free lime. (In topic of slag weathering is from the Belgian road
some countries the term ‘aging’ is preferred to authority 53 (one of the most stringent in Europe), a
‘weathering’; elsewhere, ‘maturing’ has been used.53) conference paper that was challenged on presentation
Many tests were conducted in the 1970s and 1980s, in as being over-pessimistic. 100 While that paper does
projects sponsored by the European Coal and Steel recommend weathering for 12 months, even it makes
Community (ECSC), with the aim of establishing how no mention of turning the heap over. It is not unusual
long the weathering period should be, what the effect for those remote from the practicalities of the industry
of heap height was, and so on. British work48 to overlook the costs of handling and treating slag,
examined six stockpiles ranging in size from 500 t to and to succumb to the temptation to add arbitrarily-
3000 t to establish the rate of hydration of the free chosen extra requirements ‘just to be safe’. Aggregates
lime. Although the amount of remaining free lime are low-value products where the addition of even
could still be falling after 24 months, and falling small unnecessary costs can make them uneconomic
towards a non-zero value, most of the fall occurred in compared with competing materials. Even the simple
the early months. Calcium carbonate tended to process of weathering in an open heap has its costs,
cement particles together at the surface of the including the cost of the land required and the
stockpile, forming a solid cap, although the moisture management (such as monitoring to ensure that the
contents of samples from the centre of the pile were material is not affected by other activities in the area,
regarded as high enough to show that ingress of water and that rainfall is adequate during the weathering
for hydration was not hindered. The recommendation period). The cost of turning a heap over thoroughly,

C192 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112
 Juckes The volume stability of modern steelmaking slags

even once, is likely to be prohibitive in many cases. many operators see such capital expenditure as
Thus this proposal, presented with no justifying unnecessary when natural rainfall can produce a
evidence, should be set aside as arbitrary and similar effect requiring only some forward planning
unnecessarily onerous. and some spare land (which can often be found within
In countries such as Britain, the rainfall is normally the works’ perimeter).
frequent enough to ensure that the hydration proceeds Treatment with acid rather than water offers the
continuously although even in countries with regular possibility of faster reactions, although if the acid
rainfall it has sometimes been felt desirable to spray to were also to react with the calcium silicates there
ensure that moist conditions are maintained within would be excessive consumption of reagent. Trials
the heap or to accelerate the process.20 When available, with spent pickle liquor (impure sulphuric acid) have
sea water has at times been used; while this may be been described, 76 and such treatment is reported to
cheaper in some locations, the salt content might be have provided satisfactory road aggregate from slag
undesirable in some applications. It is said that in The that had previously caused heave.20 That was in the
Netherlands, the bromine content of sea water caused 1970s; modern plants normally use processes with a
the slag to exceed environmental limits intended to pickle liquor that can be regenerated and so this is
restrict the content of organo-bromine compounds unlikely to be an option at present.
which might arise from agricultural run-off. With all weathering methods, results are likely to be
Weathering by immersion has been proposed better when the initial slag is already of a good quality –
although the cost of the necessary handling and which generally means, with a relatively low free-lime
construction is normally not considered justified. Road content. Moreover, breakdown during weathering or
tests have been described101 using slags including some aging will lead to the development of fines, with
weathered by immersion in warm water at 25–30°C possibly a lower yield of usable product. There may
(although the commercial use that followed from these even be some slags that will never produce a good
tests was of slag weathered under ambient conditions). 97 aggregate (as judged by the appropriate test method) at
A weathering routine stretching over months requires economic yield rates.
