Role of Minor Elements in Cement Manuf and Use

Portland Cement Association
Research and Development Bulletin RDIOST

Role of Minor lements in
Cement anufacture and Use
by Javed I. Bhatty
KEYWORDS: manufacturing, minor elements, portland cement, raw materials, trace elements
ABSTRACT: In this review, the effects of almost all the stable minor and trace elements on the production and
performance of portland cement have been reported. Emphasis has been given to elements that occur in natural
and by product materials used for cement manufacturing. The elements for which detailed information has been
obtained are dealt with in an order based on the periodic classification of elements. The volatilities of the elements
have also been discussed where ever necessary. Elements reviewed include: hydrogen, sodium, potassium,
lithium, rubidium, cesium, barium, beryllium, strontium, magnesium, boron, gallium, iridium, thallium, carbon,
germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium,
fluorine, chlorine, bromine, iodine, helium, neon, argon, krypton, xenon, yttrium, titanium, zirconium, vanadium,
niobium, tantalum, chromium, molybdenum, tungsten, manganese, cobalt, nickel, copper, silver, zinc, cadmium
mercury, and the lanthanides.
REFERENCE: Bhatty, J. I., Role of Minor Elements in Cement Manufacture and Use, Research and Development
Bulletin RD109T, Portland Cement Association, Skokie, Illinois, U.S.A., 1995.
MOTS CL ES: ciment portland, 616ments mineurs, 616ments trace, fabrication, mati$res premi?u-es
RESUME: Ce document rapporte les effets de presque tous les Mrnents mineurs stables et Uments trace sur la
/
production et la performance du ciment portland. Laccent a W mis sur les dldments qui se trouvent ~ Idtat
naturel clans les mat6riaux aussi bien que sur ceux des rclsidus utilisds lors de la fabrication du ciment. Les
416ments pour lesquels de linformation ddtaillde a W obtenue sent abord4s aans un ordre basal sur la classifica-
tion p(%iodique des Wments. La volatility des Wrnents est aussi traitde lorsque n6cessaire. Parmi les d~ments
couverts, on retrouve: lhydrog~ne, le sodium, le potassium, le lithium, le rubidium, le c&sium, le barium,
b&yllium, le strontium, le magn6sium, le bore, le gallium, Iindium, le thallium, le carbone, le germanium, l6tain,
le plomb, lazote, le phosphore, Iarsenic, lantimoine, le bismuth, loxygtme, le soufre, le sdh%ium, le tenure, le
fluore, le chlore, le brome, Iiode, lh61ium, le neon, largon, le krypton, le xdnon, lyttrium, le titane, le zirconium,
le vanadium, le niobium, le tantalum, le chrome, le molybdbne, le tungst$ne, le manganbse, le cobalt, le nickel, le
t
cuivre, largent, le zinc, le cadmium, le mercure et Ies lanthanides.
REFERENCE: Bhatty, J. I., Role of Minor Elements in Cement Manufacture and Use, Research and Development
Bulletin RD109T, Portland Cement Association [R61e et utilitd des Wirnents mineurs clans la fabrication du
ciment, Bulletin de Recherche et D6veloppement RD109T, Association du Ciment Portland], Skokie, Illinois,
U. S. A., 1995.
I
PCA R&D Serial No. 1990
PCA Research and Development Bulletin RD109T
Role of Minor Elements in Cement
Manufacture and Use
by Javed 1. Bhatty
ISBN 0-89312-131-2
@ Portland Cement Association 1995
Role of Minor Elements in Cement Manufacture and Use
Contents
Page
INTRODUCTION ................................................................................................................................. 1
ALTERNATIVE MATERIALS AS PARTIAL RAW FEED OR FUEL IN CEMENT MAKING ................1
DEFINITloNs ...............................................................l...i ....................................................m.............2
Major Elements ...................................................................................................................... 2
Lesser Elements ................................................................................................................... , 3
Minor Elements ...................................................................................................................... 4
Trace Elements ...................................................................................................................... 4
SOURCES OF MINOR ELEMENTS ................................................................................................... 4
MINOR ELEMENTS IN CEMENT MAKING ........................................................................................ 6
ELEMENTS IN GROUP I (Hydrogen, Lithium, Sodium, Potassium, Rubidium, Cesium)., .................. 7
Hydrogen ................................................................................................................................ 7
Lithium .................................................................................................................................... 8
Sodium and Potassium .......................................................................................................... 8
Rubidium and Cesium .......................................................................................................... 11
ELEMENTS IN GROUP II (Beryllium, Magnesium, Calcium, Strontium, Barium) ............................. 11
Beryllium .............................................................................................................................. 11
Magnesium ........................................................................................................................... 11
Calcium ................................................................................................................................ 11
Strontium .......................................................c........i ............................................................. 11
Barium .................................................................................................................................. 11
ELEMENTS IN GROUP Ill (Boron, Aluminum, Gallium, Iridium, Thallium) ....................................... 12
Boron. ................................................................................................................................... 12
Aluminum ............................................................................................................................. 12
Gallium, Iridium, and Thallium .............................................................................................. 12
ELEMENTS IN GROUP IV (Carbon, Silicon, Germanium, Tin, Lead) .............................................. 13
Carbon ................................................................................................................................. 13
Silicon ................................................................................................................................... 13
Germanium .......................................................................................................................... 13
Tin ........................................................................................................................................ 13
Lead ..................................................................................................................................... 13
ELEMENTS IN GROUP V (Nitrogen, Phosphorous, Arsenic, Antimony, Bismuth) ........................... 13
Nitrogen ................................................................................................................................ 13
Phosphorus .......................................................................................................................... 14
Arsenic ................................................................................................................................. 14
Antimony .............................................................................................................................. 15
Bismuth ................................................................................................................................ 15
,,.
Ill
Contents
Page
ELEMENTS IN GROUP VI (Oxygen, Sulfur, Selenium, Tellurium)
................................................... 15
Oxygen ................................................................................................................................. 15
Sulfur ....................................................................................................................................
Selenium .............................................................................................................................. 1;
Tellurium ............................................................................................................................<. 17
ELEMENTS IN GROUP Vll (Fluorine, Chlorine, Bromine, lodine)
.c.................................................. 17
Fluorine ................................................................................................................................ 17
Chlodne ................................................................................................................................ 19
A/ir7iteCements ....................................................j..........................................................c. 19
Bromine ................................................................................................................................ 19
lodine ...................................................................................................................................2O
ELEMENTS IN GROUP Vlll (Helium, Neon, Argon, Krypton, Xenon) .............................................. 20
TRANSITION ELEMENTS ................................................................................................................2O
Yttrium.. ................................................................................................................................ 20
Titanium ...............................................................................................................................2O
Zirconium ..............................d.............................................................................................. 21
Vanadium ............................................................................................................................ 21
Niobium ................................................................................................................................ 22
Tantalum .............................................................................................................................. 22
Chromium,... ......................................................................................................................... 22
Molybdenum .........................................................!.. ............................................................. 23
Tungsten .............................................................................................................................. 23
Manganese .......................................................................................................................... 23
Cobalt ................................................................................................................................... 24
Nickel ................................................................................................................................... 24
Copper ................................................................................................................................. 24
Silver .................................................................................................................................... 24
Zinc ...................................................................................................................................... 24
Cadmium .............................................................................................................................. 25
Mercury ................................................................................................................................ 25
THE RARE EARTHS ......................................................................................................................... 25
CONCLUSIONS ............................................................................................................................... 26
ACKNOWLEDGEMENTS .................................................................................................................. 26
REFERENCES .................................................................................................................................. 27
APPENDlx .........................................................................................!c....................................c........35
INDEX ............................................................................................................................................... 38
iv
PCA Research and Development Bulletin RDI09T
Role of Minor Elements in Cement
Manufacture and Use
by Javed 1. Bhatty*
INTRODUCTION
The purpose of this review is to col-
Iect pertinent information on the be-
havior of minor and trace elements on
the manufacture and use of cement.
Attempts have been made to identify
gaps, if any, in the information thus
far available and suggest work for
further investigations.
As cement manufacturers
continually strive to conserve re-
sources, use of alternative raw feeds
and seconda~fuels derived from con-
tinuously generated industrial by-
products isgaininginterest. The likely
concerns from alternative or new natu-
ral sources are the incorporation of
trace elements into clinker and their
effects on the performance of cement.
These effects are, to a large extent,
dependent upon the type of trace ele-
ments contained in the raw feed, their
concentration levels, and the operat-
ing conditions of the kiln.
The effects of minor elements on
the production of clinker and perfor-
mance of cement are summarized in
the appendix.
ALTERNATIVE MATERIALS
AS PARTIAL RAW FEED OR
FUEL IN CEMENT MAKING
There has been an increasing move
toward using a variety of alternative
materials in cement manufacturing,
with the multiple aims of reducing
by-product accumulation to address
environmental problems and to
achieve technical advantages during
clinker processing without sacrific-
ing the quality of cement.
Chlorideby-products, and wastes
from the soda ash industry, when
mixed with fly ash and limestone, are
reported to have produced low tem-
perature clinkers (1200C) with com-
parable compressive strength (Patel,
1989). Phosphogypsumhasbeen used
as a source of limeinkilnfeed. Though
the clinker attained a different micro-
structure, the cement compared fa-
vorably with the conventional type
(Toit, 1988). In separate studies, spent
clays from lubricating oil refining,
have also been tested as raw feed
components for clinker production
(Midlam, 1985).
Sewage sludge as a partial kiln
fuel was reported by Obrist (1987).
Heavy metals in the sludge were per-
manently withdrawn from the bio-
sphere with little toxic emissions. Or-
ganic pollutants were reliably de-
stroyed without leaving any toxic by-
products. The only exception maybe
mercury which must be controlled
adequately.
Ostrovlyanchik et al. (1986) re-
ported that the use of fly ash from coal
power plants as raw material, in place
of argillaceous material, was effective
for improving the wet process kiln
output with savings in the fuel con-
sumption.
Bhatty et al. (1985) produced an
ASTM C150 Type I cement from the
copper-nickel and taconite tailings
used as a partial substitute for ce-
ment raw feed. The resulting ce-
ment had a microstructure and
strength properties comparable to
that produced with conventional
feed.
Weatherhead and Blumenthal
(1992), of the Scrap Tire Manage-
ment Council, concluded from a re-
cent field stud y that tires can be used
successfully as an alternative fuel in
cement kilns. The fuel cost is signifi-
cantly lowered, and the production
rate is enhanced without adversely
affecting the quality of cement. No
significant change in the environ-
ment quality, due to emissions, was
noted.**
*
u!+
Senior Scientist, ConstructionTechnol-
ogy Laboratories, inc., Skokie, lllinois
60077, U.S.A.Tel: (708)965-7500
A distinctionbetween the terms tire-
derived fuel and whole tires may be
made here. The tire derived fuel (TDF)
uses shredded tires in combination with
other conventional fuels (coal, coke, oil,
gas, etc.) usually in the burner end, tire
chips are also fed to calciners, whereas
thewhole tiresare fedintothe feedendof
a precalciner or a preheater kiln or into
the calcining zone of a long kiln.
ISBN 0-89312-131-2
0 Portland Cement Association 1995 1
Use of scrap tires and lubricating
oil, as alternative fuel in cement manu-
facturing, has also been reported in a
number of test burns in Australia and
Canada (McGrath, 1993; and Heron,
1993). The tests suggested substantial
reduction in manufacturing costs, im-
provement in waste minimization, ad-
vances in resource recovery, extended
life of existing landfills, and better en-
vironmental control.
De Zorzi (1988) reported Italian
experience on the use of municipal
solid waste as a partial fuel in cement
manufacturing. The chemical and
physical characteristics of clinker and
cement were comparable to those pro-
duced conventionally. No significant
change inorganic or inorganic pollut-
ants, such as dioxins, furans, SOXand
NOX, were detected in the stack emis-
sions. There were no material han-
dlingproblems,but storage of the solid
waste, especially the refuse derived
fuel (RDF), was expensive, because it
needed to be contained in totally en-
closed compartments for technical and
environmental reasons.
Regarding Norwegian experi-
ence, Ingebrigtsen and Haugom (1988)
demonstrated that using hazardous
liquid wastes containing PCBS as a
partial kiln fuel offered an efficient
way to solve a difficult environmental
problem. For waste containing chlo-
rine levels in excess of ().()ls~o, the use
of a by-pass was recommended.
Krogbeumker (1988) also reported that
waste oils containing PCBS were tested
as effective kiln fuel with adequate
atomization of the oils into the gas
stream. The levels of polychlorinated
dibenzodioxin and dibenzofuran in
emissions were very low and close to
the limits of detection. Although these
tests were very successful, PCBS are
not burned in U.S. cement kilns.
Huhta (1990) surveyed some
twenty North American cementplants
operating with wastes as supplement
fuel, and noted that the predominant
waste being used was waste oil fol-
lowed by solvent derived fuel and
scrap auto tires; wood chips and fluid
coke were also mentioned. However,
it is projected that the tire derived fuel
(TDF) will become the most advanta-
geous fuel in the near future, because
of its availability and easy handling.
Kelly (1992), and Mantus et al.
(1992) reported that the use of wastes
as supplemental fuel in well designed
and properly operated kilns results in
metal emissions too negligible to cause
any adverse health effects. It was also
demonstrated that the cements and
kiln dusts thus produced were not sub-
stantially different from those conven-
tionallyproduced. The effects of wastes
on the emissions of organic compounds
and metals from kilns were also stud-
ied by von Seebach et al. earlier in
1990. It was reported that a virtually
complete destruction and removal of
hazardous organic compounds occurs
in the kiln. A destruction and removal
efficiency (DRE) of hazardous com-
pounds was recorded at 99.9996Y0.
DREs in access of 99.97 are routinely
achieved.
Siemering, Parsons, and Loch-
brunner (1991) have also reported on
their experiences of burning wastes as
kiln fuel and have reported both tech-
nical and economical advantages with
minimal adverse environmental im-
pact.
In a recent article, Hansen (1993)
has strongly advocated the use of solid
wastes in cement manufacturing, em-
phasizing potential environmental and
political advantages. It was suggested
that using wastes as fuel has two-fold
environmental benefits; it would not
only avoid fossil fuel extraction and
transportation, but would also mini-
mize emissions that would have oc-
curred by disposal of these wastes
through treatment or by landfilling.
Politically, the liability of landfills and
demands for waste minimization in an
environmentally sensitive society, such
as the United States, can be substan-
tially reduced by waste utilization in
cement making.
Gossman (1988) pointed out some
of the risks and liabilities associated
with the use of hazardous waste-de-
rived fuels, and proposed certain ana-
lytical means to minimize liabilities
in order to achieve full economical
and quality control advantages.
Although there are opportuni-
ties to beneficially use wastes in ce-
ment production, their total substitu-
tion in the industry is still in the ex-
perimental stages. One recommen-
dation has been to limit the use of
waste to 5/Obyweight of the raw feed
(Vogelet al.,1987). Huhta (1990), and
von Seebach et al. (1990) have re-
ported a potential of 20-307. or even
more for waste as a fuel replacement
in cement kilns; some plants have
already used 50-10O% replacement.
Nonetheless, the level of application
and degree of success largely depends
upon the waste composition in terms
of the type and concentration of mi-
nor or trace elements.
In summary, under favorable
practical conditions, wastes can have
the following combined benefits:
a.
b.
c.
d.
e.
f.
g.
Respond to commercial and en-
vironmental pressure to use al-
ternate raw materials and waste
by-products.
Recover potential energy value
from the wastes.
Conserve nonrenewable raw
materials and fossil fuels.
Enhance process efficiency.
Produce more reactive raw
mixes.
Produce cement of improved
quality.
Reduce COZ emissions.
DEFINITIONS
Major Elements
According to Rompps Chemie-
Lexikon (1987), the elements that are
more abundantly present (>.5XO) in
cement clinker are the major elements.
