CERAMURGIA INTERNATIONAL, vol. 2, n.

2, 1976 55

REFRACTORIES BASED ON LIME:

DEVELOPMENT AND PERSPECTIVES
INVITED REVIEW PAPER

F. NADACHOWSKI
Academy of Mining and Metal,lurgy, Cracow, Poland

CaO as a refractory shows specific high-temperature reactions, differing in some impor-

tant aspects from those of magnesia and even of doloma. Lime-carbon composites offer
much promise with regard to corrosion resistance to the attack of ferruginous slags. The-
re has been a considerable development of refractory lime technology over the post-war
period, including in recent years the so-called salt-lime materials of a wide range of pro-
perties. To secure future commercial manufacture, full advantage should be taken of the
specific merits of CaO, as well as of the possibilities of low-cost production. The most
promising fields of applications seem to be: full-lime linings for making pure and alloyed
steel, cement rotary kilns, glass regenerators and roofs, lime kilns and some specialized
installations.

1 - GENERAL C O N S I D E R A T I O N S stressed that for dolomite materials, impressive impro-

The abundance of raw materials and the very high
fusion point of calcium oxide are the main features
that enable one to consider this subtance a potential
basis for massive refractory production, indeed, lime
was one of the first materials used as a basic lining
for steel converters' and several technological pro-
cedures were patented as early as in the seventies of
the XIX-th century. However, being extremely difficult
to process and handle because of poor hydration re-
sistance, lime bricks were soon eliminated in compe-
tition with dolomite and magnesite. They have also
been considered inferior with regard to metallurgical
applications, since CaO is known to be subject to
heavy fluxing by Fe203 at temperatures above 1450°C -
in contrast to the behaviour of MgO.
Table I presents the author's assessment of technically
significant features and reactions of basic refractory
substances or their combinations, which have been or
could potentially be employed for lining steel furnaces.
Attention ought to be drawn to the fact that CaO
- - otherwise than MgO - - is characterized by rather
extreme properties: either very favourable or strongly
detrimental ones. Thus, the future of this novel re-
fractory seems to depend on more progress in over-
com,i,ng its natural drawbacks, as well as on finding
out specialized applications, (,also besides steel-making)
where most advantage could be taken from lime's
unique merits, including its low price.
With regard to the hydration problem, it should be
vements have been elaborated over the last decade,
such as: more efficient sintering procedures, tar
impregnation, application of new kinds of hydrophobic
substances and novel packaging techniques. All these
advances, facilitating the manufacture, handling and
storage of CaO-contai,ning bodies, can equally be applied
to pure lime refractories. This, however, had not
been fully realized, until tests conducted in recent
years confirmed the feasibility of a commercial pro-
duction of lime bricks without any major hydration
trouble (see further section 3).
Points (5) and (8) of Table I present only a simplified
picture of ~lime's specific response to the h~igh-tempe-
rature action of other substances. For a more detailed
discussion in section 2, these substances will be
arranged in two grups:
1 - potential constituents of lime-base composites,
compatible with CaO or reacting to yield refractory
products,
2 - fluxes or potential corrosive agents, reacting with
CaO to yield ~low-melting products.
2- HIGH-TEMPERATURE REACTIONS OF LIME WITH
OTHER SUBSTANCES
2.1 - REFRACTORY COMPOSITIONS
Among the potential consituents of lime-base compo-
sites, magnesia, carbon and silica appear to be the
 /

56 F. NADACHOWSKI

TABLE I - Characteristics of basi,c refractory substances employed in steel furnaces.

MgO-
MgO CaO MgO-CaO MgO-C CaO-C MgO.,Cr=O~

1 Raw material expensive cheap cheap expensive cheap expensive

2 Chemical basic strongly strongly basic strongly moderately
character basic basic basic basic
3 Hydration good very poor poor good poor very good
resistance
4 Fusion point very high very high high very high very high high
5 High-temperature
stability:
a at oxydizing good good good moderate moderate moderate
atmospheres (C burns (C burns (Cr loss by
out) out] volatization)
b at reducing moderate good moderate poor good moderate
atmospheres (some Mg (some Mg (MgO + C--* [volume
loss) loss) Mg + CO) changes)
6 Thermal shock poor moderate moderate moderate good very good
resistance (sometimes
moderate]
I Thermomecha- good or very good-strongly depending on impurities and texture:
nical behaviour
8 Corrosion
resistance to:
a ferruginous good poor poor very good good moderate
slags [as long (bursting
as C is not effects]
depleted)
b Ca-silicates moderate very good good moderate very good poor
(as long as
CaO is not
depleted)
c alkaline slags very good very good very good very good very g o o d moderate