a considerable degree of forward planning of probable
sales, and also a large storage area. In an attempt to Selected applications
shorten the weathering period, some (particularly in Within the broad field of aggregates, certain
Japan) have considered the use of higher temperatures. applications are less vulnerable to the effects of free
Simplest is the system known somewhat confusingly as lime and its hydration. Slag used in bituminous mixes
Open Yard, where the base of a large slag pit is fitted (the names used for some of these products, such as
with steam pipes.102 Slag after de-metalling is loaded bituminous mortar15 or asphaltic concrete31 may be
into the pit and steam is pumped in via the pipes, the misleading to those unfamiliar with them) can be an
flow being controlled by thermocouples. Tarpaulins example, because the fine size means that the water
over the surface increase the residence time of the steam. involved in normal processing is adequate to hydrate
After 2–3 days the steam is switched off and the most of the free lime20 and there is also an effect in that
weathered slag is recovered; the cycle takes about a the bitumen will hinder the access of water when the
week, allowing for loading and excavating the pit. This particles are in the road.31 This is to some extent
shorter time (compared with 12 months) gives operators recognised by different limits of categories for unbound
more ability to react to changing market conditions. The mixtures and for bituminous-bound mixtures in the
method does have several problems, such as a high respective European Standards.28 Similarly, ASTM D
labour requirement and a need for care to avoid 5106-91 covering steel slag aggregates for bituminous
channelling of steam that could leave zones of the pit paving mixtures does not find it necessary to mention
incompletely weathered; there can also be damage to the volume stability.104
walls of the pit as a result of the bulk expansion. A plant Self-binding composite mixes can be used in roads,
for a version of this process with a batch size of 600 t where in addition to the graded aggregate there is
and a cycle time of 3 days, known as Forced Aging, has typically 10–20% of granulated blast furnace slag
also been described. 103 which provides a slow cementitious effect so that
Temperatures above 100°C require higher pressure strength develops over a period of months; 9,10 such
if both steam and water are to be stably present, and mixes are used extensively in France.105 An accelerator
the ‘Sumitomo-Kawasaki Aging Process’ (SKAP) is normally necessary to promote the cementitious
operates under such conditions.102 Theoretical reactions, such as lime and/or gypsum at a level of
considerations predicted that at a pressure of about 1–2%. It has been proposed that using steelmaking
600 kPa and a temperature of 160°C, the hydration slag as part of the aggregate would also provide the
after 2 h would be the equivalent of that achieved by lime, and that in this way the lime would be consumed
the Open Yard system in 2 days or ambient conditions by non-expansive reactions.106 Laboratory tests
in 2 years. A plant was constructed to treat batches of suggested that expansion was inhibited 106 and road
50 t, with a total cycle time of 3 h which gave a daily tests in Belgium were considered to be successful. 107
production of 400 t. With the batches passed to the Commercial use also requires that the local road
pressure vessel in enclosed ‘“baskets’, the process is authorities accept road construction methods that
reported to be automated and only requiring one may not be familiar to them, and this could be a
operator. However, despite the apparent advantages, significant obstacle.

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112 C193
Juckes The volume stability of modern steelmaking slags

Verhasselt and Choquet,53 while investigating failures the Corus Group, for his support during that period.
attributed to steel slag, observed that no damage The author acknowledges help from colleagues in Corus
occurred where a sand layer overlay the slag. Thus they UK, the Slag Group of the Quarry Products
proposed that such a sand layer would in general reduce Association and the German Slag Institute
or eliminate surface damage, the thickness of the layer Forschungsgemeinschaft Eisenhüttenschlacken both in
depending on the amount of slag used but with a the reviewing of the manuscript and in the gathering of
minimum of 15–20 cm. This is an interesting possibility information. However, the opinions contained in this
but it would need close attention to whether a road paper are the responsibility of the author alone.
whose overall design included such a sand layer could
still provide the mechanical properties required, and at
an economic cost.
REFERENCES
1. ANON.: ‘Slag-less steelmaking at NKK Fukuyama’, Steel
Times Int., July 1998, 22, 43.
CONCLUSIONS 2. H. MOTZ and J. GEISELER: ‘Products of steel slags an
Steelmaking slag has a long history of use as an opportunity to save natural resources’, Waste Management,
aggregate with excellent properties and economic 2001, 21, 285–293.
benefits when used in appropriate situations. 3. K. HOLLIDAY: ‘Steel slag: the industrial aggregate’, Steel
However, basic steel slag usually contains phases that Technology Int., 1997/98, 58–61.
are volumetrically unstable, and these must be taken 4. H. L. ROBINSON: ‘The utilization of blastfurnace and steel

into account for successful use of slag aggregates. making slags as aggregates for construction’, 327–330;
What is needed for successful use is a rapid and 2002, (eds. P. W. Scott and C. M. Bristow), Industrial
minerals and extractive industry geology, London, The
reliable test to indicate how a slag will perform in the
Geological Society.