These are calcium (Ca), silicon (Si),
aluminum (Al), iron (Fe), and oxy-
gen (0). Carbon (C) and nitrogen
G
PCBs=polychlorinated biphenyls
2
Table 1. Typical Compositions and Physical Properties of Portland Cements
Compound Composition (O/.) Type I Type II Type Ill Type IV Type V
C,s 58 49 60 25 40
C2S 15 26 15 50 40
C3A 8 6 10 5 4
C,AF 10 10 8 12 10
Gypsum 5 5 5 4 4
Loss on Ignition 1.7 1.5 0.9 0.9 0.9
Blaine (m/kg) 350 350 450 300 350
1-day Strength (psi) 1000 900 2000 450 900
7-day Heat of Hydration (J/g) 330 250 500 210 250
(N), because of their abundance in
the raw material and the earth atmo-
sphere respectively, can also be re-
garded as major elements.
In clinker and cement analyses,
Ca, Si, Al, and Fe are expressed as the
oxide form (CaO, SiOz, A120~, and
FezOJ. However, they eventually ex-
ist as more complex compounds. The
approximate formulae of these com-
pounds, alsoknownasclinker phases,
are tricalcium silicate 3CaO*SiOz
or C#*; dicalcium silicate 2CaO*SiOz
or CZS; tricalcium aluminate
3CaO*A110~ or C~A, and tetracalcium
aluminoferrite 4CaO*AlzO~*FezO~ or
CgAF. Since the role of major ele-
ments in cement manufacturing has
been fairly well understood, only a
brief summary on the presence of
major compounds in cement is given
here.
Calcium is an essential compo-
nent of cement, which comes from
the decomposition of the primary raw
material such as limestone, chalk,
marl or cement rock depending upon
the geological location of the cement
manufacturing plant. Silicon in ce-
ment is derived from silica sand, or
from clay, shale, or slate, which are
also sources of aluminum andiron in
the raw material. Iron is sometimes
derived from iron ores, or mill scale,
and added separately if the raw mix
is deficient in iron. Aluminum may
be added with bauxite or other
sources. Auxiliary materials such as
fly ash and blast furnace slag are also
often added as raw feed substitutes.
Aground mixture of the raw ma-
terial containing major components
in a required proportion is burned in
a rotary kiln at about 14500C, where
the constituents become fully oxi-
dized and form stable solid solutions
or the phases as described above.
Impure CJS is also frequently known
as alite, and C$ as belite. After
cooling, the clinker is interground
with approximate y 5% of gypsum to
about 350 m2/kg Blaine fineness, to
obtain portland cement.
A typical composition of ASTM
Type I cement, the most commonly
used cement in general construction,
is normally 5870 CaS, 15/0C2S, 80/0
C~A, 107. CdAF, and 5?0 gypsum.
Other ASTM cement types are Type
II, III, IV, and V, which vary in com-
position and are used where special
properties are required. Typical corn-
position and physical properties of
various cement types are given in
Table 1 (adapted from CTL, 1993;
Mindess and Young, 1981).
Type III cement is a high heat of
hydration cement with high C.$ con-
tent and a finer particle distribution
and is used where rapid hardening is
required for early strength develop-
ment. Type IV is a low heat of hydra-
tion, slow setting cement because of
low C~S and high C2S contents. It is
intended for mass concrete in order to
avoid thermal cracking, but is now
rarely produced. Since the strength
development of Type IV cement is
low, Type II cement, which can be
specified as a moderate heat of hydra-
tion cement, is generally recom-
mended due to its higher strength
and market availability. For even
lower heat of hydration, Type II ce-
ment with fly ash is used. Type V
cement is also a low heat of hydration
cement because of low C~S and low
C~Acontents; it isnormallyused when
high sulfate resistance is required.
Type II is primarily used as a moder-
ate sulfate resistant cement.
A knowledge of the compound
composition can reasonably be used
to predict the properties of cement.
One of the known methods for calcu-
lating compound compositions from
the oxide analysis are the Bogue for-
mulae (1955). Although a number of
sophisticated techniques are now
available for Bogue calculations, the
simplest Bogue formulation that has
been found suitable for most applica-
tions is given in the ASTM C 150
specifications.
Lesser Elements
Fourlesserelements, i.e., sodium (Na),
potassium (K), magnesium (Mg), and
sulfur (S), which appear in virtually
all commercial clinkers at l-5y0 con-
*
In cement chemists notation S=Si02,
C=CaO, A=A1203,F=Fe203and S.S03
**
Alites and Mites are never pure forms
of C3Sand C2Srespectively. Due to the
geological source of the raw materials,
alite and belites will always have small
quantitiesof impuritiesor traceelements.
3
centration, are represented in chemi-
cal analyses as oxide forms: NazO, KZO,
MgO, and SOS. Rompps Chemie-
Lexikon (1987) has termed these ele-
ments as the secondary elements. In
cement chemists notation Na20=N,
K20=K, MgO=M, and S0,=3.
Minor Elements
According to Miller (1976) and Gartner
(1980), elements other than the major
and the lesser constituents (i.e. Ca, Si,
Al, Fe, O, Na, K, Mg, S) may be consid-
ered as minor elements with regard to
cement manufacturing. The concen-
tration levels of minor elements in the
clinker are almost always less than 17.
and are generally categorized on the
basis of the frequency with which they
occur in the raw material mix.
Trace Elements
Blaine et al. (1965) regarded the ele-
ments occurring at less than 0.02%
each as the trace elements. Accord-
ing to Sprung (1988), elements present
at levels less than 100 ppm are classi-
fied as trace elements. Because of their
extremely small concentration levels,
it seems unlikely that the presence of
trace elements will have any signifi-
cant effects on cement manufacturing.
However, their effects on clinker can
significantly change if concentrations
are increased beyond certain levels.
For the sake of convenience, the
terminology minor elements has
been used throughout the text to cover
both minor and trace elements, as de-
fined by Blaine et al. (1965) and
Rompps chemie - Lexikon (1987) re-
spectively, unless mentioned other-
wise.
Rompps Chemie-Lexikon (1987)
has exemplified the classification
of several major, secondary, and trace
elements in cement clinker in Figure 1.
Emphasis in this report is given to
the minor and trace elements because
of their likely presence not only in the
wastes but also in the conventional
raw materials, and their potential in-
1 ppq 1 ppt 1 ppb 1 ppm 0.00190
1?40
Figure 1. Concentration ranges (by mass) of main, secondary, and
trace elements in cement clinker (Sprung, 1988).
fluence on cement manufacturing
and use. It maybe pointed out that
trace elements in a raw feed at one
cement plant could significantly dif-
fer from another. As an extreme,
lead content in one plant maybe 100-
500 ppm compared to only 1 ppm in
another plant (Chadbourne, 1990).
SOURCES OF MINOR
ELEMENTS
Minor elements in cement primarily
come from the raw materials and
fuel used in cement making. Ex-
amples of these are limestone, clay/
shale, and coal. They also come from
the widely used auxiliary materials
such as blast furnace slag, fly ash,
silica sand, iron oxide, bauxite, and
spent catalysts. A secondary but im-
portant source of minor elements
comes from the wide range of indus-
trial by-products which are partially
or totally being substituted for the
primary fuel. These include petro-
!eum coke, used tires, impregnated
sawdust, waste oils, lubricants, sew-
age sludge, metal cutting fluids, and
waste solvents, as listed in Table 2.
Minor compounds found in sev-
eral raw feeds for cement manufac-
turing as quoted by Bucchi (1980) are
shown in Table 3. Similar data on
major components of raw materials
are shown in Table 4 and 5. They are
limestone and shale/clay; widely
used auxiliary raw minerals, i.e. blast
furnace slag (used up to 307. by
weight of raw material), and coal fly
ash (used up to 15/.by weight).
Minor elements found in con-
ventional kiln fuel (coal), along with
two secondary fuels (used oil and
petroleum coke) are shown in Table
6. Average values of minor compo-
nents found in typical clinkers
(Moir and Glasser, 1992) are given in
Table 7.
Although blast furnace slag can
be used up to 307. by weight, the
level of use maybe reduced due to its
magnesium oxide (MgO) content,
particularly if the MgO level is al-
ready high in the other raw materi-
als. Bauxite is reported to contain
2-87. titanium oxide (TiOz) and
0.04-0.4% chromium oxide (CrzO,).
Iron ores frequently contain chro-
mium, arsenic, cadmium, and thal-
lium, and may have adverse envi-
ronmental consequences because of
their toxicity characteristics. A list of
metals having regulatory and envi-
ronmental concerns has been speci-
fied by waste characterization regu-
lations under the Resources Conser-
vation and Recovery Act (RCRA) and
the Boiler and Industrial Furnace (BIF)
4
Table 2. Sources of Minor Elements in Cement Manufacturing
:Iements (as per group)
Sroup I
.ithium
Group II
3eryllium
Strontium
3arium
Group HI
3oron
Gallium, Iridium, Thallium
Group IV
Germanium
Tin
Lead
Group V
Nitrogen
Phosphorus
Arsenic
Antimony
Bismuth
Group VI
Sulfur
Selenium, Tellurium
Group WI
Fluorine
Bromine
Chlorine
lodine
Transition Elements
Titanium
Zirconium
Vanadium
Chromium
Molybdenum
Manganese
Cobalt
Nickel
Copper
Zinc
Cadmium
Mercury
Sources
Waste lubricating oil
Fly ash
Limestone, aragonite, slag, waste lubricating oil
Waste lubricating oil, refuse derived fuel (RDF)
Raw material, iron ore
Raw material, fly ash, coal, secondary fuel, waste derived fuel (WDF)
Raw material, coal
Fly ash, RDF, fuel
Raw material, tires, RDF, WDF, copper shale, fly ash
Coal, air
Raw material, slag, sewage sludge, sandstone, RDF
Fly ash, secondary fuel, coal, used oils
Petroleum, coke
Fuel
Coal, slag, lubricating oil, petroleum coke, pyrite, tires
Fly ash, coal, RDF, coke
Limestone, fuel
Fly ash
Coal, slag, fly ash, waste lubricating oil, chlorinated hydrocarbons, RDF, chlorine-rich fuel
Coal
Raw material, clay, shale, iron ore, bauxite, slag, RDF
Raw material, silicon ores
Petroleum coke, crude oil, black shale, substitute fuel, coke, fly ash
Bauxite, slag, recycled refractories, copper shale, tires, WDF, coal
Waste lubricating oil
Raw material, limestone, clay, shale, bauxite, slag, fly ash
Waste oil, fly ash
Fly ash, black shale, copper shale, waste oil, tires, RDF, WDF, coal, petroleum coke
Fly ash, black shale, copper shale, lubricating oil, tires
Used oil, tires, metallurgical slags, filter cake, furnace dust, RDF, WDF
Fly ash, black shale, copper shale, WDF, paint
WDF, paint fungicides
Rawmaterial includes natural materials such as limestone, clay, shale, sand, etc.
5
,
regulations that control treatment of
hazardous waste in cement kilns.
These are shown in Table 8 (Klemm,
1993). Both RCRA and BIF regula-
tions apply to wastes and require the
use of the TCLP (toxicity characteris-
tic leaching procedure) tests.
The levels of sulfur and chlorine
I
in bituminous coal, the main fuel for
Cement kilns, varies frOIn 0..5 to 4y0
and 0.007 to 0.39Y0, respectively. In
some Illinois coals, sulfur is present
up to 60/0by weight. Petroleum coke,
u~ed as an-auxilia~ fuel, contains up
to 5~0 sulfur and 0.6% vanadium OX-
ide, and can contribute certain levels
of S and V to clinker when supple-
menting for coal. Tires have a zinc
content of 1.2-2.6 Yo. However, if tires
replace 10% of the primary fuel, the
resulting zinc oxide (ZnO) contents
in clinker are increased by only ().W70
(Sprung, 1985),
Additional sources of minor com-
ponents could be the refractories,
chains, and the grinding media such
as liners and grinding balls. A dam-
aged chrome refractory lining can en-
ter into the incoming raw mix and
incorporate a detectable amount of
chromium into the clinker. Partly for
this reason, and mostly because of
problems with their safe disposal, the
use of chrome bricks is being phased
out in most parts of the world (Moir
and Glasser, 1992).
MINOR ELEMENTS IN
CEMENT MAKING
The role of minor and trace elements
in the formation of clinker and their
effect on cement properties are dis-
cussed in this report as per their oc-
currences in raw mixes. The elements
chosen for discussion are categorized
according to the periodic table, as
highlighted in Figure 2. They are
discussed in their increasing order of
atomic number. The presence of any
information gaps are identified and
referred for further investigation.
Table 3. Average Concentrations (%) of Some Minor Com~ounds in
Raw M-eals Used in European Cement Plants (Adopted from
Sprung et al., 1984; and Bucchi, 1980) -
Minor Compounds
MgO
K20
so,
Na20
TiO,
Mn,O,
P20,
SrO
Cr,O,
AS,O,
BeO
NiO
V*05
cl
F
Raw Meals
1,05
0.57
0.31
0.17
0,16
0.12
0.09
0.07
0.01
0.002
0.0005
0.003
0.024
0.02
0.06
Table 4. Concentrations (ppm) of Some Minor Elements in
Limestone and Clay/Shale (Sprung, 1985)
Minor Elements
As
Be
Cd
Cr
Pb
Hg
Ni
Se
Ag
TI
v
Zn
cl
F
Br
I
Limestone
0.2-12
0.5
0.035-0.1
1.2-16
0.4-13
0.03
1.5-7.5
0.19
n.a.
0.05-0.5
10-80
22-24
50-240
100-940
5.9
0.25-0,75
Clay/Shale
13-23
3
0.016-0.3
90-109
13-22
0.45
67-71
0.5
0.07
0.7-1.6
98-170
59-115
15-450
300-990
1-58
0.2-2.2
Table 5. Average Concentrations (%) of Some Minor Compounds in
Major Auxiliary Raw Materials, i.e. Blast Furnace (B. F.) Slag
and Fly Ash (Moir and Glasser, 1992: and Smith et al.. 1979}
Minor Compounds
MgO
K,O
so,
Na,O
TiO
Cr,&,
MnzO,
P20,
SrO
V206
B.F. Slag
7.2
0.57
3.00
0.44
0.66
n,a.*
0.64
0.03
0.06
n.a.
AS20, n.a,
n.a,= informationnot available
Fly Ash
5.28
4.05
2.25
1.99
1.21
0.03
0.14
<3.66
0.17
0.09
0.02
6
ELEMENTS IN GROUP I
(Hydrogen, Lithium, Sodium,
Potassium, Rubidium, Cesium)
Hydrogen
The role of hydrogen (H) in cement
manufacturing has not been docu-
mented in detail, because hydrogen
per se does not exist for long in the kiln
as hydrogen is highly combustible. It
is present in the kiln as water vapor,
which results from the evaporation of
physically bound moisture from the
raw material, and from the evapora-
tion of water sprayed on the raw feed
to control dust during processing.
Water vapor can also be present in the
kiln gases from combustion of fuel such
as CHA + 20Z ~ COZ + 2HZ0
(Hawkins, 1994; Miller, 1994). A por-
tion of water may also come from the
dehydration of raw materials such as
clays, where it can be present in signifi-
cant quantities depending upon their
mineralogical nature. In a wet plant,
water comes from slurry.
The water vapor present in the
kiln might have an indirect effect on
the volatility of alkalies which can in-
crease with vapor pressure at higher
temperatures, for example:
2H,0 + 21$S04 - 4KOH + 2S02 + 0,
less more very
volatile volatile volatile
Apart from that, hydrogen may not
have any significant effect on the an-
hydrous nature of clinker.
As a point of information, it may
be mentioned that early cement kilns
sometimes used producer gas as fuel.