most important ones. refractory. On the other hand, CaO.MgO exhibits a

Althou,gh the behavriour of MgO on heating in contact
w,ith CaO has been wetl known, only the proportions
covering the composition of doloma or its combina-
tions with magnesia have attracted adequate attention
so far. There is ,little information about the high-tem-
perature processes occurring with Hme containing
m,inor amounts of magnesia. The extent of solid solu-
bility of MgO in CaO as indicated by the binary phase
diagram * is larger than that on the MgO side of the
system. X-ray a,nalyses of samples cooled down from
1700°C showed that the periclase phase was absent
in mixtures up to about 5 weight per cent Mg03. The
I,atti,ce parameter of pure CaO decreased from 4,810~,
to 4.795 _+ 1 A with increasing MgO addition. This
experimental series showed that MgO does not readily
fall out of the CaO solid solution existing at high
temperatures; moreover, if some excess of magnesia is
present, it can be lost via gas phase (possibly owing
to reduction). For the practice, it can be concluded
that I,ime refractories, even those made from calcites
appreciably ,contaminated by dolom,ite, will essentially
remain monophase materials with no separate MgO
crystals. In commercial dolomite clinkers, up to 2.9%
MgO in the CaO phase has been found'. Of course,
the solid solubility on the CaO side of the system is
~avourable in that it avoids in lime bodies the forma-
tion of the 2370°C eutectic, which renders dorloma less
* All the phase diagrams referred to in this review are to be
found in Ref. 2.
higher degree of direct bonding in contact with dical-
cium ferrite melts'. Thus, to regard do,loma just as a
MgO-dHuted lime rnicrostructure, would be a,n over-
simplification. Both materials are more different in
their high-temperature behavio,ur, than it mdi,g,ht be
concluded from their mere chemical composition.
Carbon as a substance compatible with CaO deserves
a particular attention. It is capable of ;improving lime's
corrosion resistance as well as its thermomechanical
behaviour, while being itself somewhat protected from
quick oxidation by the framework of interconnected CaO
crystals. It has to be stressed that MgO, in contrast
to lime, ,can be reduced by C at steelmaking tempe-
ratures, yield,i,ng gaseous reaction products: Mg + CO,
which tend to escape from the brick's pore system.
This can be concluded not only from the existing free
energy data 6. ?, but also from a number of experiments
carried out independently over recent years ,_10.
The phenomenon of magnesia , consumption ~ by car-
bon at high tem,peratures has also been clearly evi-
denced for doloma.
The combinations of lime with silica are known to be
high,ly refractory (reaction products me l.ti,ng above
2000°C); a good example of making practical use of
this fact is the s~abilized dolomite. W,ith a large excess
of SiO,, however, the refractory sil,icates; 3OaO.SiO2
and 2CaO.SiO= are replaced by 3CaO.2SiO2 (r,anki,rHte}
or CaO.SiO, (woHastonite), melting well below 1600°C.
For doloma, the magn,itude of the silica contents
enabling the formation of non-refractory si.l,icates: mer-
REFRACTORIES BASED ON LIME: DEVELOPMENTAND PERSPECTIVES
winite or monticell,ite are less then those corre-
sponding to rankinite or woll,astonite formulas - - due
to the ,, dilution ,, of CaO by MgO. Also, because of
the 1800°C eutectic between calcium ortohosilicate and
MgO, this last oxide can be regarded as a flux in this
particular case.
Similar limitations apply, of course, to possible combi-
nations of lime with magnesium silicates, such as
forsterite.
When a corrosive action of silicate slags is envisaged,
the consequences of the formation of high-melting
calcium silicates in the contact area become parti-
cularly favourabie ". Such behaviour of lime refractories
contrasts with that of magnesite bodies with a forste-
ritic matrix. This matrix can readi,ly be destroyed by
steelmaking slags; as a result, zoning and s,palling
occur, whi,ch are not observed with lime or doloma.
The reactions of CaO - - with silica as a body consti-
tuent involve, u.nfortunately, some rather detrimental
side effects. These are:
1. expansion accompanying the formation of refrac-
tory silicates at grain boundaries, resulting in most
cases in serious texture embrittlement,
2 - ,, dusting- phenomenon on cooling due to calcium
orthosil,icate ~ " transformation, while stabi,lization
attempts sometimes turn ou,t to be less effective than
with dolomite.
The behaviour of lime-silicon carbide combinations
exposed to aqir at elevated temperatures is simila,r to
the b,e,h,aviour of th.o,se contain.ing sil,ica - - since SiC2 is
the only sol,id oxy,dation product. The reactions i,nvolved
herewith are somewhat complicated by gas evolution
{CO,} as wel,I as by possible temporary liqu,id formation
around the SiC grains. Bursting effects are often
observed.