long term, and suitable thresholds against which to
5. K. A. HOLLIDAY: ‘Steel slag: the high performance industrial
judge test results with regard to the intended aggregate’, Steel World, 1997, 2, 11–14.
application. In most cases, pretreatment of the slag is 6. H. K. EGGLESTON: ‘Use of blast furnace and steel slags as a
also necessary to minimise any expansive potential rail ballast material in U.S.A.’, Proc. Utilisation of
within the slag. Steelplant Slags Symp., Illawarra, February 1979, 75–80;
Atmospheric weathering is usually found to be an Parkville, Australasian Institute of Mining and Metallurgy.
adequate pretreatment although a range of techniques is 7. T. MERKEL: ‘Successful utilisation of steel slags in
available to accelerate the process. The European Germany’, 87–99; 2001, (eds. J. Geiseler and H. Motz),
Standard expansion test and the established weathering Proc. 2nd Eur. Slag Conference, Düsseldorf, 9–11 October
routines provide a good basis for the evaluation and 2000, Duisburg, Euroslag.
8. J. ALEXANDRE et al.: ‘Utilization of BOF slag in Europe
utilisation of slags, although both may yet be improved
meets high standards’, 168-171; 1993, Proc. 1st Eur.
or refined as further experience is accumulated. In
Oxygen Steelmaking Congress, Düsseldorf/Neuss, 21–23
Europe, limits are not set by the Standards but must be June 1993, Düsseldorf, Verein Deutscher Eisenhüttenleute.
decided for each application by the design engineer. 9. J. GEISELER: ‘Use of steelworks slag in Europe’. Waste
It is important to be aware that expansion results Management, 1996, 16, 59–63.
given by an individual test method, quoted as a 10. J. GEISELER: ‘Steel slag – generation, processing and
percentage, are particular to those test conditions and utilization’, 87-97; 1994, (eds. P. Mahant, C. Pickles and W-
cannot be compared directly with results from tests K. Lu), Proc. Int. Symp. on Resource Conservation and
using a different regime. Equally, they do not Environmental Technologies in Metallurgical Industries,
automatically imply that a similar expansion, or Toronto, 20–-25 Aug. 1994, Montreal, Canadian Institute
indeed any expansion, will be seen in the application of Mining, Metallurgy and Petroleum.
11. DEPARTMENT OF THE ENVIRONMENT: ‘Hardcore’, Building
where the slag may be used.
Research Establishment Digest 276, 1983, London,
Potential areas for improvement of the European
HMSO.
Standard are the development of routines for the 12. C. B. CRAWFORD and K. N. BURN: ‘Building damage from
expansion testing of slag samples lacking certain size expansive steel slag backfill’, Proceedings of the American
fractions, and the selection of a determination method Society of Civil Engineers, J. Soil Mechanics Foundations
for free magnesia. Division, 1969, 95, 1325–1334.
Despite treatments, there may be certain slags that 13. J. P. GNAEDINGER: ‘Open hearth slag – a problem waiting to
will never give a commercial yield of aggregate happen’, J. Performance Constructed Facilities, 1987, 1,
meeting the specifications for some applications. This 78–83.
would have to be determined for any particular case 14. B. DEO and R. BOOM: ‘Fundamentals of steelmaking

by taking into consideration the relevant test methods metallurgy’, 146–160; 1993, New York, Prentice Hall
International.
and limits as well as the local economic conditions.
15. P. MIKLOS: ‘The utilization of electric arc furnace slags in
Denmark’, 101–110; 2001, (eds. J. Geiseler and H. Motz),
Proc. 2nd Eur. Slag Conference, Düsseldorf, 9–11 October
ACKNOWLEDGEMENTS 2000, Duisburg, Euroslag.
Much of the information contained in this paper was 16. N. C. JONES: ‘The successful use of electric arc furnace slag in
gathered while the author was employed by Corus UK asphalt’, 111–121; 2001, (eds. J. Geiseler and H. Motz),
and he wishes to thank Dr R. B. Smith, Director Proc. 2nd Eur. Slag Conference, Düsseldorf, 9–11
R&D Products at the Teesside Technology Centre of October 2000, Duisburg, Euroslag.