The gas was generated (as a mixture of
CO and Hz) by the action of steam on
hot coal or charcoal as follows:
H20+C~CO+H,
Currently, no kilns in the USA
Canada use this technology.
or
Groups
1
2
6
7 1= !3s AC Unq Unp Unh Uns
Lanthan~de
Series
Act inide
Series
.
L? d
PrNd@mlam EU Kid lb DY Ho Er6 Tm6 ~
.
Th Pa
,
Ua NP93 Pu Am Cm Bk
v
Cf
98
Figure 2. Elements from the periodic table selected for studies.
Table 6. Average Concentrations (ppm) of Some Minor Elements in
Coal aid Used Oil (Sprung; 1985; and Weisweiler and
Kr6mar, 1989)
Minor Elements Coal Used Oil Petroleum Coke
Sb 1.19 n.a.* 0.0429
.4s 9-50 <0.01-100 0.6
Ba 24.5 0-3,906 8.4
Be 2.27 n.a. n.a.
Cd 0.1-10 4 n.a.
Cr 5-80 <5-50 11.0
Pb 11-270 10-21,700 8.7
Hg 0.24 n.a. n.a.
Ni 20-80 3-30 208.0
Se 3.56 n.a. 0,1
Ag 0.06 n.a. n.a.
TI 0.2-4 <0.02 0.1
v 30-50 n.a. 778.0
Zn 16-220 240-3,000 n.a,
Sr n.a. n.a. 4.3
cl 100-2,800 10-2,200 n.a.
F 50-370 n.a. n.a.
Br 7-11 n.a. n.a.
I 0.8-11.2 n,a. n.a.
n. a.= information not available
7
Lithium
Lithium (Li) is found in some waste
materials such as used lubricants, but
occurs only in traces in the kiln raw
,
feeds and common fuels.
Lithium might behave somewhat
differently from sodium or potassium
in that it would tend to form a rela-
tively nonvolatile oxide (LizO) at el-
evated kiln temperatures, Gouda
(1980) reported that LizO is most reac-
tive in lowering the temperature
of the initial liquid phase; the
effectiveness has been shown as
LizO>NazO>KzO, The presence of L<O
also disturbs the course of the burning
process during which lime dissolves
in the liquid phase and results in higher
reactivity. As a negative effect, Li10
also inhibits the conversion of CZSto
C,S. The effects are more pronounced
with Li.O comuared to Na.O and K.O.
Ra~garao(1977) poin~ed out t~at
up to l% of Li10 in the raw mix im-
parts a mineralizing effect, but lime
fixation is impaired afterwards. At a
lower LizO addition (0.1-0.3% by
weight), limestone dissociation acti-
vation energy is reduced, and mineral
formation becomes more intensive.
If present in adequate amounts as
an admixture, Li can have beneficial
effects on cement properties, since it is
known to greatly reduce the alkali-
silica reaction (ASR) in concrete. Re-
cent studies by Stark et al. (1993) have
demonstrated that Li salts like LiOH
and Li carbonates (if added in appro-
priate amounts) reduce the ASR sig-
nificantly. It is conceivable that Li in
clinkers could also have the same af-
fect on ASR.
Sodium and Potassium
Since both sodium (Na) and potas-
sium (K) occur together in raw feed,
and by virtue of similarities in their
behavior in cement manufacture, it is
appropriate to discuss them together,
Sodium and potassium are mainly
derived from the raw materials; their
Table 7, Average Concentrations of Some Minor Compounds
Foundin Conventional Clinkers (Moir and Glasser, 1992)
Minor Compounds
MgO
K,O
so,
Na20
TiO,
Mn20,
P*05
SrO
Minor Compounds
ZnO
Cr,O,
V*05
cl
As,O,
Cuo
PbO
CdO
T120
Mean Value (%)
1,48
0,73
0.80
0.16
0.27
0.06
0.10
0.09
Mean Value (ppm)
120
103
100
90
56
55
16
0.5
0.3
Table 8. Elements of Regulatory and Environmental Concern
(Klemm, 1993)
Elements
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium (Total)
Chromium (Vi)
Lead
Mercury
Nickel
Selenium
Silver
Thallium
RCRA
Metals
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
RCRA Limit
* Using TCLP
1.0 mg/L
5.0 mg/L
100 mg/L
0.007 mg/L
1.0 mg/L
5.0 mg/L
not defined
5.0 mg/L
0.2 mg/L
70 mg/L
1.0 mg/L
5.0 mg/L
7.0 mg/L
BIF
Metals
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
G RCRA . Resource Conservation and Recovery Act
TCLP = Toxicity Characteristic Leaching Procedure
* BIF = Boiler and Industrial Furnace
BIF
Carcinogen
Yes
Yes
Yes
Yes
8
main carrier is clayey rock. Sedimen-
tary rocks, including the carbonate
ores, sometimes contain soluble alkali
salts. Lea (1971) has quoted the occur-
rence of Na and K (by weight O/.)in
different components of raw materi-
als used for cement manufacturing as
shown in Table 9.
Table 9. Presence of Sodium and
Potasium in Different
Raw Materials (Lea, 1971 )
7. by wt.
Na20 K20
Typical raw mix
0.13 0.52
Limestone
0.26 0.11
Chalk
0.09 0.04
Marl
0.12 0.66
Clay
0.74 2.61
Shale
0.82 4.56
Alkalies frequently occur in auxil-
iarv raw materi~ls su~h as blast fur-
na~e slag and fly ash as shown in Table
5. NazO and KZO in European fuels
range between 0.05 -O.6?40and ().5-2%,
respectively (Bucchi, 1980); for typical
raw feed, their average concentration
Ievek are 0.177. and ().57Y0, respec-
tively, as shown in Table 3.
Jawed and Skalny(1977, 1978) and
Skalny and Klemm (1981) have re-
viewed in detail the effects of alkalies
in cement manufacture and use. NazO
and KZOare volatile in nature, giving
rise to a cycle inside the kiln. The
extent of alkali volatilization varies
with raw material composition; for
instance, volatilization of alkalies in
clays is higher than those found in
feldspar. About half of the total alka-
lies by weight in the feed are volatil-
ized between 8OO-1OOOCas the mix
nears the burning zone, but condenses
at cooler parts of the system, such as in
suspension preheater riser ducts or in
chain systems in dry kilns. The forma-
tion of rings and coatings on kiln lin-
ing resulting from this heating-cool-
ing cycle are generally attributed to
alkali condensation and reaction with
refractories or incoming material. To
%
800
600-
400 \
200
NaCl
30
20
10
1000 1100 1200 1300 1400 1500
Temperature, C
Figure 3. Vapor pressure of Na and K chlorides and sulfates
(Bucchi, 1980).
avoid excessive buildups in the kiln or
preheater vessels, a percentage of gases
may be bled through a by-pass, so that
the alkali sulfates and chlorides maybe
continuously removed and end up in
the cement kiln dust (CKD). Thus,CKDs
collected from by-pass dust collector
are typically high in alkali contents.
Usually potassium compounds are
more volatile than the sodium com-
pounds.
According to Bucchi (1981), the in-
tensity of the alkali cycle depends upon
the nature of their presence in raw ma-
terial, on operating practices, and on
type of kiln. The retention of alkalies in
clinker is generally higher for high effi-
ciency kiln systems (Lea, 1971). With
gas and oil as fuels, the alkalies tend to
volatilize more as compared to coal
used as a fuel. This may be due to the
high intensity of the flame with oil and
gas compared to coal.
In the presence of chlorides and
sulfate, the volatilization behavior of
both Na and K is modified greatly, as
shown by the vapor pressure-kiln tem-
perature relationship in Figure 3. The
vapor pressures of alkali carbonates
resemble those of sulfates and they ex-
hibit similar effects. In the presence of
sulfur, alkalies preferentially form sul-
fates. If their amount is more than the
required stoichiometric balance, the
excess will be dissolved in the silicates,
aluminates, and ferrites. The common
alkali sulfate phases formed are K2S01,
E
also known as arcanite, sodium
potassium sulfate, also known as
aphthitalite of a general solid solution
composition (K,Na)2S01*, and NazSO1,
also known as thenardite (Taylor,
1990).
According to Skalny et al. (1981),
the ratio of Na to K in cement raw
materials in the North America and
Europe varies. There is usually a sub-
stantial excess of KZO over NazO.
Therefore, in the presence of suffi-
cient amount of SO~a range of double
alkali sulfates, as described later in
this report, is formed depending upon
the KIO to Na20 ratio. If KZO is in
excess of that required to produce
aphthitalite, it forms arcanite.
Burning conditions also signifi-
cantly influence the formation of sul-
fate so that oxidatizingconditions pro-
duce calcium-potassium sulfate and a
reducing condition produces sodium-
potassium sulfate. Potassium is twice
as likely to produce soluble sul-
fates as sodium. According to Pollitt
and Brown (1968), the calcium potas-
sium salt, calcium langbeinite
2CaSOAKzSOq**, is also sometimes
found.
Introducing SO, jointly with K20
and NazO into clinker melt leads to
phase separation. Since alkalies re-
.
Commonly written as K3N54in cement
chemists notation
**
Also written as 2CS.KS-
9
duce the melt temperature, and the
rate of C$ formation is proportional
to the amount of liquid phase, a posi-
tive effect on C$ formation could be
expected. However, Johansen (1977)
reported that C~S, with or without the
presence of alkali, has the same
amount of free lime after firing at
1400-15000C. Alkali sulfate melt and
clinker liquid are immiscible phases.
Alkalies inhibit the formation of C,S
from CzSand lime bystabilizinglower
energy CZSin the absence of sulfates.
After allocating for the sulfates,
the remaining alkalies are distributed
between silicates, aluminates, and
aluminoferrite. Lea (1971) has re-
ported ranges of alkalies in the major
clinker phases shown in Table 10.
The values are in general agree-
ment with those quoted by Taylor
(1990) tin the distribution of alkalies
in different clinker phases.
Gartner (1980) and Gies et al.
(1986) reported that in the absence of
SO~, Na20 is preferentially incorpo-
rated in CqA by replacing CaO
and forms alkali-aluminate
of an approximate composition
NaO*8CaO*3AlzO~*, thereby reducing
its reactivity. This results in clinkers
rich in free lime and aluminate, and
can reduce the burnability. K is sub-
stituted in C$ as a compound with
an approximate composition of
KzO*23CaO*12SiOz,** and the overall
reactivity of clinker is decreased due
to the slower reaction with CaO to
form C~S in the burning process. In
the presence of sulfate, KZOincreases
the C,Areactivity(Strungeet al., 1986).
Richartz (1986) reported that SOS re-
duces the extent of alkali solid solu-
tion in C~Aand hence the reactivity,
but improves the cement properties.
The mineralizing effectiveness of
alkalies (in terms of decreasing melt
viscosity, and free lime contents in
clinker) also appears to be a function
of their cation size, electronegativity,
or the ionic potential. Such relation-
ships for K, Na, Li and other relevant
cations are given in Table 11 (Grachian
et al.), and in Figure 4 (Teoreanu and
Table 10. Range of Alkali Distribution in Clinker Phases (Lea, 1971)
I
Clinker Phase
L
C3S
C*S
C,A
C,AF
Na,O (wt.%)
0.1-0.3
0.2-1.0
0.3-1.7
0.0-0.5
K,O (wt.%)
0.1-0.3
0.3-1.0
0.4-1.1
0,0-0.1
Table 11. Effect of Ionic Potential of Minor Elements on the
Melt Viscosity (Grachian et al., 1971)
Effect of Different Ions Ionic Potential of Elements
on Melt Viscosity (ratio of number of iogic
(in decreasing order) charge/cationic, Rvl in Al)
Be+2
Mg+2
.942
Li+l
Ba+2
Na+l
K+l
5.71
2.50
1.65
1.22
1.39
0.91
0.68
7
I
[Cao]o= Free CEO in the Absence of Mineralizer (%) Mg+2
[@O], K Free Cso in the Presence of Mineralizer (%) G
6
5 ~+2
G
4-
0 0.1 0.2
0.3 0.4 0.5
Field Strength, m-2
Figure 4. Mineralizing effectiveness of cations for clinker with
LSF=O.96, SM=2.2, AF=2.O at 1350C (Teoteanu and Tran von Huynh,
1970).
Tran van Huynh, 1970) respectively.
It might be mentioned that although
alkalies, NazO in particular, may act
as fluxes, they are technically less
desirable compounds than many of
the other available minor compounds
@ucchi, 1980).
If present in excess, alkalies often
lead to higher pH and better early
strength, but lower later strengths.
They are not desirable because of
*
Commonly written as NC8A3
**
Also written as KC,3S,j
10
their deleterious alkali-silica reaction
(ASR) with reactive aggregates that
leads to expansive reactions and can
cause serious cracking in concrete. ASR
can be prevented with proper use of
pozzolans.
Butt et al. (1971) reported that the
deleterious effects of alkalies on the
mechanical properties of cement may
be reduced by gypsum addition to the
raw feed. They considered this be-
cause of the possible elimination of
solid solutions of alkalies with clinker
minerals. One possible speculation
derived from the microscopic
studies by Prout (1985), is that
gypsum would either increase
the volatilization, or eliminate
NaO8Ca0-3Al,0~ or K,0*23CaO12SiOz
formation. According to Lokot et al.
(1969), the addition of gypsum to raw
feed produces cement of high 28-day
strength, enhancing kiln output and
fuel savings.
Rubidium and Cesium
The remaining Group I elements, ru-
bidium (Rb) andcesium (Cs),arefound
only as traces in cement raw mix or in
the fuel. Rubidium generally occurs in
cement at 0.017. or less (Blaine, 1965).
Both Rb and Cs are expected to
behave similarly to Na and K, in that
they would both form stable sulfates
and volatile chlorides in the kiln
(Gartner, 1980). On the other hand,
their concentrations may be too low to
effectively influence the clinker forma-
tion or cement properties.
ELEMENTS IN GROUP Ii
(Beryllium, Magnesium, Calcium,
Strontium, Barium)
Beryllium
Beryllium (Be) would be present only
in trace amounts in the raw feed and
fuel (see Tables 4 and 6). It is found
only occasionally in the fine fractions
of fly ash, an auxiliary material fre-
quently used as substitute raw mate-
rial. Beryllium is found at a 55 ppm
levelin=4 pm fraction compared to 12
ppm in >45 p,m fraction of fly ash
(Davison et al., 1974).
It maybe suggested that because
of its low volatile oxides, beryllium
would stay in the clinker, Nonethe-
less, beryllium has not been measured
in significant amounts in clinkers to
have any measurable effects on clin-
ker formation or cement use. Beryl-
lium in todays cements has occured
up to 3 ppm (PCA, 1992).
Magnesium
Magnesium (Mg) in portland cement
is mainly derived from magnesium
carbonates present in the lime-
stone in the form of dolomite
CaCO,*MgCO,, while smaller
amounts coming from clay and shale
(Lea, 1971), ordiopside(Fundal, 1980).
If present in small quantities, mag-
nesium improves the burnability of
clinker (Christensen, 1978). Accord-
ing to Long (1983), the behavior of
MgO in clinker formation primarily
depends upon the cooling rate. When
clinker is burnt at high temperature
(>15Cr0C) and rapidly cooled, it re-
tains the bulk of the MgO mostly in
aluminate and ferrite phases, with a
lesser amount in alite. Under condi-
tions of slow cooling, ody 1..57. of
MgO is retained in solid solution and
the rest is crystallized as large periclase
crystals. MgO in cement is usually
limited to under 5Yo, because MgO
content in excess of 2?40can occur as
periclase (Taylor, 1990), The presence
of larger crystals of periclase in ce-
ment slowly reacts with water to form
expansive Mg(OH)z and can lead to
destructive expansion of concrete.
ASTM C150 specifications allow MgO
contents up to 6% in portland cements.
Magnesium salt solutions (sulfate
and chloride) are aggressive towards
concrete and react with the calcium
hydroxide phase to form basic salts.
The reactions are expansive and may
lead to deterioration of concrete.