Of less immediate significance, but with some pro-
s pects for future development, are the combinations
of lime with followi,ng oxides:
P20~, which forms with C aO refractory phosphates
4CaO.P20, and 3CaO.P20,; there exist also high-melting
solid solutions with calcium orthosilicate. Lime bodies
have been shown to be very resistant to attack by
phosphate containing melts".
Zr02, which reacts to yield CaO.ZrO~, of a fusion point
around 2400°C, compatible also with 2CaO.SiO,; in
mixtures CaO-ZrO=-SiO2 the - dusting ,, effect on cooling
was noticed.
TiO~, which forms with CaO refractory titanates
3CaO - 2TIC, and CaO • TIC=; these are compatible with
calcium orthosilicate as well.
Considering the topic of refractory compositions of
lime with other substances as a whole, it must be
remembered that CaO is inferior to MgO in that it
does not form high,melting compounds with AhO,
{except in AI~O, rich composition'} and Cr~O, {unless
the atmosphere is reducing which would enable the
formation of the refractory CaO. Cr20,}.
Thus, no equivalents of such valuable combinations, as
magnesia-chrome {.see Table I] and magnesia-spinel,
can be expected with m,ateria~ls based on lime or
doloma.
2.2-COMPOSITIONS YIELDING LOW-MELTING PRO-
DUCTS
Among the substances capable of attacking lime re-
fractori,es under working conditions, iron oxides should
be considered the most {mportant ones. The reaction
product is d,i,c~lcium ferrite, whose low fusion point
{around 1450°C} contrasts unfavourably with that of
magnesiofernite, which is known to enter a highly
refract(~ry solid solution when MgO ,is the substance
under attack.
Thus, at typical steelmaking temperatures {around
1600°C], there is a heavy fluxing of lime and no imme-
57
diately damaging reaction with magnesia. It has to
be mentioned that with doloma, the amount of liquid
phase resulti,ng from the action of a ferrug,inous slag
in not less, and even slightly more, than with pure
CaO. This can be conci,uded from appropriate phase
diagrams, as we,II as from special experiments. The
actu,al degree of slag satura,tion with both CaO and
MgO '' as well a,s the possibility of , washing o u t ,
isolated MgO crystals" play here a decisive role.
Thus, the usual MgO content in doloma does not
help, what might at first be expected, improve its
corrosion resistance to Fe20, action.
It is important to real,ize that the picture outlined
above can change i,f CaO is replaced by the CaO-C
combination, indicated in Table I. Then, the attacking
iron oxide undergoes a reduction by carbon and there
i,s no corrosion .effect as long as the latter is not
depleted inside the working layer of the br,ick.
Among other fluxes of some significa,nce the copper
oxides and the boric oxide have to be mentioned. The
first yield liquid i,n reaction with CaO somewhat above
1000°C. The second forms a series of low-melting
(roughly in the range of 1000-1500°C) calcium borates,
which is a behaviour not very different from that ob-
served within the B203-MgO system.
As already mentioned, the reaction products of AI203
and Cr20, added to a I.ime body are not refractory
compounds. This involves a risk with instaJl,lations, in
which bricks containi,ng large amounts of th,ese oxides
wou,ld work in contact with lime-base bricks at tem-
peratures exceedi+ng those corresponding to liquid
formation in the appropriate systems. On the other
hand, small additions of R203 oxides can in some cases
be useful in promoting the sintering of lime materials.
In the mixtures of calcium oxide with alumina, the
lowest eutectic temperature lies under 1400°C and
from among the existing calcium aluminates, the only
one compatible with I,ime is 3CaO.AI20,. The reactions
of CaO with other phases in this sys,tem, and also
with barium aluminates, are of some interest to tech-
nology and involve expansion effects; no use, however,
can be made of the cementing power of these com-
pounds because of lime's hydration susceptibility.
With alumino-silicate materials, CaO-bodies interact in
a damaging way because of the eutectic liquid forming
around 1350°C.
The reactions of lime in mixtures with chromium oxide
in air are somewhat more compl,icated beca,use of
the partial oxydation of Cr203 and the formation of
chromate-type compounds. The ternary phase 9CaO.
4CrO~. Cr~O,, often referred to as the , 941 ,,-com-
pound has a very low fusion point {not much above
1200°C} and is compatible with both CaO and MgO;
it also shows solid solubility in calcium orthosilicate.
One peculiar technological possibility is to impregnate
the pores of a burned lime br,ick with the - 9 4 1 ,
melt ".
Among fluxes which can be useful in bringing down
the temperature required to s inter CaO, calcium fluo-
ride should be mentioned, with an eutectic well under
1400°C, further decreas,ing to as low as 1250°C, if
calcium orthosi,l, icate is also present.
The attack of alkalis does not affect lime noticeably