C194 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112
 Juckes The volume stability of modern steelmaking slags

17. A. R. LEE: ‘Blastfurnace and steel slag: production, Düsseldorf, 9–11 October 2000, Duisburg, Euroslag.
properties and uses’, 23; 1974, London, Edward Arnold. 39. J. P. GNAEDINGER and R. J. GNAEDINGER: Discussion on ref.
18. M. S. MILLMAN: ‘Secondary steelmaking developments in 12, Nov. 1970, 2131–2132.
British Steel’, Ironmaking Steelmaking, 1999, 26, 169–175. 40. A. MONACO and W-K. LU: ‘The effect of cooling conditions
19. W. POSCH, H. PRESSLINGER and H. HIEBLER: ‘Mineralogical on the mineralogical characterization of steel slag’,
evaluation of ladle slags at Voestalpine Stahl GmbH’, 107–116; 1994, (eds. P. Mahant, C. Pickles and W-K. Lu),
Ironmaking Steelmaking, 2002, 29, 308–312. Proc. Int. Symp. on Resource Conservation and Environ-
20. J. J. EMERY: ‘Slags as industrial minerals’, 127–141, 1978, mental Technologies in Metallurgical Industries, Toronto,
(ed. B. M. Coope), Proc. 3rd Industrial Minerals Int. Conf., 20–25 Aug. 1994, Montreal, Canadian Institute of Mining,
Paris, 13–15 Mar. 1978, London, Metal Bulletin Ltd. Metallurgy and Petroleum.
21. J. S. SAHAY, O. P. NAGPAL and S. PRASAD: ‘Waste management 41. C. B. CRAWFORD and K. N. BURN: Reply to discussions on ref.
of steel slag’, Steel Times Int., 2000, 24, 38–40; 43. 12, July 1971, 1026–1029.
22. N. BANNENBERG and K. J. ARLT: ‘Utilisation of used 42. L. CLARK (Chairman): ‘The thaumasite form of sulfate
refractory material and slag as secondary raw materials’, attack. Risks, diagnosis, remedial works and guidance on
Veitsch-Radex Rundschau, 1997, no. 1, 3–10. new construction’, Report of the Thaumasite Expert
23. G. THORNTON and D. ANDERSON: ‘Low phosphorus basic Group, Department of the Environment, Transport and
oxygen steelmaking practices in British Steel’, Ironmaking the Regions, London, 1999.
Steelmaking, 1994, 21, 247–251. 43. J. GEISELER and R. SCHLÖSSER: ‘Investigations concerning
24. L. M. JUCKES: ‘Investigation of the connection between test the structure and properties of steel slags’, 40–42; 1989,
results found in the laboratory on volume stability and the Proc. 3rd Int. Conf. on Molten Slags and Fluxes, Glasgow,
values found in practice for LD slags’, ECSC Final Report 1988, London, The Institute of Metals.
EUR 13430 EN, Commission of the European 44. F. WACHSMUTH et al.: ‘Contribution to the structure of
Communities, Luxembourg, 1991. BOF-slags and its influence on their volume stability’, Can.
25. H. PRESSLINGER, M. MAYR and R. APFOLTERER: Metall. Q., 1981, 20, 279–284.
‘Quantitative phase evaluation of converter slags’, Steel 45. R. O. RUSSELL et al.: ‘Everlasting BOF linings at LTV Steel?’,
Res., 1999, 70, 209–214. 220-225; 1993, Proc. 1st Eur. Oxygen Steelmaking
26. D. M. PROCTOR et al.: ‘Physical and chemical characteristics Congress, Düsseldorf/Neuss, 21–23 June 1993, Düsseldorf,
of blast furnace, basic oxygen furnace, and electric arc Verein Deutscher Eisenhüttenleute.
furnace steel industry slags’, Environ. Sci. Technol., 2000, 46. J. GEISELER et al.: ‘Untersuchungen zum Hydratation-
34, 1576–1582. sverhalten von synthetischen Magnesiowüstiten’, Steel
27. R. INOUE and H. SUITO: ‘Hydration of crystallized lime in Res., 1987, 58, 210–214.
BOF slags’, ISIJ Int., 1995, 35, 272–279. 47. V. S. RAMACHANDRAN, P. J. SERAD and R. F. FELDMAN:
28. H. MOTZ: ‘The European standardisation of slags’, 151–162; ‘Mechanism of hydration of calcium hydroxide’, Nature,
2001, (eds. J. Geiseler and H. Motz), Proc. 2nd Eur. Slag 1964, 201, 288–289.