Calcium
The role of calcium (Ca) in cement
manufacturing has alread ybeen dealt
with in the section of major elements.
Strontium
A major portion of strontium (Sr)
found in clinker as SrO comes from
limestone and aragonite.
Strontium as SrO, frequently oc-
curs in clinkers. The mean value
quoted by Moir and Glasser (1992) in
Table 7 is O.09%. Brisi et al, (1965) and
Gilioli et al. (1972, 1973), demonstrated
that small amounts of S@ favor alite
formation, but at 4-5y0 addition, Sr
preferentially distributes in belite
rather than alite, Sr in belite inhibits
alite formation. Phase equilibrium
studies indicate that Sr in raw feed
also favors free lime formation, with
SrO preferably going into solid solu-
tion and displacing CaO from other
compounds, The tendency of free
CaO release during clinkering makes
SrCOq more labile than SrSO~, and the
clinkers having a high lime saturation
factor (LSF) maybe more vulnerable
to free lime expansion during hydra-
tion.
Butt et al, (1968) reported that the
hydraulicity and strengths developed
by Sr-doped alites are significantly
lower than the normal alites. This
may be attributed to the smaller sizes
of the lattice voids in strontium-in-
corporated alite.
Kantro (1975) reported a slight
set acceleration effect withS~lz~ 6HZ0
used as an admixture in CaS paste.
Barium
Barium (Ba) occurs in varying
amounts in limestones, mostly as bar-
ite (BaSOd). It can also occur in clayey
sediments in appreciable amounts.
The average amount of barium in ce-
ment is 280 mg/kg. The average for
CKD is 172 mg/kg (PCA, 1992).
11
Timashev et al. (1974) reported a
decrease in clinkerization temperature
from 1450 to 1400C and increase in the
clinker production rate from 8.2 to 9
tonnes/hr, when using raw mixes con-
taininghigheramounts of barium. They
also noted an improvement in the min-
eralogical composition of the resulting
clinker. However, Kurdowski (1974)
reported only a marginal usefulness of
BaO when added in small amounts,
stating that it did not significantly af-
fect either the properties of the liquid
phase or the rate of lime assimilation;
Ba replaced Ca in all the clinker phases,
except for the ferrite phase. The opti-
mum BaO concentration was between
0.3 to 0.57., preferably for clinker con-
taining less flux (silica modulus >30)
and high CIS levels.
According to a number of studies,
Ba also appears tobe an effective activa-
tor of hydraulicity and strength. The
strength obtained from Ba incorporated
clinkers is 1O-2O7Ohigher than that of
regular clinker of all ages tested under
identical conditions (Kurdowski, 1974;
Butt et al., 1968; Kurdowski et al,, 1968;
Kruvchenko, 1970; Peukert, 1974).
Barium can be present in used oils.
Excessive amounts in raw mix can in-
crease the free lime content of clinker
due to CaO displacement and can cause
expansion in concrete under certain cir-
cumstances. It can also lead to paste
shrinkage.
ELEMENTS IN GROUP Ill
(Boron, Aluminum, Gallium, Iridium,
Thallium)
Boron
Boron (B) is generally found in traces (3
ppm) in most cement raw materials,
particularly those containing iron ore.
Fromearlystudiesby Mircea (1965),
it appears that BzO~reacts with CJS to
form CZS, C~BS*, and free lime. Upon
further addition of BzO~,C~Scompletely
disappears. Timashev (1980) established
a relationship between the electronega-
tivity of boron and the melt viscosity,
0
CaZn VBe NiKCr AsPb S
957
Cd Cl TI
Figure 5. Relative volatilities of elements in clinker burning in a
cyclone preheater kiln (Sprung, 1988).
Restive volatility as a percentage of ratio between the total
external and internal balance for a given element.
and noted a similarity between be-
rates, phosphates, and sulfates. Boron
inhibited the formation of C$ and af-
fected the stability of the other major
clinker phases. In the presence of bo-
ron C$ is decomposed to a stabilized
C2S as follows:
C,S ~ C2S + Cao
It was also pointed out that although
B20q may not be a useful addition for
regular alite clinker required for early
strength development, it might be use-
ful as a mineralizer for clinkers rich in
belite. Gartner (1980) has reported on
the effectiveness of BzO~to stabilize
/1-C2Sand to improve its hydraulicity.
According to Miller (1976), boron can
also stabilize ~-CzSin alumina andiron-
poor systems.
However, Miller (1976) has cau-
tioned that the indiscriminate addi-
tion of boron can produce unpredict-
able hydration results. Gartner (1980)
explained that this behavior of boron
is probably sensitive to the presence of
other trace elements. Bozhenov et al.
(1962) reported that even small addi-
tions of BzO~(-0.040/.), as an admix-
ture, to cements can have adverse ef-
fects on setting properties. These ob-
servations indicate that B20~is a strong
retarder of cement hydration.
Aluminum
Role of aluminum (Al) in cement
manufacturing has been dealt with in
the section of major elements.
Gallium, Iridium, and
Thallium
Gallium (Ga), iridium (In), and thal-
lium (Tl) are found only in traces in
raw material; their typical concentra-
tions in coal are 5-10 ppm, 0.07 ppm,
and 1.1 ppm respectively. Thallium
and gallium are also found sometimes
in the coal fly ashes. Thallium may
also be found in some pyritic minerals
used as an iron source for raw feed.
The average concentration of thallium
in cement is 1.08 mg/kg, ranging from
nondetectable to 2.68 mg/kg. The av-
erage concentration of thallium in
CKD is 43.24 mg/kg (PCA, 1992).
*
Bis B103in C5BS
12
Although thallium occurs in traces
in the raw feed, it is the most volatile
element* after mercury in the kiln (melt-
ing point=30~C), and is most likely to
concentrate in the kiln dust. The volatil-
ity of T1relative to other elements in the
kiln is shown in Figure 5 (Sprung et al.,
1984). Sprung et al. determined the
volatility on the basis of the difference
between the external and internal bal-
ances of individual elements during the
clinker burning in a cyclone preheater
kiln. Iridium is also volatile and largely
ends up in the kiln dust. Since thallium
may concentrate in the fly ash from the
coal firing power plants, in the cement
kiln operation it tends to build up in
extremely large internal cycles if no dust
is discarded.
ELEMENTS IN GROUP IV
(Carbon, Silicon, Germanium,
Tin, Lead)
Carbon
Carbon (C) is a major component of fuel,
It is also present as carbonate in the
limestone. A significant amount of car-
bon can also present in flyashas unburnt
coal.
Carbon as C02 is extensively present
in cement kiln systems, but is not present
in any significant levels in clinker. Be-
cause of the limestone and fuel that are
used in the kiln, the gases emitted from
the kiln system are constituted mainly
of COz,~O, and N2. Limestone (CaCO~)
decomposes to CaO and C02 at about
9000C. Roughly for every ton of clinker,
one ton of COZis generated in the kiln,
which essentially is released through
stack emissions.
Silicon
Role of silicon (Si) in cement manufac-
turing has already been discussed in the
section on major elements.
Germanium
Germanium (Ge) is a trace element
found in raw material and coal.
Germanium oxide (GeOz), is not
volatile (Gartner, 1980), and is likely
to concentrate in clinker. When present
in larger amounts, GeOz can form
C~G**, tricalcium germanate with
CaCO~at 1500C and isstablebetween
1335C-1880C. At temperatures be-
low 1335C, C,G decomposes to CZG
and free lime (Hahn et al., 1970;
Boikova et al., 1974). These forms of
calcium germinates are similar to C~S
and CZSrespectively. COGis hydrau-
lic and produces calcium germanate
hydrate (C-G-H) and calcium hydrox-
ide (CH) with water, whereas ~G is
assumed to be non-hydraulic. Ac-
cording to Gartner (1980), it is un-
likely that the trace amounts of Ge
would seriously affect the formation
of clinker and the properties of the
resulting cement.
Tin
Tin (Sri) is a trace element in both the
raw feed and fuel.
Tin is reasonably nonvolatile
(boiling point=2265C). Tin oxide
(SnO) or natural cassiterite melts at
1630C and sublimes between 1800
and 1900C. It is very likely that tin
will stay in the clinker. The presence
of trace amounts of tin in clinker
should not affect cement properties,
although not much is known about
the effect of tin in clinker manufac-
ture.
Lead
Lead (Pb) can be present in trace
amounts in raw material mainly in
clay and shale. It would be present at
appreciable levels in coals, used oils,
lubricating oils, and scrap tires. In fly
ash, lead tends to concentrate in the
fine fractions (Coles, 1979), Lead lev-
els in coal, used oil, and petroleum
coke are shown in Table 6. Another
source of lead could also be the lead
shot from shot gun shells used to
shoot out rings.
The effect of lead in cement
manufacturing and properties has
been studied in some detail, Lead
compounds are fairly volatile. They
tend to vaporize in the kiln, and exit
the kiln as fines and are collected in
the kiln dust.
There is also evidence that de-
spite the partitioning of lead into the
CKD, some lead can still be retained
in the clinker (Davison et al. (1974),
and Berry et al. (1975)). However, Pb
has been shown to have no adverse
effect on cement properties if present
below 70 ppm. The effect of lead
levels higher than that in clinker is
uncertain (Sprung et al., 1978). Ac-
cording to a recent PCA study (PCA
1992) the average lead levels in the
CKDS and cements produced in
North America are 434 ppm and 12
ppm respectively.
Some research on the effect of
lead compound additions on hydrat-
ing cement properties has recently
been studied, where Bhattyand West
(1992) have noted that additions ei-
ther as a soluble compound (PbNO~:
7,300 ppm level ) or insoluble oxide
(PbO:38,000ppm level) substantially
retards the hydration of pastes, but
enhances the workability, The retar-
dation effects are more pronounced
with oxides. The initial setting time is
increased with a consequent loss in
early strength, but the 28- and 90-day
strengths are comparable to or higher
than those of the control.
ELEMENTS IN GROUP V
(Nitrogen, Phosphorus, Arsenic,
Antimony, Bismuth)
Nitrogen
Nitrogen (N) can be present up to
0.01%by weight in the raw materials,
but in coal and other fuels nitrogen
can be as high as 1-2Y0, often as
hetrocyclic nitrogen compounds.
Clinker made under reducing
conditions tend to have up to 0.057. N
*
Nonvolatile elements are often called
refractory elements.
G= GeO,
13
as nitrides. Under normal oxidizing
conditions, nitrogen in clinker is
present only at a few ppm.
High concentration of nitrogen,
higher residence temperatures, par-
tial pressure in the flame zone, and
the subsequent oxidation of nitrogen
leads to the formation of several ox-
ides of nitrogen (NO and NOZand
NZO1) in the kiln emissions collec-
tively known as NOX. Total NOXre-
sults from fuel nitrogen NO, thermal
NO, and prompt NO. In the cement
manufacturing, fuel nitrogen NO and
thermal NO play a significant role.
The prompt NO which is formed by
the participation of CH in the oxida-
tion of nitrogen in air, plays a less
significant role (Bretrup, 1991).
The quantity of thermal NO
formed is closely related to the burn-
ing zone temperature (BZT). Accord-
ing to Lowes et. al (1989), a reduction
in BZT from 15000C to 1300C can
reduce the NO, levelsby200-400 ppm.
Nitrogen in coal orotherfuels,present
at about the 1-2% level, is considered
significant in producing NO emis-
sions from cement plants. However,
it is not known to the degree in which
the nitrogen in the kiln raw feed also
contributes to NO, emissions (Gartner,
1980). In precalciners, fuel nitrogen
may play a role, but in the burning
zone the temperature is so high that
thermal NO is virtually in equilib-
rium.
Phosphorus
Phosphorus (P) as phosphates is
present in limestone and shale (Moir
et al. 1992); they are also present in
sandstones, sands, and in detritalclays
(Bucchi, 1980). Phosphorus also oc-
curs in the blast furnace slags, electric
furnace slags, convectorslags, and fly
ash which are often used as substitute
raw feed for cement manufacturing.
Phosphate is found in sewage sludge
which is a potential partial kiln fuel.
Cement clinkers contain typically
around 0.2% PzO~(Lea, 1971). A high
PzO~concentration decomposes C~S
to CZS and excess lime. If PZ05 is
present in excess of 2..57. by weight,
the formation of free lime occurs
(Nurse, 1952). However, by correct
proportioning and proper burning,
sound clinker can be produced, but
cement hardening becomes slower.
Matkovich et al. (1986) reported
higher hydraulic actively for (xCzS
stabilized by PZ05 than for the &CzS.
Odler et al. (1980-1) reported
the addition of hydroxyapatite
Ca~(PO1)~OOHleads to an increased
formation of free lime at 1300C,
being directly proportional to the
PzO~content. This was attributed to
the preferential stabilization of CZS
solid solution and formation of free
lime at increasing P205 additions.
However, Halicz et al. (1983) dem-
onstrated that a satisfactory C~S
phase in clinker was formed by add-
ing PzO~in the raw feed and main-
taining lime salmation factor (LSF)
and silica ratio (SR) at 1.0 and 2.75
respectively.
In a CaO-CzS-C~P* system at
1500C, raw mix with more than a
few percent P,O, does not yield C,S.
However, in the presence of fluo-
rine, the tolerance to PzO~is some-
what improved. It is very likely that
the thermodynamics of the system
favor the fluoride-aluminum-CIS
solid solution rather than P-C$ solid
solution (Gurevich et al., 1977) and
apparently form a fluoroapatite
phase (10Ca0.3Pz05*CaFz) which is
dissolved in C,S. Gartner (1980)
suggested that chlorides may
also help stabilize PzO~ in C~S by
forming a stable chloroapatite
(10CaO*3P,0,*CaC12) which also
forms a stable solid solution with
fluoroapatite.
Coleman (1992) reported that
an appropriate level of PzO~in clin-
ker reduces the negative effects of
alkali on the strength properties of
cements. He reported that in ce-
ment clinkers with normal NazO
contents of 0.8Y0, the maximum 28-
day strength was achieved at 1.07.
PZ05 level.
Arsenic
Arsenic (As) bearing mineral arseno-
lite or claudite AszO~ (or AslOG), oc-
curs only in small amounts in coal
and used oils, and are unlikely to
influence cement manufacturing in
any way. Smith et al. (1979) have
indicated that in coal-fired power
plants, As tends to concentrate in the
fly ash, but its concentration level, as
detected by the XRF method, is ex-
tremely low. It tends to concentrate
in the fine fractions of fly ash where
the levels can go up to 70 ppm.
Weisweiler et al. (1989) has reported
up to 5 ppm of As in raw material and
only 0.6 ppm in petroleum coke. Ar-
senic levels found in various materi-
als are shown in Tables 4-6. The aver-
age concentration of As in cement
and CKD is 19 mg/kg and 18 mg/kg
respectively (PCA, 1992).
Although AszO~is volatile (sub-
limes at 1930C) and should be ex-
pected to condense on kiln dust par-
ticles, Weisweiler et al. (1989) ob-
served that a substantial amount of
As is incorporated in the clinkers,
and only a negligible portion of As
ends up in the dust. The cause of As
entering into clinker was attributed
to the excess CaO, oxidizing condi-
tions in the kiln, and high kiln tem-
perature. Under oxidation condi-
tions, As is primarily oxidized to
AszO~and forms a series of low vola-
tile calcium arsenates, among which
Ca,(AsO,), is more stable at 13000C.
Czamarska (1966) found that 0.157.
AS+5significantly decreased the rate
of C~S formation at 1450C.
As a metalloid occurring in dif-
ferent oxidation states, arsenic can
have complex effects on the hydration
properties of cement (Conners, 1990).
Tashiroet al. (1977) reported that AszO~
only slightly retards the paste hydra-
tion when added up to 5Yo. It was
found that the As leaching rate from
hardend cement mortars using either
ordinaray water or sea water, although
measurable, was very low.