in most cases, contrary to what is observed with many
traditiona,I refractories.
To complete this short survey of the specific reactions
of calcium oxide as a refractory the effect of gases:
CO2 and SO2 should not be omitted. Under 900°C, CaO
binds quite readily carbon dioxide, with heavy CaCO,
crystallization inside the pore system of the lime ma-
terial. With SO=, CaSO, and CaS form ac,co,rding to
the equation:
4CaO + 4SO,--~ 3CaSO, + CaS
When CO is present ,in the atmosphere, the su,lphide
is the only reaction product".
58
3 - DEVELOPMENT: TRADITIONAL TECHNOLOGICAL
PATTERNS
A renewed interes~ in lime refractories began during
the second world war and the early post-war period.
The CaO bricks were found worth mentioning in the
comptehensive book on refractories by Konopicky".
They have mainly been considered for selected appli-
cations with attention foSused at sintering additives
capable of raising the hydration resistance,
Among these additives, miscellaneous substances, raw
and technical materials were tried, such as"-": iron
ore, basic and acid slags, clay, feldspar, phosphates,
oxides of re, AI, Si, Cr, Mg, P, Ti, Mn, Zr, Sn, Co, Ni,
Mo, V, Th - - some of them obviously without much
chance of a commercial ap.pl'i.cation. As the most
promising fluxes del,aynig .lime's hydration decay, Fe20,
{possibly in the form ~of precipitated hydroxide} and
TiC2 were chosen. Calcium oxide refractory cruoibles
containing about 5% titania (in form of 3CaO.2TiO~]
were recommended for .melting phosphates 1'. In ano-
ther work ~°, 3-5% TiC2 was indicated as an optimum
addition for sintering lime ol,inkers, more titania having
been rather detrimental because of excessive 3CaO.
2T.iO2 formation.
Si,nteri.ng additives: Fe~O, and alumina-silica mixtures
were later put into patent specificatio,ns2'. Very good
service of such bricks ,i.n Hme-buming kil,ns was
reported 22
Comprehensive data have also been accumulated cha-
racterizing .pure C aO as a potential refractory, with
epeci,al regard to sintering behaviour, density and its
effect on hydration rate 23,2,. Bodies with minor mine-
ralizer contents were also included~'.
Much attention was devoted to slip casting procedures
both using organic =l,iqu.ids2, =~, and water suspensions
of Ca{OH)2"; 98% densities with CaO grain size of
the order o.f 10p:m were obtained after firi~n,g the
articles at ,n,o hi ghe~ than 1400°C.
There has been a considerable interest in using CaO
crucibles in the preparation of very high purity metals,
such as U arid Pu for atomic energy applications".2',
as well at ,Pt and Pa ~'.
In studies concerning the temperature dependence of
grain growth, higher activatio,n energy was estimated
for calcia than for magnesian; also data on CaO grain
growth, dihedral angle values in contact with dicalcium
ferrite and other melts were re,ported '~. Admixtures
of 1-5 mole ,per cent of SrO were found to inhibit
sintering in CaO, increasing the activation energy of
d ensffication'L The water vapour increases the rate
of initial sintering of calcia".
In the early sixties the use of lime linings for oxygen
steel converters was suggested", 3, and patented ~.
About the same time, a commercial ,prod,uction of a
fused pure lime grai,n (under the name of Kristallkalk}
was started in West Germany", mainly for metallurgical
purposes. Herewith, the benefits in the desulphuration,
dephosphorization and desoxidation processes of allo-
yed steel,s were stressed ~.~',". Later, more work on
fused refractory lime was ~eported '°.''. One of the
interesting modifications of this novel material is the
addition of zirconium dioxide, forming the highly re-
fractory CaO-ZrO2 matrix. The good results in attaining
highest steel purity with linings based on the • Kri-
staHkalk, were confirmed for electric arc furnaces '2,
as well as high-frequency rinduction on,es '3, where,
however, the high cost of fused I.ime and rather short
I,ining I,ives were somewhat discouraging.
A similar appl,ication of fused lime has been realized
in U.S.A., with a development of sintered direct-bonded
materials ,in view". In regard to hydration decay, fused
lime was found not to be as much s~perior to a well-
si.ntered cl,inker"." as previously expected. This was
attributed to a rather rapid crystall.ization of hydrate
F. NADACHOWSKI
laths inside the cleavage planes of well-developed
CaO grains.
Detailed publications concerning various technological
aspects of the manufacture of sintered lime refracto-
ries started to appear abou,t a decade ago. Properties
of burned products were reported" and their use in
oxygen steelmaking furnaces was recommendod".
In another comprehensive study, technological data con-
cerning burned, tempered and pitch-impregnated lime
bricks were presented", with rather good spalling
resistance and high hot strength values reported• In
some bodies, AI20, additions to pure sintered and
fused Hme were tried.