Conference, Düsseldorf, 9–11 October 2000, Duisburg, 48. G. H. THOMAS: ‘Investigations on LD slag with particular
Euroslag. reference to its use for road construction’, ECSC Final
29. D. C. GOLDRING and L. M. JUCKES: ‘Petrology and stability Report EUR 8622 EN, Commission of the European
of steel slags’, Ironmaking Steelmaking, 1997, 24, 447–456. Communities, Luxembourg, 1983.
30. W. GUTT and P. J. NIXON: ‘Steel-making slag as a skid 49. M. SPANOVICH and R. FEWELL: Discussion on ref. 12, Sept.
resistant roadstone’, Chem. Ind., 17 June 1972, 503–504. 1970, 1808–1810.
31. B. S. HEATON: ‘Steel furnace slag as an aggregate in asphaltic 50. L. M. JUCKES: ‘Improved utilisation of blast furnace and
concrete’, 81–85; 1979, Proc. Utilisation of Steelplant Slags steel works slags’, ECSC Final Report EUR 11681 EN,
Symp., Illawarra, February 1979, Parkville, Australasian Commission of the European Communities, Luxembourg,
Institute of Mining and Metallurgy. 1988.
32. A. VERHASSELT and F. CHOQUET: ‘Stabilité dimensionelle 51. A. SUZUKI, J. HARUNA and K. ARAI: ‘Hardening of BOF slag
des scories LD’, La Technique Routière, 1985, 4, 4–23. by carbon dioxide processing’, Abstracts from
33. L. M. JUCKES: ‘Dicalcium silicate in blast-furnace slag: a Presentations to 98th ISIJ Meeting, Nagoya, 16–18
critical review of the implications for aggregate stability’, October 1979, Trans. Iron Steel Inst. Jpn., 1980, 20, 310.
Min. Process. Extract. Metall. (Trans. Inst. Min. Metall. 52. BRITISH STANDARDS INSTITUTION: ‘Tests for thermal and
C), 2002, 111, C120–C128. weathering properties of aggregates – Part 2: Magnesium
34. BRITISH STANDARDS INSTITUTION: ‘Tests for chemical sulfate test’, BS EN1367-2:1998, London, British
properties of aggregates – Part 1. Chemical analysis’, BS Standards Institution.
EN1744-1:1998, London, British Standards Institution. 53. A. VERHASSELT and F. CHOQUET: ‘Steel slags as unbound
35. H. M. L. SCHUUR and C. P. BROADBENT: ‘Slag utilisation in aggregate in road construction: problems and
The Netherlands’, 231–239; 1991, (ed. S. J. Cribb), Conf. on recommendations’, 204–211; 1989, (eds. R. H. Jones and A.
The Economic Treatment of Mineral Wastes, Bath, 21–22 R. Dawson), Proc. Int. Symp. on Unbound Aggregates in
June 1990, Lichfield, MIRO. Roads (UNBAR 3), Nottingham, 11–13 April 1989,
36. R. K. TAYLOR and J. C. CRIPPS: ‘Mineralogical controls on London, Butterworths.
volume change’, 268–302: 1984, (eds. P. B. Attewell and R. 54. L. FULLALOVE: ‘Damage scares fail to halt steel slag use’,
K. Taylor), Ground movements and their effects on New Civil Engineer, 12 April 1984, 4–5.
structures, Glasgow and London, Surrey University Press. 55. J. J. BAILEY and H. M. REITZ: Discussion of ref. 12, Sept.
37. A. SEKI et al.: ‘Development of dusting prevention stabilizer 1970, 1810–1813.
for stainless steel slag’, Kawasaki Steel Technical Report, 56. A. VERHASSELT and F. CHOQUET: Reply to discussion on ref.