*
P=P20,
14
Antimony
Antimony (Sb) occurs as traces in
cement raw materials. It has been
reported to occur at 0.08 ppm in the
raw feed and 0.0429 ppm in petro-
leum coke (Weisweiler et al., 1989),
Sprunge (1985) has quoted 1.19ppm
Sb in coal. According to measure-
ments in BIF certification of compli-
ance (C. O. C.) and other authors, the
Sb levels in raw materials are higher.
Like arsenic, a considerable por-
tion of antimony is incorporated in
clinker in the form of low volatile
calcium antimonates under oxidiz-
ing kiln conditions at high tempera-
tures (Weisweiler et al., 1989),
The mechanics of stable calcium
antimonate is more likely the same as
for arsenate formation. The oxides,
SbzOj, natural seranmontite, and
valentinite, are not very volatile at
kiln temperatures; they sublime at
1550C. Although usually not de-
tected in cement and CKD, Sb levels
as high as 4.0 and 3.4 mg/kg have
been reported for cement and CKD,
respectively (PCA, 1992).
Bismuth
Bismuth (Bi) occurs as a trace element
in the raw feed and fuel. The stable
oxide BizOqis not volatile at clinker-
ing temperature (boiling point
=186WC). Little is available on the
influence of Bi in cement manufac-
turing and cement hydration, but,
owing to trace concentration, it is
conceivable that the effects will be
practically insignificant.
ELEMENTS IN GROUP VI
(Oxygen, Sulfur, Selenium,
Tellurium)
Oxygen
The role of oxygen (0) per se on the
manufacture and use of cement has
not been studied. Nonetheless a con-
siderable portion of raw material and
clinker phases incorporate oxygen
Possible carry-through
of complex calcium
sulfides in clinker
S-2 present as organic
and inorganic forms in
fuel, etc
ReducedS Species
S02 prominent
Molten sulfates
in vapor pressure
Sulfites, SO; in solids Sulfate solids
which become S03vapors
increasingly unstable
with rising temperature
IntermediateS Species OxidizedS Species
Increasing Oxygen Pressure ~
Figure 6. Formation of different sulfur species in cement clinkering
(C~oi and Glasser, 1988).
in one form or the other. Raw mate-
rial is primarily composed of CaCO~
(-75%),Si0, (-20%), and A1,O, (-2%).
CaCO~ in the raw mix is derived from
limestone; SiOz and AlzOqfrom clays,
shales, sandstones, and bauxite, and
FezO~from iron oxides andiron ores.
The clinker is formed by heating
a powdered raw material of an ap-
propriate proportion to 1400-1550C
in a kiln having a z-s~. oxygen level.
As stated previously, the final four
phases in clinker are in the fully oxi-
dized forms. They are: tricalcium
silicate 3CaOSiOz, known as alite;
dicalcium silicate 2CaSiOz, known
as belite; tricalcium aluminate
3CaOA110q, known as aluminate,
and tetracalcium aluminoferrite,
4CaOA120~FezO~,known as ferrite.
The importance of oxygen levels
is also related to the effect on the
environment of the kiln and the kind
of reactions that are favored. Thus,
the presence of oxydizing or reduc-
ing atmosphere greatly influence the
reaction into which the various ele-
ments will enter. Clinker made un-
der oxidizing conditions tends to in-
corporate trace metals of higher oxi-
dation states than clinker prepared
under reducing conditions. Ex-
amples of chromium and sulfur can
be cited here. Cr+s would tend to
form under oxidizing conditions, in-
stead of Cr+3, which results under
reducing conditions. Cr has also been
reported to occur as CrA, Cr~s, and
Cr+5(Johansen, 1972), but eventually
they disproportionate to more stable
Cr+3or Cr+swhen mixed with water.
Alkali sulfates formed in the kiln
are preferably decomposed under re-
ducing conditions. Kilns having
strongly oxidizing conditions and low
burning zone temperature tend to
retain more sulfur in clinker than
those produced under reducing con-
ditions and for high burning zone
temperature. Thus, the oxidation or
reducing conditions in the kiln can
lead to significant phase modifica-
tions in clinker.
Clinker produced under reduc-
ing conditions are brownish as com-
pared to darker gray clinkers made
under oxidation conditions, most
probably because of the oxidation
state of iron. Burning conditions ma y
also have an effect on the crystallinity
of major phases. The effects can be
pronounced if trace metals are also
present.
Sulfur
SUIfur (S) is frequently present in coals
and some fuel oils; sulfates and sul-
fides are also often present in the
limestones. Clayey sediments, marls,
also contain both sulfides and sul-
fates. Lecher et al. (1972) have re-
15
ported occasional use of gypsum and
anhydrite as mineralizers and modifi-
ers of the alkali cycle in the kiln.
Sulfides and sulfur from raw mate-
rials and fuel are oxidized and are in-
corporated into the solid phases as sul-
fates in the clinker, though some sulfur
as SOZwill almost always escape with
the exiting gases.
Sulfur forms volatile compounds
and its behavior in a kiln is a complex
one. Depending upon the burning con-
ditions in the kiln, both oxidized and
reduced species may occur in solid,
molten and vapor phases, as explained
by Choi et al. (1988) in Figure 6. Under
oxidizing conditions at high tempera-
ture, the formation of SOzis most likely.
In the presence of lime, S02 is partly
removed to form CaSO1 by the follow-
ing mechanism:
S02 + CaO ~ CaSO,
CaSOz + l/20z ~ CaSO1
In the presence of alkali, alkali sulfates
are formed which are later condensed at
the lower temperature regions. These
condensates, from liquids and solids,
contribute to build up problems in
various kiln systems. Intermediate
compounds such as sulfospurrite,
2C2SOC~,and the ternary compound
sulfoaluminate C1@ also condense
at lower temperatures.
Another well known problem of
sulfur being volatile is its cycle of
vaporization and condensation with
alkalies. They are volatilized at high
temperatures and subsequently con-
dense on the relatively cooler incom-
ing raw feed resulting in high sulfur
and alkali levels in the middle zone
of kiln, especially with preheater.
The use of an alkali by-pass is often
effective to break this cycle and lead
to the reduction of sulfur and alkalies
in the incoming kiln feed. However,
alkali sulfate levels are significantly
increased in the by-pass dust, which
is captured by the dust-collector and
generally discarded.
Sulfates preferably combine
with alkalies to give alkali sulfates
in clinker as (K, Na)#O1, known as
aphthitalite, or K2S01 known as
arcanite. If sulfate is ptesent in ex-
cess, the balance between alkali is
achieved by forming calcium lang-
beinite, Caz~(SO,)Y which is stable
up to 10110C in a CaW1-KzWi sys-
tem. However, this phase is known
to evaporate inconWuently at high
temperatures, and vaporizes K and S
(Arceo et al., 1990).
Major alkali salts formed with
sulfates and their approximate melt-
ing temperatures according to
Gartner et al. (1987) and Skalny and
Klemm(1981) are shown in Table 12.
Strungeet al. (1985) reported that
increasing sulfate contents distinctly
decreases alite, increases belite; the
aluminates and ferrite contents are
unchanged in clinkers irrespective of
their silica modulus (SM) values. On
the other hand with increasing SM,
irrespective of the sulfate, the alite
contents are higher, belite are un-
changed, and aluminates and ferrite
are somewhat lower. Relationships
between clinker phases and sulfate
content in the clinker are shown in
Figure 7. With increasing sulfate
Table 12. Major Alkali Sulfates Formed During Clinkering and their Approximate Melting Temperatures
(Adopted from Skalny and Klemm, ~981; and Gartner et aL~1987)
Alkali Compounds Chemical Formulae Melting Temperature C
Potassium Sulfate (arcanite) K,SO, 1074
Sodium Sulfate (thenardite) NapSO, 884
Calcium Sulfate (anhydrite) CaSO, 1450
(Decomposes to CaO + S03
and 02at about 1200C)
Sodium Potassium Sulfate (aphthitalite) K, S0,Na2S0,
or 968
(K, Na)2S0,
Calcium Potassium Sulfate (calcium Iangbeinite) 2CaS0,+K2S0,
or 1o11
Ca,K2(SO&
Calcium Potassium Sulfate (syngenite) K2SO~CaSO;H20
or 1004
Ca, K2(S0,)ZOHZ0
(Partial decomposition at
lower temperature)
16
contents, the alite crystals in clinker
grow larger, and the tendency ofbelite
inclusion in alite is progressively re-
duced. The crystal size of aluminate
and ferrite phases are also signifi-
cant y reduced.
Gies et al. (1986, 1987) reported
the development of a belite-rich ce-
ment by using increased sulfate con-
tents in alkali free raw materials; this
clinker showed reasonable hydraulic
activity which was attributed to the
presence of 0.6-0 .8% sulfate in belite.
The rate of clinker cooling did not
have any significant effect on the
strength properties of resulting ce-
ment pastes. To the contrary, Gartner
(1980) suggested that sulfate in clin-
ker is rather unreactive and does not
necessarily contribute to set control
or to the hardening of paste. So, even
a high sulfate clinker may require
additional sulfate, which generally
comes from gypsum interground with
clinker to achieve adequate set con-
trol. This, however, depends upon
the C~A content, and sulfate should
not exceed the maximum limit speci-
fied by ASTM C150 without the sul-
fate expansion test. It might be noted
that excessive sulfate in cement can
lead to expansion problems in con-
crete. Clinkers might also contain
certain amounts of unreactive sulfate,
which unfortunately can lead to other
problems due to insufficient avail-
able sulfate for reaction with the alu-
minate phase.
Another related concern is the
level of SOz in the kiln exhaust area.
Very frequently, 15-40% of pyritic (sul-
fide) sulfur in raw material is con-
verted to SOZ in the emissions
(Neilson, 1991).
It should be pointed out that in
the preheater system much of the SOZ
in the kiln is taken up by the incoming
raw material. This reaction is also
observed in plants which use kiln
exhaust to provide heat to the raw
milling system. Significant amounts
of SOZmay still escape if its original
concentration is high, or if reducing
conditions are generated locally.
SM=l .6
Belite
d
Aluminate
Ferrite
I
SM=2.4
Belite
/
I
Ferrite
SM=3.2
Alite
/
Belite
Aluminate
Ferrite
0123
0123 0123
SOS Content, % mass
Figure 7. Different phases of clinker as a function of S03 content and
different values of silica modulus (Strunge et al., 1985). -
Selenium
Selenium (Se) could be associated with
sulfur in coal, but only in traces. It is
also present in fly ash where it tends to
concentrate in the fine fractions (Coles,
1979). Selenium is usually not detect-
able in cement but is detected in CKD in
small amounts (PCA, 1992).
Selenium is volatile (boiling
point=684C) and expected to end up
in kiln dust or in the emissions. Sele-
nium could form less stable selenates
(SeO,), which are unlikely to stay in
clinker (Gartner, 1980). Since their con-
centration is extremely low in the kiln
feed, it is very unlikely that they will
have any significant effect onthemanu-
facture or properties of cement.
Tellurium
Like selenium, traces of tellurium (Te)
are generally associated with sulfur in
coal.
At optimum kiln temperature tel-
lurium could be somewhat volatile de-
pending upon the form in which it is
present (amorphous form boiling
point= 990C; rhombohedral form
boiling point =1390C). Gartner (1980)
suggests that tellurium might form un-
stable tellurates in clinkers and end up
in the kiln dust or the emissions.
ELEMENTS IN GROUP WI
(Fluorine, Chlorine, Bromine, lodine)
The halogens fluorine, chlorine, bro-
mine, and iodine, are frequently found
in kiln raw feed and primary as well as
alternative fuels, and therefore play an
important role in cement manufactur-
ing. Some halides such as fluorides are
also frequently used as mineralizers in
clinker production andinlow-tempera-
ture manufacturing of belite-rich ce-
ments. Mishulovich (1994) addresses
halides as catalysts for calcination. Con-
centration of halogens found in raw
materials and fuels is given in Tables 3,
4 and 6.
Fluorine
Fluorine (F) is commonly present in
limestone, clay/ shale, and coal (Sprung
17
et al., 1968, 1985) as a minor element
and plays an important role in cement
making. In raw feed, fluorine could
be up to 0.06%by weight (see Table 3),
whereas in limestone and clay/shale
it can go upto 940 and 990 ppm respec-
tively (Table 4).
Calcium fluoride (CaF2) isalsofre-
quently added to raw meal as a miner-
alizer and flux to lower the burning
temperature and accelerate the forma-
tion of C,S (Klemm et al., 1976, 1979).
Miller (1976) has, however, cautioned
not to use fluoride beyond 0.2570 to
avoid adverse effects on clinker be-
havior by selectively incorporating it
into the aluminates or silicate phases
at certain burning temperatures. At
lower temperatures, fluoroaluminates
(C1lA+CaF,) are formed, which are de-
composed at high temperatures to CqA
and fluorides. These fluorides are then
incorporated into silicates at higher
temperatures to form often stable
fluorosilicates but their excessive
amounts can cause decomposition of
alite.
Gartner (1980) also reported the
formation of alkali fluorides as NaF
and KF at higher alkali presence; these
fluorides being somewhat volatile
(boiling points 1700 and 1500C re-
spectively) are expected to end up in
the fine kiln dust. However, Sprung
et al. (1968) reported that between
887. to 987. of fluorides are incorpo-
rated in the clinker and only a small
fraction end up in the kiln dust, prob-
ably as CaFz Fluoride emissions were
reported low (0.009-1 .42 mg F/Nm3)
depending not necessarily on the mag-
nitude of fluoride balance but on the
efficiency of the precipitators.
Akstinat et al. (1988), reported
that fluorides have no adverse effects
on the cement production process,
and the fluoride cycle does not cause
any operational problems like coat-
ing, because of their presence in small
amounts. However, recent experi-
ences have shown that use of fluoride
based compounds can occasionally
cause plugging. Gartner (1980) re-
ported that the presence of fluorides
600
3oo-
0
40
{r ~
3-day
1
20
0
I I I
0
0.5 1.0 1.5 2.0
Fluoride (Yo mass)
Figure 8. Effect of fluoride on strength and setting time of high alite
cements (Moir, 1983).
beyond ()..5~o can cause both opera-
tional and quality control problems,
which, under certain situations, can be
controlled by PzO~addition. Goswami
et al. (1991), Bolio-Arceo et al. (1990),
and Gilioli et al. (1979), have reported
the formation of spurrite (2Cz9CaCO~),
and fluor-ellestadite that cause kiln
deposits, but the resulting low burn-
ing temperatures control the alkali
cycle and reduce the alkali-sulfate de-
posits.
Palomo et al. (1985) suggested that
0.2?4. fluoride promotes low tempera-
ture formation of aluminates such as
fluorinated CIZA,, C,A, and CZAS
(gehlenite); however, the final alumi-
nate mineralogy was not significantly
affected, as both ferrite and CqAwere
present at 1250C and above. Perez
Mendez et al. (1986) reported that with
the addition of 0.5-1.50/. fluorides, as
CaFz, clinkering reactions were com-
pleted in 0.5 hr at 13540C; the clinkers
had much of C$ developed, with
P-C,S, C,AF, and C,A also present
therein. Imlach (1974) observed that
fluoraluminate CllAToCaFz, forms at
fluorine levels of about 0.5% in clin-
kers fired below 1320C or slowly
cooled from 1340C to 12650C.
Fluoroaluminate imparts rapid setting
to cement pastes compared to the nor-
mal cements.
According to Aldous (1983), and
Shame et al. (1987), the presence of F
and Al beyond the threshold level ren-
ders C,S a rhombohedral symmetry,
which is associated with improved hy-
draulic properties. Moir (1983) dem-
onstrated that by optimizing the levels
of F, alumina, alkalies, and sulfates,
the C3S in clinker could be maximized
to enhance the setting properties of
18
cement. Figure 8 shows the relation-
ship between the fluoride addition and
compressive strength of cement pastes
at various curing ages. An optimum
fluoride addition for maximum
strength at early ages (24 hours) was
0.27., for later strengths (7 days and 28
days) addition of ().75Y0 were accept-
able.