Foil,owing earlier suggestions" a commercial produc-
tion of tar-bonded lime shapes for LD converters was
organized in Poland during 1968-71 ","; l~ey showed
a slightly better over-all performance than the tar-dolo-
mite ones of an equivalent i,mpurity content. Because
of the difficulty of frequent changing the type of ma-
terial processed in a single plant, and following the
development of burned lime brick technology elsewhere,
the manufacture of tar-lime shapes was later aban-
doned. However, enough information was accu,mulated
to formulate a general ,idea about the wear pattern
of lime-type converter linings. While dicalcium ferrite
forming remained the chief corrosive reaction as
with dolorna, a marked decrease of the penetration of
si,licate slag components was observed, with heavy
3CaO.SiO2 crysta]lization in the contact area.
Similar tests with tar-lime shapes for steel oxygen
converters were conducted in Bulgaria'°; good results
in sintering domestic limestones as well as in service
performance were reported. Also, the possible carbon
oonsu,mption by reduction of Fe20,,.MgO and SiC2 in
dolomites was indicated as an argument for using
lime". It has to be mentioned that all these results
somewhat disagree wi~h the rather discouraging data
obtained in slag erosion tests"•
Recent years have brought a renewed interest in
research connected with characterization of refractory
CaO products, si.ntering problems and methods of
improving hydration resistar~ce.
A comprehensive study of physical and chemical pro-
perties as well as fabrication methods of pure lime
ceramics was published ~ extending appreciably the
existing knowledge in this field• In connection with
the assessment of the sinterability of CaO, the electric
conductivity of the activated oxide was studied"• With
regard to hydration problems, an unconventional me-
thod of increasing li,me's resistance was described ",
in which a protective CaCO, ,layer is formed on the
surface of lime bodies i,n a CO, atmosphere below
900°C•
Further sinteri,ng procedures were patented, including
the use of mineralizers"• Calcium fluoride was found
to be particularly effective i,n lowering the tempera-
ture of advanced densification", also in fabrication of
~ransparent polycrystalline CaO by hot pressing ". Lime
refractories of high refractory properties were obtained
from a commercially available calcium hydroxide",
sufficient si,ntering temperatures having been 1450°C;
the particular application i.n view was a pebble bed
heat exchanger.
More pub,l.ished data characterizing pure CaO ceramics
included those based on a plasma fused CaO", as
we,ll as a comp,ari,son of si,ntered MgO and CaO pro-
ducts, where lime's lower recrystallization tendency,
higher .evaporation and spal,l,i,ng resistance were
stressed ~.
Much work on lime refractories, co.nc.erni,ng their
characteri,sti,cs, sintering phenomena and m~nufacture
technology of shaped producs from fused and sintered
grain, have been conducted over a number of years
in the German Democratic Republic. A comprehensive
report of the whole problem was published" including
REFRACTORIES BASED ON LIME: DEVELOPMENT AND PERSPECTIVES
an extensive H.terature review. A continuation of this
work appeared recently ,2
In the .early seventies a pi,lot production of burned,
tar-impregnated bricks, based on a lime clinker sin-
tered in a rotary kiln, has been organized in Poland.
This enabled the rea,lization of a number of commer-
cial tests extending cons,iderably the existing applica-
tion .experience of these materials.
Although hydration still remained a ,problem in tran-
sport, storing ~nd bricklaying organization, it has been
shown in practice not to be an impediment to massive
manufacture and delivery over longer routes. Good
application results have been obtained in glass furnace
regenerator checkers of several w o r k s " as well as
in the sinteri,ng zone of a 2.4 m diameter cement kiln,
where a .record life was reported, a quick forming of
a stable coating being the remarkable feature of the
lime li,ning. Many smaller-scale tests were also made,
showing good corrosion resistance of I,ime bricks
in the bottoms of soaking pits, in units producing
ferro.manganese, lead and si,lver; first trials in copper
converters were ]ess successful. In several tests in
electric steel furnace walls, somewhat shorter average
lives than with standard basic brick were obtained.
Most of these results have recently been surveyed by
the present author'°; a classifi'cation of lime bricks
was also suggested, and characteristics of bricks of
two principal brands constituting a combination of
lime and carbon (denominated - C a l c a r , brick) were
given.
It is i,nteresting to note that in technological develop-
ments and patent specifications use has been made of
nearly all the refractory combinations of lime with
other substances reviewed i,n section 2.1.