October 1986, no. 15, 16–21. 53, 235-256; 1989, (eds. R. H. Jones and A. R. Dawson),
38. M. REX: ‘Blastfurnace and steel slags as liming materials for Proc. Int. Symp. on Unbound Aggregates in Roads
sustainable agricultural production’, 137–149; 2001, (eds. J. (UNBAR 3), Nottingham, 11–13 April 1989, London,
Geiseler and H. Motz), Proc. 2nd Eur. Slag Conference, Butterworths.

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112 C195
Juckes The volume stability of modern steelmaking slags

57. ANON.: ‘Steelphalt: the alternative solution for the roads of 75. AMERICAN SOCIETY FOR TESTING AND MATERIALS:
tomorrow’, Steel World, 1999, 4, 60–61. ‘Standard method for autoclave expansion of Portland
58. J. GEISELER and H. MOTZ: ‘Untersuchung über den cement’, ASTM C 151–98a, Philadelphia, American
Zusammenhang zwischen im Laboratorium ermittelten Society for Testing and Materials.
Versuchsergebnissen zur Raumbeständigkeit und dem 76. J. J. EMERY: ‘A simple test procedure for evaluating the
Praxisverhalten von LD-Schlacken’, ECSC Final Report potential expansion of steel slag’, 90–103; 1974, Selected
EUR 13966 DE, Commission of the European workshop papers, Ottawa, Roads and Transportation
Communities, Luxembourg, 1992. Association of Canada.
59. AMERICAN SOCIETY FOR TESTING AND MATERIALS: 77. BRITISH STANDARDS INSTITUTION: ‘Methods of test for
‘Standard test method for potential expansion of soils for civil engineering purposes’, BS 1377: 1975,
aggregates from hydration reactions’, ASTM D 4792–95, London, British Standards Institution.
Philadelphia, American Society for Testing and Materials. 78. AMERICAN SOCIETY FOR TESTING AND MATERIALS:
60. H. KOLLER: ‘Practical experience in road construction using ‘Tentative method of test for bearing ratio of laboratory-
LD slag’, Information Day on Utilization of Blast Furnace compacted soils’, ASTM D 1883–61T, Philadelphia,
and Steelmaking Slags, Liège, 27 January 1988, Brussels, American Society for Testing and Materials.
Commission of the European Communities (D.G. XII), 79. BRITISH STANDARDS INSTITUTION: ‘Armourstone – Part 1:
Paper III.5. Specification’, BS EN 13383-1: 2002, London, British
61. BRITISH STANDARDS INSTITUTION: ‘Methods of testing Standards Institution.
cement – Part 2: Chemical analysis of cement’, BS EN 196- 80. BRITISH STANDARDS INSTITUTION: ‘Armourstone – Part 2:
2: 1995, London, British Standards Institution. Test methods’, BS EN 13383-2: 2002, London, British
62. P. CATOUL et al.: ‘Dosage conductimétrique rapide de la Standards Institution
chaux libre dans les scories Thomas et LD-AC’, Centre 81. BRITISH STANDARDS INSTITUTION: ‘Tests for thermal and
Nation. Rech. Métallurg., Oct. 1964, no. 1, 75–79. weathering properties of aggregates – Part 3: Boiling test for
63 AMERICAN SOCIETY FOR TESTING AND MATERIALS: ‘Sonnenbrand’ basalt’, BS EN 1367-3: 2001, London,
‘Standard test methods for chemical analysis of hydraulic British Standards Institution
cement’, ASTM C 114–99, Philadelphia, American Society 82. BRITISH STANDARDS INSTITUTION: ‘British Standard
for Testing and Materials. Guide to use of industrial by-products and waste materials
64. BRITISH STANDARDS INSTITUTION: ‘Quicklime, hydrated in building and civil engineering’, BS6543: 1985, London,
lime and natural calcium carbonate – Part 2. Methods of British Standards Institution.
chemical analysis’, BS6463: Part 2: 1984, London, British 83. BRITISH STANDARDS INSTITUTION: ‘Hot rolled asphalt for
Standards Institution. roads and other paved areas – Part 1. Specification for
65. E. E. PRESSLER, S. BRUNAUER and D. L. KANTRO: constituent materials and asphalt mixtures’, BS594: 1992,
‘Investigation of the Franke method of determining free London, British Standards Institution.