Chlorine
As mentioned above, chlorine (Cl) as
chlorides is frequently found in lime-
stone, clays and in some cases in both
the primary and secondary fuels. In
limestone and clay the predominant
chloride is sodium chloride (Akstinat
et al., 1988). Some coals can contain up
to 0.28/oCl, mainly as rock salt (NaCl).
The formation of stable yet vola-
tile alkali chlorides NaCl (boiling
temperature= 1413C) and KC1 (sub-
liming temperature= 1500C) at clin-
kering temperature is well known.
Both the chlorides volatilize in the
burning zone and condense in the
cooler parts to form kiln rings or
preheater build-ups which impair
plant performance. Bhatty (1985) also
concluded that agglomeration due to
the presence of molten alkali chlorides
was one of the major reasons for the
build-ups. Cl also enhances the for-
mation of spurrite and sulfospurrite
(2C,S.CaSO,). In cases of plants with-
out preheater, the volatile chlorides
end up in the kiln dust. In preheater
kilns, up to 9%Jochlorides are recap-
tured by the incoming feed in the cal-
cining zone (Ritzmann, 1971); the con-
centration of chloride at that point
could be extremely high (>lYo) com-
pared to that of raw feed (-0.017.).
Relative volatility of Cl, and other ele-
ments in the kiln system is already
shown in Figure 5 (Sprung et al., 1984).
The wet processing plant and grate
preheater may tolerate raw feed with
higher chlorides, but the limits prima-
rily depend upon the efficiency of dust
collecting and the level of kiln dust
recycling. With the advent of the al-
kali by-pass, the chlorine cycle can be
broken at the most intense point of
kiln and the alkali chloride can be
conveniently directed to the dust col-
lectors. Otherwise, as reported by
Norbom (1973), a total chloride intake
of 0.015% (in both raw material and
fuel) can result in build-ups in a
preheater without a by-pass.
Since most of the chlorides are
volatile, the amount retained in clin-
ker is extremely small (d.03~0). VOla-
tile chlorides react readily with alka-
lies, so that the alkali level in the clin-
ker is often reduced when chloride is
present. The combined influence of
alkali chloride on cement properties is
therefore regarded as insignificant. In
some cases, calcium chloride is added
to the kiln for the express purpose of
increasing alkali volatilization and re-
moval, and result in the production of
a low alkali clinker. According to
Mishulovich (1994), the addition of
calcium chloride and chlorine-con-
tainingorganiccompounds at the clin-
kering stage, accelerated both lime re-
action and alkali volatilization. In a
preheater klin, the addition of calcium
chloride in the burning zone, resulted
in 2070 increased production with cor-
responding fuel saving.
In waste-derived fuels such as
waste-oils contaminated with chlo-
rides, chlorinated hydrocarbons and
scrap tires, the chlorides would occur
indifferent compounds at much higher
concentrations (Akstinat et al., 1988),
and cause serious operational prob-
lems even in kilns equipped with by-
pass. In order to make their use fea-
sible, a larger portion of by-pass dust
would have to be discarded to prevent
building up a large chloride cycle
High chlorides in the raw feed
have also been reported to form con-
densation plumes in the emission
stacks in long wet or dry kilns which
are difficult to remove at times. Such
detached plumes are generally the re-
sult of NHAC1 formation. Excessive
chlorides can also have a deleterious
effect on kiln basic brick lining.
Chlorides, particularly CaClz, ac-
celerate the hydration and hardening
of cement paste and increase the very
early strength but, at the same time,
chloride ions are also known to pro-
mote corrosion of steel reinforcing
bars in concrete.
AliniteCements: The development
of less energy intensive alinite ce-
ments from the CaClz incorporated
raw material has generated great in-
terest (Nudelman, 1980). The for-
mula ascribed to the alinite phase is
close to 21 CaO6SiOzA110q* CaClz
with some MgO inclusion (Lecher,
1986). The burning temperature for
alinite clinker is between 1000-11 OOC.
The raw mix is composed of 6-2370
CaClz by weight. MgO is added to
stabilize the alinite phase at 60-80?40,
belite at l&30~o, calcium alumino-
chloride at 5-1OYO, and calcium
aluminoferrite 2-107. (Bikbaou, 1980).
Ftikos et al. (1991) reported that the
strength development of alinite ce-
ment was comparable to that of regu-
lar portland cement.
Bromine
With some exceptions, bromine (Br)
plays a minor role in cement manu-
facturing. Bromine occurs only as a
minor element in raw materials, i.e.
limestone (6 ppm), clay (10-58 ppm),
and coal (7-1 lppm). (Akstinat et al.,
1988) and Sprung et al. (1985). Bro-
mine has also been detected at mea-
surable levels in some of the fly ashes
generated at coal operated power
plants.
Bromine is volatile and expected
to end up instackemissions (Akstinat,
1988). Under oxidation conditions,
bromine gas (Br2) would form and
end up in emissions. Retention of
bromine in clinker is negligible. Al-
kali bromides can also be found in
cement kiln dust. Between 510 ppm
of bromine was reported in one CKD
sample using fly ash as a partial raw
feed (Klemm 1995). At higher levels
of bromides, the formulation of bro-
mine-alinites analogous to chlorine-
alinites, as mentioned above, has also
been reported by Kurdowski et al.
19
Role of Minor Elements in Cement Mmzufactureand Use
(1987, 1989). Bromine-alinites are
much more reactive than the alites
(I@rdowski et al, (1989).
Kantro (1975) reported that at
equivalent concentrations CaBrz is a
stronger accelerator for C~Spastes than
the chlorides or iodides.
Iodine
The presence of iodine(I) in limestone
and clay is negligible. Up to 0,75 ppm
in limestone, 2.2ppm in clay and shales
(Mantus et al.), and between 0.8 to
11.2 ppm is found in coal (Sprung
1985).
Because of the low levels of io-
dine in the feed, the effect on the burn-
ing process is negligible. Iodine salts
are volatile in nature and mostly end
up in emissions. Conversion of io-
dine gas (IJ from iodides is easier
than bromides. Their concentration
in clinker is detected at very low
levels. There is no literature report on
iodine presence in the CKD. The con-
centration of iodine in CKD is ex-
pected to be extreamly low, maybe in
the ppb, because of its presence in
small amounts in the raw materials.
CaIz is reported to accelerate C~S
pastes though not as effective as bro-
mides or chlorides (Kantro, 1975).
ELEMENTS IN GROUP Vlll
(Helium, Neon, Argon, Krypton,
Xenon)
Helium (He), neon (Ne), argon (Ar),
krypton (Kr), and xenon (Xc), being
inert gases, are not known to impart
any noticeable effect on clinker
manufacturing or cement hydration
properties.
TRANSITION ELEMENTS
(Yttrium, Titanium, Zirconium,
Vanadium, Niobium, Tantalum,
Chromium, Molybdenum, Tungsten,
Manganese, Cobalt, Nickel, Copper,
Silver, Zinc, Cadmium, Mercury)
Ti
v
Cr
Mn
co
Ni
Cu
Zn
Aluminoferrite
I I I I I t
01234 5 0 0.5
Weight Y.
Belite
r
Aluminate
;oo15i
Figure 9. Distribution of transition elements in clinker phases
(Hornain, 1971).
Table 13. Relative Ratios of Ti02 in Different Clinkers Phases,
(After Different Workers)
Clinker Hornain Regourd Knofel
Phases (1971) et. al. (1974) (1977)
Alite 1 1 1
Belite 2 1.7 2
Aluminate 0.8 3.3 3
Ferrite 6 10.8 7
TiOp in Clinker (wt.A) 0.78 (not reprinted) 1.0
The elements 21-30,39-48, and 57-80
in the periodic table are known as the
transition elements. Not all of these
elements have been studied in cement
manufacturing, but the ones that have
been studied in some detail are dealt
with in this section. Some of these
transition elements are introduced
into the clinkering process through
the use of spent catalysts as an alu-
mina source.
Yttrium
Isomorphismbetweenyttrium (Y) and
calcium frequently occurs in natural
materials; for instance fluoroapatite,
Ca2Ca~(P01)F,can contain up to 10.6%
YzO~(Povarennykh, 1966). But pre-
sumably in cement raw materials,
yttrium occurs only in traces.
Yttrium substitutes for Ca in both
C~Sand CZS(Boikova, 1986). It yields
both triclinic and monoclinic forms
of C~S. In a CZS-Yg(SiOi)~system, the
region of homogeneity can exist up
to 35% YA(SiOA)~by weight (Toropov
et al., 1962-2).
Yttrium chloride is reported to
have an accelerating effect on CqS
paste when added as an admixture
(Kantro, 1975).
Since yttrium is unlikely to vola-
tilize at kiln temperature(melting
point= 1522C), it can hardly be ex-
pected to concentrate in the kiln dust.
It should preferentially become in-
corporated in clinker.
Titanium
Titanium (Ti) as oxide could be
present in typical cement raw mate-
rial at the ().()2-O.4~0level by weight
(Bucchi, 1980). Gartner (1980) re-
ported a higher concentration of O.1-
20
1.0?4.Ti02 in many raw mixes. Con-
centrations of TiOz in some of the
auxiliary raw materials is even
higher. Blast-furnace slag for in-
stance, can contain 1.!7~0TiOz, and
the bauxites may have between 2-
8% TiOz by weight.
TiOzisarefractory material (boil-
ing point= 2500-3000C) and is es-
sentially incorporated in clinker. At
low levels the effects of Ti on the
manufacturing of cement is insig-
nificant (Miller, 1976), higher levels
of up to 2% may improve the com-
pressive strength of clinker (Knofel,
1979). Hornain (1971), and Marinho
et al. (1984), reported that TiOz is
preferentially distributed in ferrite
phase. Distribution of other selected
transition elements indifferent clin-
ker phases, as determined by
Hornain (1971), is also shown in Fig-
ure 9. Relative ratios of TiOz distri-
bution in clinker phases as reported
by different workers is also given in
Table 13 for comparison. Titanium
from ilmenite (FeTiOJ additions to
kiln feed has been used to produce a
patented buff-colored cement.
Knofel (1977) observed a sharp
reduction in alite with equal gain in
the belite phase when Ti02 was in-
creased in the raw mix; the variation
in ferrite and aluminate was not sig-
nificant. Calcium titanate (CaTiOJ
is apparently the major phase present
in clinker. It was also reported that
about 1ZOTiOz addition in the raw
mix reduces the melt temperature
by 5O-1OOC,probably because of a
favorable relationship between ionic
potentials and the melt viscosities as
shown in Figure 10, This relation-
ship was developed by Timashev
(1980). It shows that increasing the
ionic potential of transition elements
in groups of elements with equiva-
lent atomic radii decreases the clin-
ker melt viscosity.
Although TiOz enhances the
early hydraulicity of alite (Kondo,
1968), the clinkers have shown slow
initial setting. However, 1% TiOz
clinker have roughly 207. higher
-600
- 400
- 200
-o
0.115 0.130 0.145 0.160
Viscosity, Ps sec
Figure 10. Relationship between viscosity and ionic potential to
radius ratio, and cation-oxygen bond of transition elements at
1450C (Timachev, 1980).
3-and 90-day strengths (Knofel, 1977,
1979).
Zirconium
Zirconium (Zr)isconcentrated mostly
in siliceous ores which can be used as
a raw feed component (Miller, 1976).
Blaine (1965) reported about 0.5%
zirconium, probably in the fully oxi-
dized form of ZrOz, in US. clinkers.
Kakali et al. (1990) found no signifi-
cant change in the burning and cool-
ing conditions for clinker prepared
with 0.73-1 .45% ZrzOJ; the principal
phases, alite, belite, aluminate, and
ferrite, were satisfactorily crystal-
lized. However, ZrzO~changed the
size and shape of alite, while the type
of belite crystal was modified. Zr20~
also imparted a noticeable color
change in clinker (Kakali, 1988).
A significant retarding effect
and a subsequent delay in strength
for cements prepared with ZrO con-
taining raw mixes was also reported
(Kakali et al. , 1989). However, ear-
lier studies by Blaine et al. (1966)
indicated that smaller ZrO additions
increased the early compressive
strength of cement.
Vanadium
Vanadium (V) occurs at a measurable
level in cement raw material (10-80
ppm inlimestone,98-170 ppm in clay/
shale, and 30-50ppm in coal) (Sprung,
1985). It is also present in fly ash
where it tends to concentrate in the
finer fractions (Coles, 1979). Fairly
high levels of vanadium are also re-
ported in crude oils (Gartner, 1980).
In one study, Weisweiler et al, (1990)
has reported nearly 800 ppm vana-
dium in petroleum coke used in ce-
ment manufacturing. Ash from pe-
troleum coke also contains very high
levels of VzO~(up to 607.). Because
the petroleum coke has a low overall
ash content, Moir et al. (1992) found
no more than 0.08% VzO~ in clinker
produced in modern cement plants
that use 50% petroleum coke as a sub-
stitute fuel.
Use of vanadium is known to de-
crease the melt viscosity primarily be-
cause of its higher ionic potential as
21
shown in Figure 10. Vanadium is
present as VzO~in cement clinker. It
concentrates in alite and forms larger
crystals. However, according to
Hornain (1971), vanadium preferably
concentrates in belite rather than alite,
as shown in Figure 9. VzO~is unlikely
to vaporize at normal kiln tempera-
tures. On the other hand, vanadium
present in fuel may not have adequate
contact with the reacting mass in the
kiln and largely ends up in the kiln
dust as suggested by data from
Weisweiler et al. (1990).
Odler et al. (1980-1) reported that
l% V20~ can significantly reduce the
free lime in clinker when fired at
1200C. Xinji et al. (1986) used V20~ for
stabilizing B-CZSin clinker apparently
by substituting V01-3 for Si014.
A concentration of 1.57. V20~ is
reported to increase hydraulicity of
alite; however, higher concentrations
adversely affect the grindability of re-
sulting clinkers. High VzO~levels as
found in some crude oils could also
deteriorate kiln lining in some cases
(Gartner, 1980). V,O, in clinker can
also increase sulfate expansion under
certain circumstances (Blaine et al.,
1966).
Niobium
Niobium (Nb) is another element to be
found in traces in cement raw materi-
als. Weisweiler et al. (1990) has re-
ported more than 30 ppm niobium in
the raw feed of a German plant.
Because of the low level presence
in the raw mix, niobium would have
very little effect either on the clinker
formatitm or on the cement hydration
properties. Kakali et al. (1990) reported
a very feeble effect of Nb+5addition (up
to 1.5% by weight) on the mineralogi-
cal texture and the viscosity of clinker
melts because of its low ionic charge to
atomic radius ratio.
Cementpastesprepared from these
clinkers did not show any noticeable
change in their setting or strength prop-
erties when compared to regular ce-
ment pastes (Kakali et al., 1989).
Table 14. Chromium Distribution in Typical Clinker* Phases
Containing 0.55YI0Cr,O, (Hornain, 1971 )
Phases Cr(%)
Belite 0,87
Ferrite 0.55
Alite 0.39
Aluminate 0.04
*The clinker contained C,S=76.3Y0, C,S=9. 1A, C~A=5.3/, and C,AF=8/.
Because niobium is a high tem-
perature metal (melting point
=24680C), it would unlikely concen-
trate in the kiln dust or in the stack
emissions.
Tantalum
Tantalum (Ta) is only a trace element
in cement raw material. It reported to
be present at less than 9 ppm in raw
material and 0.3 ppm in the oil coke
used as fuel in cement manufacturing
(Weisweiler et al., 1990).
Since tantalum is present as trace
in both the raw feed and fuel, it is
unlikely to impart any noticeable ef-
fect on the clinker formation and ce-
ment use. Weisweiler et al. (1990)
have reported 14.3 ppm and 3.3 ppm
tantalum respectively in clinker and
kiln dust prepared from a raw mate-
rial containing 8.9 ppm tantalum.