4-DEVELOPMENT: SALT-LIME REFRACTORIES
The use of the so-called salt phase in making lime
refractories can be regarded as a new element, greatly
extending the technological possibilities. This element
received only .a limited attention in previous publica-
tions; it now appears, ,however, that a significant part
of the forthcoming development will go along this
I,ine.
The salt phase contained in the lime-base mass plays
the role of a temperatury working medium of special
kind, intensifying important ceramic processes. Unlike
tradition,al flu~es, it forms very early on heating (at
300-800°C) a liquid of high fluidity wetting very well
the CaO crystals and promoting a vigorous grain
growth". The mai,n component of the salt phase is
calcium chloride 65, whose behaviour o,n heating inside
a refractory body is characterized by a gradual high-
~emperature hydrolysis. In the range of 800-1200°C a
peculiar microstructure forms, consisting of a conti-
nuous framework of dense aggregates of well-de-
veloped CaO crystals wetted by the salt liquid and
large rounded pores ~. Such a mi,crostructure is very
resistant to further volume changes (even on heating
to 1700°C), in spite of the step-by-step transforma-
tion of the .salt phase into secondary CaO. The feature
of volume stabillity on firing i,s characteristic even for
bricks made directly from a CaCO3 mass with an
appropriate salt addition.
The actual development of salt-lime refractories is
concentrated on two main brick types: - D - (dense)
and , P ~ (porous).
Type - D ,, bricks, based on a pure salt-lime calcine,
are characterized by a predominantly fine-grained, very
uniform texture and can reach cold crushing strengths
up to 200 MN/m 2 (2000 kG/cm2), with porosities under
10%. During one-sided heating, some increase of the
hot face porosity occurs due to the loss (transfor-
mation} of the salt ,phase; however, this does not
invite slag infiltration owing to the gas overpressure
59
created ilnside the refractory '°
The technology of the = P ~ type refractories is unu-
sual" ,in that the bricks are formed from a raw ground
limestone mass (contai,ning salt) and fi~ed to obtain
highly porous, but essentially non-shrinking products;
these are to be then impregnated wi~h a large amount
of tar or pitch, to create a calc,ium oxide-carbon com-
posite (de,nomi,nated - Calcar P ,). This initial procedure
is being further developed in order to attain sufficient
strength also without impregnation. Of particular in-
terest seems to be the so-called calcite brick - - un-
burned and resistant to hydration, with a high cold
crushing strength, showing little hot face shrinkage
even at 1700°C.
Some application data are avai,l,able so far only for
the porous type of salt-lime bricks.
A coked Ca,lcar P block inserted into a conventional
tar-dolomi,te lining of an oxygen steel converter did
not exhibit any deeper wear. Thi's would indicate that
a much increased carbon content could possibly be a
match for the enhanced porosity of this material.
Several small,scale tests with , Calcar P , were con-
ducted in steel ladle linings, always showing an
excellent corrosion resistance in comparison with the
surrounding traditional fireclay products. However, full-
scale ladle linings could only be made with non-impre-
gnated, low-strength bricks, because of the difficulty
of coking ,larger brick quantities. Even so the iron
oxide at-Lack turned out to be negligible, the main
wear reason having been connected with the material's
excessive thermal expansion and local erosion by the
steel stream during pouring in.
P-bricks of the same type were also tried as roofs
and walls of smal,I furnaces producing Na-Ca-glass,
showing no corrosion damage. The result of the first
roof test of unburned calcined shapes under similar
working conditions was also encouragling.
Apart from salt-lime bricks, also masses of this type
with somewhat different compositions were used for
gunning hot steel furnace walls. They showed good
adherence to basic linings and interesting effects of
retarding iron oxide attack.
5 - PERSPECTIVES
The general conclusion from the existing publications
reviewed in previous sections is that the fu,nd,a,mental
knowledge about lime's be haviour as a refractory has
already been accumulated. Extensive informations con-
cerning the physical and chemical pro,perties of pure
substance CaO; elaboration of sintering procedures
with various starting materials i nolud,ing appropriate
kinetic data; evalL~ation of lime's hydration and corro-
sion response under different conditions; experiments
with lime-base composites i.nclud~ing sophisticated tech-
nologi,cal procedures; tens of patents {most of them
not indicated in this short review}; advanced appli-
cation tests in various industrial branches - - a,l:l this
seems to create a sufficient basis for the development
of I,ime as a commercial refractory in a not very