calcium hydroxide and free calcium oxide’, Anal. Chem., 84. BRITISH STANDARDS INSTITUTION: ‘Coated macadam for
1956, 28, 896–902. roads and other paved areas – Part 1. Specification for
66. C. M. MÜLLER and W. FIX: ‘Bestimmung von Freikalk in constituent materials and for mixtures’, BS4987: Part 1:
Stahlwerksschlacken – Auswahl eines Lösungsmittels’, 1993, London, British Standards Institution.
Arch. Eisenhüttenwes., 1974, 45, 685–691. 85. J. GEISELER et al.: ‘Absenkung der Freikalkgehalte von LD-
67. H. WITZER and W. FIX: ‘Bestimmung von Freikalk in Schlacken im flüssigen Zustand’, Stahl Eisen, 1987, 107,
Stahlwerksschlacken – Schnellverfahren mittels Leitfähig- 39–45 (403–9).
keitmessung’, Arch. Eisenhüttenwes., 1974, 45, 791–794. 86. J. GEISELER et al.: ‘Reduction of the free lime content of
68. M. BARTL and D. PEKÁREK: ‘The quantitative determination BOF slags in liquid state’, Stahl Eisen, 1987, 107, 107.
of uncombined calcium hydroxide and oxide in clinker and 87. M. KÜHN et al.: ‘A new BOF slag treatment technology’,
cement by X-ray diffraction’, Analyst, 1972, 97, 848–853. 445-453; 1997, Proc. 2nd Eur. Oxygen Steelmaking
69. L. VANLERBERGHE, R. DUMAREY and L. VAN BLAERE: Congress, Taranto, 13–15 October 1997, Milan,
‘Problems in the determination of free CaO in BOF slag’, Associazione Italiana di Metallurgia.
Proc. 46th Chemists’ Conference, Scarborough, 10–12 May 88. M. KÜHN, P. DRISSEN and H. SCHREY: ‘Treatment of liquid
1994, 75–81, Grangetown, British Steel Technical. steel slags’. 123–135; 2001, (eds. J. Geiseler and H. Motz),
70. F. M. LEA: ‘The chemistry of cement and concrete’, 3rd edn, Proc. 2nd Eur. Slag Conference, Düsseldorf, 9–11 October
111–112; 1970, London, Edward Arnold. 2000, Duisburg, Euroslag.
71. J. PIRET et al.: ‘Recherche pour une meilleure valorisation 89. R. SCHEEL and H. PETERSEN: ‘Zur Aussortierung von LD-
du laitier de haut fourneau et de la scorie LD’, ECSC Final Schlacken mit geringem Freikalkgehalt’, Stahl Eisen, 1977,
Report EUR 11750 FR, Commission of the European 97, 555–557.
Communities, Luxembourg, 1988. 90. C. YONGQUAN and C. QIZHONG: ‘Experiment on crushing
72. JAPANESE STANDARDS ASSOCIATION: ‘Iron and steel slag EAF slag’, SEAISI Q., 1993, 22, 81–85.
for road construction (English translation)’, JIS A 5015, 91. D. G. MONTGOMERY and G. WANG: ‘Instant-chilled steel slag
1992, Tokyo, Japanese Standards Association. aggregate in concrete – strength related properties’, Cement
73. B. L. FARRAND and J. J. EMERY: ‘Recent improvements in the Concrete Res., 1991, 21, 1083–1091.
quality of steel slag aggregate’, 99–106; 1994, (eds. P. 92. R. MOUSEL et al.: ‘Steelplant slag granulation system’, 172-
Mahant, C. Pickles and W-K. Lu) Proc. Int. Symp. on 175; 1993, Proc. 1st Eur. Oxygen Steelmaking Congress,
Resource Conservation and Environmental Technologies Düsseldorf/Neuss, 21–23 June 1993, Düsseldorf, Verein
in Metallurgical Industries, Toronto, 20–25 Aug. 1994, Deutscher Eisenhüttenleute.