Chromium
Chromium (Cr) can be present in raw
feed immeasurable quantities. Sprung
(1985) has reported up to 16 ppm in
limestone, nearly 100 ppm in clay and
shales. Coals and used oils may con-
tain up to 80 ppm and 50 ppm Cr
respectively. Some of the auxiliary
raw materials, such as bauxites, which
are used up to 4/0 in cement manufac-
turing, may contain between
0.04-0.40/. CrzO~. In addition to that, a
proportion of Crcanalsoentercement
from the grinding media during raw
meal preparation and finished cement
grinding, and refractory linings.
The presence of Cr in raw materi-
als is known to reduce the viscosity of
clinker melt due to its high ionic
charge as is shown in Figure 10. Miller
(1976) has reported improved clin-
ker burnability at 1/0CrzO~addition.
Chromium can exist in a number of
oxidation states in clinker, the most
stable being Cr+3and Cr+b. Their for-
mation is sensitive to the oxygen level
in kiln. High oxygen tends to form
Cr%compounds as chromates which
are readily soluble in water and mark-
edly affect the hydration characteris-
tics of the paste. Reducing condi-
tions favor the formation of Cr+3com-
pounds which are less soluble in mix
water.
Under oxidation conditions, Cr
can also exist as Cr~ and Cr+5in C2S,
which can then disproportionate to
the more stable Cr+3 and Cr% upon
mixing with water (Feng Xiuji, 1988).
Johansen (1972) has reported Cr,
Cr-b, and Cr+5 in alite substituting
for Si+4. Hornain (1971) reported that
Cr preferentially resides in belite fol-
lowed by ferrite, alite, and alumi-
nates, as shown in Table 14 (see also
Figure 9), Although Cr+b can be
present in both alite and belite, it is
reported to be stabilizing the ~-CzS
form (Hornain, 1971, and Kondo,
1963). Subarao et al. (1987) devel-
oped an active belite-rich cement
from raw feed containing 4-5% CrzOJ
by weight. Imlach (1975) used O.11-
I.qzy. Cr203 in the raw feed as a flux.
The resulting cement exhibited im-
proved 8- and 24-hour strengths, but
28-day strengths always decreased.
A significant portion of Cr can
also enter the finished cement from
chrome-rich grinding media (Klemm,
1994). It is reported that the level of
22
Cr4in ground cement is almost doubled
by the use of high-chromium alloy balls
during grinding. A number of patents
report the use of inorganic reductants
to control the Cr+Aleaching from ce-
ment. Most of these patents are of
European origin and use ferrous sul-
fate heptahydrate, ammonium-ferrous
sulfate, and manganese sulfate during
intergrinding to convert Crk to Cr+3.
Chromium is known to accelerate
the hydration of paste and improve the
early strength, and has thus been used
to develop high strength cements. Re-
cent studies (Bhatty et al., 1993) have
shown that 0.7570 addition of chromium
as chromium chloride and nitrate, ac-
celerate paste hydration and result in
high initial hydration peaks. The work-
ability and the initial setting times are
reduced, but the early strengths (3 days)
are significant yimproved over the con-
trol. The 28- and 90-day strengths are,
however, close to those of the control.
The addition of insoluble chromium
oxide (Cr20~), even up to 1.37., did not
significantly affect the hydration or the
strength behavior of the pastes. The
degree of Cr stabilization in cement
matrices as determined by leachability
in both these cases was almost 100Yo.
Chromium may also contribute to high
sulfate expansion, increased 24-hour
shrinkage, and reduced autoclave ex-
pansions.
Although a major portion of chro-
mium is incorporated in clinker, usu-
ally tied up in belite, ferrite, or sulfate
phases, chromium can be found in the
CKD. Between 100-1000 ppm of Cr
have been reported in CKD (Lee et al.,
1973; Howes et al., 1975), although re-
cent studies (PCA, 1992) have shown
only between <0.01-264 ppm in CKDS
produced by burning conventional fu-
els, and between <0.01-299 ppm in
CKDS produced by waste derived fu-
els. Detectable levels of 20.6 mg/sec
and 12.5 mg/sec have also been found
in kiln emissions using conventional as
well as waste fuels respectively (Mantus
et al., 1992). In U.S. cement, total chro-
mium is reported to be between 20 and
450 ppm.
Molybdenum
Molybdenum (Mo} is potentially an
important trace element in lubricat-
ing oil (Gartner, 1980). In coal fly ash,
MoOS can be as high as 1.5% by
weight.
Up to 0.05?o of Mo has been re-
ported incliners (Blaine et al., 1965).
Molybdenum, having small radius
and a high charge number, is an ef-
fective reducer of the clinker melt
viscosity as shown in Figure 10.
Kakali et al. (1990) reported the for-
mation of large round alite crystals in
clinker prepared with up to 1.57.
M003 addition, with some modifica-
tions in belite. However, cement
pastes prepared from these clinkers
exhibited no adverse effects on the
engineering properties (Kakali et al.,
1989).
Tungsten
Tungsten (W) is trace metal in raw
mix and is expected to appear in traces
in the clinker. Very little work has
been reported on the effect of tung-
sten on clinker formation and use.
Kakali et al. (1990) noted that the
addition of up to 1.5?4.WO~in the raw
mix changed the shape of alite crys-
tals, making them bigger and more
roundish; the belite formed was of
type III and, to some extent, con-
tained secondary dendritic crystalli-
zation probably because of excessive
Si~ replacement by W%. Dissolution
of W% in the melt decreased the vis-
cosity because of its large charge to
radius ratio, as is also exhibited in
Figure 10.
Ivashchenko (1991) reported that
addition of W% also improved the
granulometric composition of clin-
ker and decreased dusting. Improved
hydraulicity was expected because
of enhanced activity of ferrite and
alite modification in the clinker. How-
ever, cement pastes prepared from
these clinkers did not show any sig-
nificant change in the setting or
strength properties when compared
to theregularones (Kakaliet al., 1989).
Tungsten is a very high temp-
erature melting metal (melting
point=3410C). Since itwill not volatil-
ize at kiln temperatures, its presence in
the CKD, or stack emissions, is exceed-
ingly remote<
Manganese
Manganese (Mn) inclinkercomesfrom
both the primary and auxiliary raw
feeds. Limestone can contain up to
1.91% Mnz03 as the carbonate mineral
rhodochrosite, whereas shales and
bauxite canhaveup to O.59% and O.37%
by weight respectively (Bucchi, 1981).
In blast furnace slags, M~O~ can be
present up to 1.2% and in coal fly ash
up to 1.447. by weight.
Cement produced from slags can
contain more than l% Mnz03 and usu-
ally imparts a brown color to cement
(Lea, 1971). The polymorphism of sili-
cate in clinker is affected by the pres-
ence of manganese oxides in the raw
material. Knofel et al. (1984) reported
that the limit of MnzO~ substitution in
CJS is approximately 2.2% at 1550C.
At lower concentrations, say -0.1XO
M~O~, single substitution of Si- by
Mn+4 takes place, whereas at 2.27.
MnzO~concentration, a double substi-
tution of Si4 by Mn4 and Ca+2by Mn+2
is possible. The stabilized CaS poly-
morph was identified as monoclinic;
Gutt and Osborne (1969) reported it to
be triclinic. Miller (1976) demonstrated
that at low concentrations (<0.7%), Mn
stabilizes monoclinic alite, but at high
concentration and in the presence of
fluoride, triagonal alite with markedly
high hydraulicity is formed.
Manganese can occur in a number
of oxidation states depending upon
the burning conditions in the kiln and
can impart different colors in clinkers,
ranging from reddish-brown to blue.
Puertas et al. (1988) have studied the
influence of kiln atmosphere on Mn
solid solutions in C~Sand C2S. It was
reported that under reducing condi-
tions isomorphous replacement of Ca+2
by Mn+2 occurs, while in air having
higher oxygen level, MnA replaces Si~.
23
According to Knofel et al. (1983)
alite content of clinker increases with
Mn addition, with maximum alite at-
tained at 0.57. MnOz and 1?4. Mn20~.
High Mn content promotes the forma-
tion of belite in the silicate phases, but
is more preferentially incorporated
into the ferrite phase through the for-
mation of alumino-manganite, such
as CAAMn (see Figure 9). This re-
duces C~A and marginally increases
free lime, thus reducing the early corn-
pressive strength of the pastes.
Manganese will not volatilize
at kiln temperature (boiling point=
1960C), and is unlikely to concentrate
in the CKD or be found in stack emis-
sions.
Cobalt
Cobalt (Co) is present in traces in the
raw mix; the maximum reported con-
centration is 23 ppm COO. It has also
been found at much higher levels (up
to 1.27~0) in some of the coal fly ashes
that could be used as partial cement
raw feed (Bucchi, 1981).
The bulk of cobalt that is present
in the raw mix is incorporated in clin-
ker. The CoO level reported in cement
is <130 ppm, but the amounts detected
in the alite and belite phases are only
in traces as the bulk of cobalt is concen-
trated in the ferrite phase by replacing
Fe3+and forming the C~ACo phase
(see Figure 9). Cobalt can also give
color to cement.
Sychev et al. (1964) demonstrated
that Co somewhat reduces the hydrau-
lic activity of alite and increases clinker
hardness. According to Miller (1976),
cobalt increases the water demand and
marginally reduces the late strength of
cement paste.
Cobalt is unlikely to vaporize in
the kiln (boiling point= 287@C), thus,
concentrations in CKD or in stack gases
are expected to be exceedingly small.
Nickel
Sprung (1985) has reported traces of
nickel (Ni) in limestone (1.5-7.5 ppm),
clay or shale (61-71 ppm), coal (20-80
ppm), used oil (3-30 ppm), and petro-
leum coke (208 ppm). In coal fly ashes,
NiOispresentup to 1.9% (Bucchi, 1981).
Nickel preferentially concentrates
in the ferrite phase, followed by alite,
aluminate, and belite as shown in Fig-
ure 9 (Hornain, 1971). Between 0.5 to
1.07. nickel stabilizes alite (Rangaro,
1977). NiO substitutes for CaO up to 4
mole 70in alite and stabilizes the mono-
clinic form (Enculeseu, 1974). This alite
modification apparently enhances the
l-day and 5-year compressive strength.
Miller (1976) reported that water soluble
nickel compounds act as accelerators
and tend to give high early strengths.
Kantro (1975) and Zamorani et al.
(1989)) also found NiCl, to be an accel-
erator for C~Spastes when used as mix
solution.
Mostly, Ni compounds are non-
volatile, yet, owing to the volatile na-
ture of some compounds, such as
NiCO~, nickel could end up in the kiln
dust, although recent PCA studies has
shown a maximum of only 60 mg/kg
Ni in the CKD. The average amount of
Ni in cement is 31 mg/kg (PCA, 1992).
Copper
Bucchi (1981) has quoted an average of
16 ppm copper oxide (CUO) in the raw
mixes, and a <0.13Y0 in coal fly ash,
On average, 90 ppm CUO occurs in
commercial clinkers Bucchi (1981).
Copper preferentially concentrates in
the ferrite phase followed by alite, alu-
minate, and belite (see Figure 9,
Hornain, 1971). Miller (1976) reported
that under oxidizing conditions, the
small amount of copper present asCuO
stabilizes alite, whereas under reduc-
ing conditions, copper as C~O ad-
versely affects both the alite and belite
phase formations. CUO can also
function as a flux, as it decreases
the melt temperature considerably
(Rumyanstev et al., 1968). Odler et al.
(1980-1,2) found that 1% CUO addition
was effective in reducing free lime at
much lower melt temperatures. It may
be mentioned that CUO accelerates C3S
formation whereas CUZOinhibits it.
Soluble copper salts are retarders
and give low heat of hydration
(Takahashi et al., 1973, Miller, 1976;
Tashiro et al., 1977). The effect is more
pronounced ontheC~Aphase (Tashiro
et al., 1979). The addition of copper
also gives low sulfate expansion in
certain cases (Miller, 1976).
Copper oxides are volatile at
kiln temperature (melting points
CUO=1326C, CUZO=1235C). As a
result, copper has been found up to
500 ppm in some U.S. cement kiln
dusts (Howes et al., 1975).
Silver
Silver (Ag) is present only in traces
(<0.250 ppm) in both the kiln raw
material and coal; in coal it may occur
as silver sulfides ,or as a complex,
Since silver occurs in traces, it is
not expected to significantly contrib-
ute in the clinkering process. Silver is
present at 9.2 ppm in cement; it is
reported in CKD at 6 ppm for kiln
operated with conventional fuels and
at 2.5 ppm for kilns using waste fuels
(PCA, 1992).
Zinc
Zinc (Zn) is a trace element in the raw
mix, reporting 22-24 ppm in limestone,
59-115 ppm in clay or shale, and
16-220 ppm in coal. However, it can
be present up to 3,000 ppm in used
oil as a potential secondary fuel (see
Table 6), or 10,000 ppm in used tires.
Its concentration is also reported to be
significant in alternative raw materi-
als such ascertain metallurgical slags,
basic oxygen furnace (B.O.F.) dust,
and B.O.F. filter cake (Miller, 1976,
1994).
Between 80-90% Zno in the raw
mix typically becomes incorporated
in clinker (Sprung et al., 1978; Knofel,
1978). Approximately half of the zinc
is distributed in silicates with prefer-
ence for alite while reducing belite;
the other half is distributed into the
matrix with preference for the ferrite
phase (Knofel, 1978; Tsuboi
1972). According to Hornain
et al.,
(1971)
24
zinc in clinker is preferentially re-
tained in ferrite followed by alite,
aluminate, and belite (Figure 9). ZnO
additions accelerate the clinker for-
mation. Alite and CZ(AF) formations
increase at the expense of belite and
C~Adue to ZnO doping (Odler et al.,
1980-3).
Stevula and Petrovic (1981) pre-
pared a triclinic modification of C,S
of the type T1-TI1from mixtures of
0.75-1.5% ZnO and pure C~S, fired at
about 1600C and slowly cooled. Ad-
ditions of 3.0 and 4.5y0 ZnO formed
rhombohedral C~Swith no free ZnO.
Boikova (1986) reported the change
in C~S symmetry from triclinic to
monoclinic and to rhombohedral with
increasing ZnO additions.
Up to 1.0% ZnO in the raw mix
decreases free lime considerably
(Odler et al., 1980-1,2), retards the
hydration, and reduces strengthwhen
added in excess of 1.0%.(Odler et al.,
1980-3). Similar observations were
reported by Knofel (1978). Miller
(1976) suggested the likelihood of re-
ducingZninclinker by preferentially
vaporizing it where the liquid phase
is low, thus reducing the potentially
deleterious effects on cement setting.
ZnO as an admixture also im-
parts a severe retarding effect on ce-
ment hydration; early strength is re-
duced,andthelate strengths (28-days
and beyond) are increased. In fact,
zinc also increases the late strengths
(5-10 years) but decreases the paste
shrinkage during the early ages of 1
and 28 days (Miller, 1976). Arliguie
et al. (1982,1985, 1990) demonstrated
that C~S, C~A, and cement hydration
are delayed by the formation of pri-
mary zinc hydroxide and its conver-
sion to a crystalline form around the
anhydrous grains. Miller (1976) re-
ported the formation of a complex
calcium hydroxo-zincate intermedi-
ate compound that inhibits C$ hy-
dration.
According to Sprunget al. (1978),
the volatility of zinc for preheater
kiln could be 1O-2OYO.For a multi-
stage preheater kiln, the capture of
ZnO would be more effective and
could result in the total incorporation
into the clinker. An average of 149
ppm zinc has been reported in the
CKD from the U.S. plants using con-
ventional fuel and 150 ppm for those
using hazardous waste fuel (CRI, in
Mantus, 1992); thecorrespondingzinc
levels in the plant emissions are only
2.97 and 1.53 mg/see, respectively.