distant future - - taking of course into account the
abundance, cheapness and purity of the raw material.
In accordance wi,th what already had been indicated
in section 1, the most immediate steps to be taken in
order to further this development appear to be:
a - a concrete utilization of the specific features of
this novel refractory group and
b-a ra~ion,al decrease in production costs, which
could render economical many applications previously
considered too expensive with regard to refractory
~pending.
Under a both the possible favourable :influence of lime-
base .linings on metallurgical and other industrial pro-
cesses is to be taken into account, and the chances
60
of attai,n,ing in some cases better lining live,s than
those of traditiona~l refractories used so far.
Under b, switching over from fused to si,ntered lime
seems to be a step of most importance and sufficiently
substantiated a,t present, espec;ia,l~ly if the double-stage
procedure {calcin,ation-pel,letizati,on-final sintering} is
considered; also, the low-cost salt-lime technology of-
fers here fu~rther possibi'li~ies, the extreme case being
the calcite bricks, competitive even to fireclay and
silica.
It should be kept i,n mind, too, that in quite a number
of ,regio,ns the replacement of doloma refractories by
l.ime ones will - - both for economical and purity
reasons - - be the most rational decision once the
new technology becomes familiar. For example, the
local cost of iirnestone foi ~ the Bulgarian metallurgical
plant ,, Kremik, o v t s i , is .estimated at one third of
that of dolomite ,8.
Some ,application problems arising from what had
been postulated under a are discussed in the fol,lowing
sections.
5.1 - STEEL FURNACES
As already poin,ted out, there is a lot of data indicating
the remarkable effect of lime linings on steel purity 38.,8,
especia, Hy with regard to very low sulphur contents,
not to be attained unless special desoxydizing ope-
rations, or a vacuum treatment are employed ,9 70. Since
most of these results were reached with fused CaO
refractories, their high ,price has been regarded as a
serious obstacle to further expansion. It should be
realized, however, that there is no practical reason
for not using the cheaper sintered I,ime with which
similar effects of steel purity can be attained. Further-
more, with the expected diversification of the proper-
ties and costs of various types of lime-base bricks,
it seems now feasible to Hne all the parts of steel-
making units with these refractories, including electric
furnace roofs and ladles. This last application of lime
bricks would ,also eliminate sources of many types
of exogenic inclusions .i,n steel, such as si,licates and
spinel {MgO.AhO,), as well a,s enable a better control
of microcontaminants content. I.n addition to that, an
increased MgO-content in slag is con,sidered undesi-
rable in making alloyed steel.s 7' and in refining under
the synthetic CaO-~hO3 slag'Q.
With such a I,ime-lined steelmaking assembly some
mismatch of the durability of various parts of the
whole production line might emerge at first. While,
for instance, ladles would probably show a prolonged
life, the resistance of CaO-based furnace walls, espe-
cially the , hot spots ),, could hardly be expected to
equal the present performance of specialized magnesia-
base basic brickrs. It should be remembered, however,
that the use of CaO-C composites {, Calcar = refrac-
tories) might offer an answer to this problem, if
effective methods of perpetuating the presence of car-
bon i,nside the refractory microstructure could be ela-
borated. The development of special gunning composi-
tions seems to be one of the possible solutions. In
contrast to lime, any combination of magnesia with
carbon is, as already pointed out, princ.ipally incom-
patible under modern steelmakin,g conditions; the more
so if the working temperatures should be subject to
further rise 72, which, of course, cannot be ruled out
for the future.
With highly phosphorous slags in making certain steel
brands, lime refractories, shown to dissolve ,less ra-
p,idly than does magnesia ,5, appear to be an obvious
solution once the misunderstand,ing about their pro-
du,ction costs ceases to exist.
5.2 - CEMENT KILNS
Taking into accoLmt the chemical si,milarity of lime
materials to the cement clinker, as well a,s the lack
F. NADACHOWSKI
of low-melting reaction products, a good performance
of lime lin'i,ngs in the sintering zones of cement ro-
tary kilns can logically be anti:ci,pated. Appropriate sug-
gestions have been made some time ago 7','8, while,
however, the refractory costs appeared to be pro,hibi-
tive. Here again the pilot production of , Calcar K ,
brick made from sintered limestone showed that this
problem could be overcome. In the recent commercial
test mentioned in section 3, good prospects for the
appl,icatio,n of these bricks in cement kilns were con-