Montreal, Canadian Institute of Mining, Metallurgy and 93. W. B. FEATHERSTONE and K. A. HOLLIDAY: ‘Slag treatment
Petroleum. improvement by dry granulation’, Iron Steel Eng., 1998, 75,
74. A. OKAMOTO, E. FUTAMURA and K. KAWAMURA: 42–46.
‘Hydration behaviour of LD slag at autoclave test’, Trans. 94. ANON.: ‘Blast granulation system of BOF slag’, Trans. Iron
Iron Steel Inst. Jpn., 1981, 21, 16–24. Steel Inst. Jpn., 1986, 26, 840.

C196 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112
 Juckes The volume stability of modern steelmaking slags

95. K. KANAMORI: ‘Safe disposal of molten LD converter slag of the new aging process of steel-making slag’, SEAISI Q.,
using rapidly rotating roller’, Trans. Iron Steel Inst. Jpn., 1997, 26, 37–48.
1973, 13, 255–264. 103. K. TANIGAWA, K. OKUDA and T. KUMAMOTO: ‘Recent
96. G. H. THOMAS: ‘Progress in the utilisation of steel slags in technology and developments for efficient slag processing
the UK’, 77–86; 2001, (eds. J. Geiseler and H. Motz), and utilization’, SEAISI Q., 1993, 22, 49–59.
Proc. 2nd European Slag Conference, Düsseldorf, 9–11 104. AMERICAN SOCIETY FOR TESTING AND MATERIALS:
October 2000, Duisburg, Euroslag. ‘Standard specification for steel slag aggregates for
97. P. ANDRIEUX: ‘Planches experimentales à base de scories bituminous paving mixtures’, ASTM D 5106–91,
LD’, Information Day on Utilization of Blast Furnace Philadelphia, American Society for Testing and Materials.
and Steelmaking Slags, Liège, 27 January 1988, Brussels, 105. J. M. PRUNEVIEILLE: ‘Slag bound mixtures in French road
Commission of the European Communities (D.G. XII), construction – history and developments’, 63–75; 2001,
Paper III.6.1. (eds. J. Geiseler and H. Motz), Proc. 2nd Eur. Slag
98. A. HILTUNEN, J. PUTRO and E. PÖYLIÖ: ‘Manufacture, use Conference, Düsseldorf, 9–11 October 2000, Duisburg,
and improved utilization of by-products of blast furnace Euroslag.
steel works in Finland’, Paper presented at Seminar on the 106. N. F. BEST: ‘Volumetric stability of weathered LD slags
Steel Industry and Recycling, Düsseldorf, 24–27 April containing both free lime and periclase’, ECSC Final
1995, Geneva, United Nations Economic Commission for Report EUR 10753 EN, Commission of the European
Europe (Working Party on Steel). Communities, Luxembourg, 1987.
99. R. J. COLLINS and P. T. SHERWOOD: ‘Use of waste and 107. J. PIRET, A. LESGARDEUR and A. DELMARCELLE:
recycled materials as aggregates: standards and ‘Utilisation de la scorie LD en construction routière’,
specifications’, Report prepared by the Building Research ECSC Final Report EUR 7631 FR, Commission of the
Establishment (BRE) for the Department of the European Communities, Luxembourg, 1982.
Environment, 7–8, HMSO, London, 1995.
100. L. M. JUCKES: Discussion on Ref. 53. In Proc. Int. Symp. Author
on Unbound Aggregates in Roads (UNBAR 3),
Nottingham, 11–13 April 1989, 235; (eds. R. H. Jones and L. M. Juckes graduated in geology from the University of
A. R. Dawson) London, Butterworths. Natal, South Africa, and in 1969 he was awarded a PhD by the
101. J. BONNOT et al.: ‘Études pratiques sur les scories LD University of Birmingham, UK. He then worked in the steel
utilisées en technique routière’, ECSC Final Report EUR industry on raw materials and environmental matters until his
7909 FR, Commission of the European Communities, retirement in 2000. He was in the Ironmaking Department of
Luxembourg, 1982. Corus Research, Development and Technology during the
102. S. MORISHITA, H. KIODE and K. KOMAI: ‘The development work on which this paper is based.

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) December 2003 Vol. 112 C197