firmed. In addition to prolonged life, a nondestructive
character of calcium carbonate crystallization under
the co.ating was observed. The phenomenon of texture
embrittlement and heavy crack,i,ng resulting from the
reaction of CaO with CO2 gas, sometimes blamed for
premature failu(res of dolomite linings, was absent in
case of lime brick. The effect of CaCO, build-up
in the pore space, assuming the form of tight cry-
stalline layers, was to m.arked,ly densify and strengthen
the texture with no ,hartm to the brick's high hot
strength. Si,nce, however, no data are available yet
from large units of 5 m diameters and more, new
problems may emerge during further commercial expe-
ri,ments. In has to be added that the development
program mes will probably include also kiln sections
other the sinteri.ng zone and besides pure I,ime bo-
dies, lime,silicate compositions, whose un,ique advan-
tage in the retention of clinker coatings was reported".
5.3 - GLASS FURNACES
Although al,I aspects of the reported good performance
of Hme refractories i,n glass tank regenerator chambers
are still far from bei,ng thoroughly elaborated, the
future of this application, in the Pol'ish industry at
least, seems to be dependent only on the progress in
brick supply. Mere research is ,of course needed con-
cerning the ,microstructure changes under various work-
ing conditions, including a comparison with the exten-
sive experimental data accumulated so far for the
magnesia-base checker brick. Paradoxically, the hydra-
tion susceptibility of lime refractories has been wel-
comed in some glass works, as it facilitated a quick
pulling down of a wornou,t construction.
Although the tests with lime-base roofs of glass tanks
are less advanced at present {no data avai,lable for
furnaces of normal size}, the prospects appear to be
equ,aHy good as for regenerators. The price of calcite
shapes will probably be competitive with silica, while
their higher refractory properties and corrosion resi-
stance can hardly be disputed. A ,serious factor retar-
ding the development of this application is, apart from
brick availability, the difficulty in testing roofs con-
stru,cted of mixed materials, as the reactions of lime
with most traditional refractories are damaging at
glass tank working .temperatures.
5.4 - MISCELLANEOUS INSTALLATIONS
An obvious application of li,me refractories is the lime
burn,ing kiln, where excellent commercial results have
been obtained 7,. A prolonged life can also be antici-
pated in the industry of phosphorus compounds, consi-
dering the high melting points of reaction products
of CaO with P205 as indicated in section 2.1.
Small scale .experiments were encouraging i,n the
bottoms of soaking pits for steel ingots as well as
in miscell,aneous installations of the non-ferrous metal
industries already mentioned .in section 3.
Under consideration are the chances of making use
of dense lime .shapes in coke ovens as wel,I as in
Cowper stoves of blast furnaces.
In high-temperature vacuum processes, where low
oxygen levels are required, advantage can be taken
of lime's ]ower tendency to volatilize tharn that of
other basic oxides ,8, especially with regard to future
REFRACTORIES BASED ON LIME: DEVELOPMENTAND PERSPECTIVES
more demanding wort~ing conditions.
Among special applications requiring refractory service
at very high temperatures, the pebble heat exchangers
are of particular interest for pure lime bodies s'.
It can also be assumed with some probability that
lime brick ,could find rat.ional applications and show
good performance in some special,ized high-temperature
chemical installations, such as soda regeneration cham-
bers, kilns in the processing of barium compounds
and others.
6 - CONCLUDING REMARKS
Existing data concerning the properties and behaviour
of I.ime as a refractory create, in the author's opinion,
a sufficient basis for developir~g its manufacture on
a commercial scale. Following facts shou,ld help such
a development:
-- hydration is no more an unsurmountable barrier to
making and employing lim,e-base brick and masses
-- lime is a really cheap ~efractory and in most cases
there is .no need for using it in the expensive fused
form
-- new technological processes, specific for CaO and
including salt components are being developed; they
should facilitate making I,ime products of a very wide
range of properties and cost
-- in most applications which involve iron oxide attack,
lime-carbon composites offer a solution for prolonging
lining life in comparison to that of lime alone
--specific features of CaO render this most basic
refractory more attractive than doloma and magnesia
for some important applications in the steel, cement
and glass indu,stries, where commercial tests have
already been well advanced; also highly specialized
uses in various mod,eirn installations are probable.
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Received December 23, 1975.