Cadmium
Cadmium (Cd) occurs in traces in the
raw materials and fuels. The average
amount of Cd in cement has been
reported tobe0.34mg/kg(PCA, 1992).
Cadmium in the raw feed reacts
with the constituent of kiln gas and
can form halides or sulfates, both are
readily vaporized at peak kiln tem-
perature (Kirchner, 1985). The form
of cadmium incorporated in clinker is
not known; however, with increasing
chloride input in the kiln, the concen-
tration of Cd in clinker is known to
decrease. The addition of CdClz in the
raw mix has the same effect. In a
cyclone preheater kiln, 74-88?4. of the
total Cd entering the kiln is incorpo-
rated in the clinker as opposed to 25-
64% for that produced in the grate
preheater kilns; the remaining Cd is
captured in the kiln dust (Weiswerler
et al., 1987).
Cadmium is also volatile in na-
ture, although not as volatile as thal-
lium or chlorine. Volatility of cad-
mium relative to other elements in the
kiln feed is shown in Figure 5 (Sprung
et al., 1984). CdO is reported to in-
crease the burnability of the clinker by
lowering the melt temperatures
(Rumyanstev et al., 1968), whereby
Cd+2 most likely enters the silicate
phases (Ramankulov et al., 1964).
Some improvement in burnability of
clinker with CdO addition was also
observed by Odler et al. (1980-1).
Recent studies (Bhattyet al., 1993)
have shown that high CdOconcentra-
tions retard the cement hydration, but
the strength properties are not af-
fected. Addition of soluble cadmium
salts (CdC12) has no apparent effect on
cement hydration. Cd is not leached
from the cement pastes when used as
CdO and CdC12admixtures.
Mercury
Mercury (Hg) is a trace element.
It is highly volatile and vaporizes at
much lower temperatures (boiling
point=557C).
Mercury is somewhat inert, and
very little is known on its interaction in
the clinker making process. It is very
likely that mercury and its compounds
would volatilize in the pre-calcination
region at temperatures closer to 400C
and escape with the stack gasses. Total
mercury is well below detection limits
for most North American cements.
Recent studies (Bhatty et al., 1993)
have shown that mercury compounds
(bothinsolubleHgOand soluble HgC12)
impart little effect on the paste hydra-
tion and strength properties.
THE RARE EARTHS
Elements 51-71 are commonly known
as the rare earths or lanthanides.
They are present only as traces in raw
materials and cement clinkers. Owing
to their presence at extremely low lev-
els, they have not been a subject of
extensive studies in cement manufac-
turing.
Since the rare earths have verysimi-
lar properties to one another, it is as-
sumed that they all will have some-
what similar effects on the clinker for-
mation.
Boikova et al. (1964, 1966, 1986)
and Toropov et al. (1963) observed the
substitution of rare earths for Ca in
both C$ and CZS. The solid solution of
C~S with oxyorthosilicates of lantha-
num (La) and scandium (SC) results
from the similarities in ionic size, and
chemical properties between Ca, La,
and SC. Formation of C$ solid solution
with gadolinium (Gal), neodymium
(Nd), and Erbium (Er) have also been
reported. Jantzen et al. (1979) reported
25
!
that nearly 157. of Nd/SiaOlz can be
dissolved into ~-C2S,which have iden-
tical hydraulicity to that of regular ~-
CZS. La stabilizes all modifications of
C~Ssolidsolutions (Stevula et al,, 1981;
and Sinclair et al. 1984). Gd gives the
triclinic and monoclinic formulations,
whereas SCproduces only the triclinic
C# solid solutions. Leaching of Nd
stabilized in cement pastes is also fairly
low.
Lanthanum also stabilizes the
solid solution of CZS by substituting
for Ca+2 (Toropov et aL, 1962-1,-2).
Based on the observations on the rare
earths, La, Nd, Gd, and Sc, Boikova
(1986) assumed thattheremaining rare
earths, for having similar chemical and
ionic characteristics, would isomorph-
ously substitute for Ca+2 in C~S and
CZS. As a result, a larger distribution
of rare earths in wastes could be ex-
pected in the clinker silicate phases.
Rumyantsev et al. (1970) reported
that the addition of LazO~in the raw
mix accelerates the formation of clin-
ker under laboratory conditions. The
engineering properties of the result-
ing cements were also enhanced when
compared to control. LaCl~ acceler-
ates the C$3 hydration when added as
admixture (Kantro, 1975).
The idea of studying rare earths in
cement manufacturing also stemmed
from the possibility of using various
medium to low level radioactive
wastes that frequently contained sig-
nificant amounts of rare earth ele-
ments.
Studies by Jantzen et al. (1982),
and Boikova (1986) indicated that 20-
3070 loading of radioactive waste corn-
posed of La20~, UOq, CeOz, and other
oxides, give optimum elemental re-
tention in clinker at processing tem-
peraturesof - 11OOC-12OOC. Volatil-
ization and activation of radionuclides
occured above 1200C, whereas clin-
keringat 1000C produced incomplete
reaction.
Jantzenet al. (1979) developed clin-
kers by incorporating 15-20% by
weight of simulated radioactive wastes
and firing at about 1200C. A number
of wastes were designed to incorpo-
rate varying combinations of Cs*, Cc*,
Nd, Sr*; Lu*, Yb, other Lanthanons;
and Sr, Nd, La, Y*, and Ba silicates.
The resulting clinkers were tested for
their hydraulic reactivities. The clin-
kers were slow to react, but the ulti-
mate hydration products were prima-
rily stable insoluble calcium silicates
hydrates which had reasonable distri-
bution of the radionuclides. Sichov
(1968) reported that La,Nd, and Ce all
enhanced the hydraulicity of alite.
Rare earths are expected to have
low volatilities (Klein et al., 1975) and
are very unlikely to be found in the
kiln dust or in stack emissions.
CONCLUSIONS
The effects of almost all the stable mi-
nor and trace elements on the produc-
tion and performance of portland ce-
ment have been reported. Emphasis
has been given to elements which oc-
cur in natural and by product materi-
als used for cement manufacturing.
The elements for which detailed infor-
mation has been obtained are dealt
with in an order based on the periodic
classification of elements. The vola-
tilities of the elements have also been
discussed where ever necessary. Ele-
ments reviewed include hydrogen, so-
dium, potassium, lithium, rubidium,
cesium, barium, beryllium, strontium,
magnesium, boron, gallium, iridium,
thallium, carbon, germanium, tin,lead,
nitrogen, phosphorus, arsenic, anti-
mony, bismuth, oxygen, sulfur, sele-
nium, tellurium, fluorine, chlorine,
bromine, iodine, helium, neon, argon,
krypton, xenon, yttrium, titanium, zir-
conium, vanadium, niobium, tanta-
lum, chromium, molybdenum, tung-
sten, manganese, cobalt, nickel, cop-
per, silver, zinc, cadmium, mercury,
and the lanthanides.
The review indicates that al-
though certain elements have been
studied in detail for their role in the
clinkering process and cement prop-
erties, data on a number of elements is
available only to a limited extent, Al-
though some progress has been made
in understanding the role of these el-
ements on clinker properties, interac-
tion between their nature and the
major clinker components still needs
to be properly understood
Use of trace elements as fluxes or
mineralizers to enhance the clinker-
ing process is also being realized, yet,
understanding of the underlying
physico-chemical mechanism and the
potential energy saving aspect re-
quires additional input.
Now that the technological ad-
vances in cement manufacturing are
in place, efforts can be directed to-
wards exploring the following aspects
of clinker-element interaction:
1: Make use of the minor elements
present in raw materials and
fuels to enhance the clinkering
process and the performance of
cement.
2: Make use of the minor elements
in conserving energy during clin-
ker production; elements with
proven fluxing/mineralizing
characteristics could be prime
examples.
ACKNOWLEDGMENTS
This report (PCA R&D Serial No. 1990)
was prepared by Construction Tech-
nology Laboratories, Inc. (CTL) with
the sponsorship of the Portland Ce-
ment Association (PCA Project Index
No. 93-01). The author wishes to ac-
knowledge the contributions of W.A.
Klemm and F.M, Miller of CTL for
carefully reviewing the manuscript.
The contents of the report reflect the
views of the author who is respon-
sible for the facts and accuracy of the
data presented. The contents do not
necessarily reflect the views of the
Portland Cement Association.
*
Cs =Cesium,Ce =Cerium,Sr =Strontium
Lu=Lutetium,Yb=Ytterbium,Y=Yttrium
26
PCA Research and Development Bulletin R13109T
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34
APPENDIX. A Summary of Possible Effects of Minor Elements on the Formation of Clinker and Properties
of the Resulting Cements
Trace Elements Affects on Clinker Formation Affects on Cement Properties
Group I
Hydrogen not known not known
Lithium forms oxiide, lowers phase temperature reduces alkali-silica reactivity
(ASR) in concrete
Sodium lowers melt temperature, promotes internal cycle, enhances early strength, increases
causes phase separation, forms complex ASR susceptibility
chloride/sulfate compounds
Potassium lowers melt temperature, promotes internal cycle, enhances early strength, increases
causes phase separation, forms complex ASR susceptibility
chloride/sulfate compounds
Rubidium in traces, forms chlorides/sulfates n.a.
Cesium in traces, forms chlorides/sulfates n.a.
Group II
Beryllium in traces no measurable effects
Magnesium improves burnability, goes into aluminate and cause magnesium expansion,
ferrite phases, forms periclase soluble salts are corrosive
Strontium small amount favors alite formation, large amounts lime expansion, low hydraulicity,
cause belite formation, also promotes free- Iow strength
lime formation
Barium reduces melt temperature, replaces Ca in all clinker activates hydraulicity, improves
phases except ferrite, also improves clinker strength
mineralogy
Group Ill
Boron decomposes C~S, stabilizes pCpS, promotes free- unpredictable hydration and
lime formation setting properties
Gallium in traces, volatile n.a,
Iridium in traces, volatile n.a.
Thallium in traces, highly volatile, goes into CKD, also forms n.a.
internal cycle;
Group IV
Carbon COZ in emissions n.a.
Germanium replaces Si in C~S to form tricalcium germanate C,G is hydraulic but C2G is not,
(C,G) that reduces to dicalcium germanate small amounts ineffective
(C2G) and free-lime
Tin stays in clinker, no effect if in traces no measurable effects
Lead volatile, goes to CKD but some stays in clinker, retards of hydration, but final
effects at higher levels uncertain strength reasonable
n.a.= information not available
35
APPENDIX. A Summary of Possible Effects of Minor Elements on the Formation of Clinker and Properties
of the Resulting Cements (Continued)
Trace Elements Affects on Clinker Formation Affects on Cement Properties
Group V
Nitrogen NOXemission n.a.
Phosphorus decomposes C~S to C$ and free lime, reduces slows hardening
negative effects of alkalies
Arsenic volatile, goes to CKD, also incorporates in clinker retards hydration
as low-volatile calcium arsenates, reduces C~S
formation
Antimony incorporates in clinker as calcium antimonates n.a.
under oxidizing conditions and at high
temperatures
Bismuth n.a. n.a.
Group VI
Oxygen enhances incorporation of metals with high n.a.
oxidation states, modifies phases, formation,
results in darker clinkers (reducing condition
gives lighter clinkers)
Sulfur volatile, promotes formation of complex alkali aids set control, causes sulfate
sulfates, sulfur cycle, causes plug formation, expansion
gives SOZ emissions
Selenium in traces, volatile, goes to CKD or emissions, may n.a.
also form unstable tellurates
Tellurium in traces, volatile, goes to CKD or emissions, may n.a.
also form unstable tellurates
Group W
Fluorine lowers melt temperature, enhances C,S formation no adverse effect on hydration,
and alkali fluorides, excess levels cause and strength
operational problems
Chlorine volatile, promotes chlorine cycle, causes ring accelerator, corrosive to steel
formation, preheater build-up, can form enforcements in concrete
chlorine alinites
Bromine volatile, may form bromine alinites accelerator for C~S pastes
lodine in traces, volatile accelerator for C.$5 pastes
Group Vlll
Helium no known effect no known effect
Neon no known effect no known effect
Argon no known effect no known effect
Krypton no known effect no known effect
Xenon no known effect no known effect
n.a.= information not available
36
APPENDIX. A Summary of Possible Effects of Minor
of the Resulting Cements (Continued)
Trace Elements
Transition
Elements
Yttrium
Titanium
Zirconium
Vanadium
Niobium
Chromium
Molybdenum
Tungsten
Manganese
Cobalt
Nickel
Copper
Silver
Zinc
Cadmium
Mercury
Lanthanides
Scandium
Lanthanum
Cesium
Neodymium
Uranium
Gadolinium
].a.= information not a
Elements on the Formation of Clinker and Properties
Affects on Clinker Formation
substitutes Ca in C~S and C2S
goes in ferrite, decomposes alite to belite, reduces
melt temperature, gives buff-color cement
modifies alite and belite crystals, imparts color
goes into alite, forms larger crystals, reduces melt
viscosity, free lime, effects grindability, lining
feeble effect
reduces melt viscosity, goes largely to belite,
improves grindability, imparts color
reduces melt viscosity, forms large roundish alite
crystals, modifies belite crystals
reduces melt viscosity, forms large roundish alite
crystals, forms type III belite crystals
goes to ferrite, can substitute both Si and Ca in C~:
imparts reddish brown to blue color
goes to ferrite, replaces Fe in ferrite, imparts color,
increases hardness
goes to ferrite, replaces Ca in alite and stabilizes
monoclinic form, volatile, reports in CKD
goes to ferrite, can adversely effect alite and belite
formation, lowers melt temperature, free-lime
in traces, no known effect
enters belite and alite, modifies alite crystals,
reduces free-lime, improves clinkering
forms volatile halides/sulfates, enters CKD, reduce:
melt temperature, improves burnability
somewhat inert, volatile, goes in stack gases
replaces Ca in C.$3 and C2S, forms solid solution
with C~S of triclinic nature
replaces Ca in CaS and C2S, forms solid solution
with C&, enhances clinkering
gets uniformly distributed in clinker, have very
little volatilization
forms solid solutions with C~S and CZS, replaces
Cain C~S and C2S
gets uniformly distributed in clinker, shows little
volatilization
forms both triclinic and monoclinic phases with
C,S, replaces Ca in C,S and C,S
able
Affects on Cement Properties
accelerator
slows initial setting, improves
strength
retarder, low early strength
increases hydraulicity, causes
sulfate expansion
little effect
increases early strength, causes
sulfate expansion
no adverse effect
no significant effect
reduces early strength
increases water demand, reduces
hydraulicity and strength
enhances strength, soluble salts
function as accelerators
soluble salts as retardes, reduces
sulfate expansion
no known effect
oxide as admixture is retarder, low
early but high late strengths
oxide as admixture is retarder
little effect
no known effect
accelerates alite hydration
accelerates alite hydration
improves alite hydration, low
leaching
n,a.
n.a.
37
Index
A
Alinite cements, 19
bromine alinite, 19,20
chlorine alinite, 19
Alkalies (sodium and potassium), 8
alkali-cycle, 9
alkali sulfates, 9, 16
in clinker, 10
in raw materials, 9
volatilization behavior, 9
Aluminum, 2, 3, 12
Antimony, 5, 7, 8, 15, 26, 35
Aphthitalite, 9, 16
Arcanite, 9, 16
Argon, 20, 26, 36
Arsenic, 5, 6, 7, 8, 13, 14, 26, 36
calcium arsenates, 14
effect of burning conditions, 14
effect on hydration, 14
volatility, 12
ASR (alkali silica reaction), 8,11
B
Barium, 5, 7, 8, 11, 12, 26, 35
effect on free lime, 12
Beryllium, 5, 6, 7, 8, 11, 26, 35
BIF (boiler and industrial furnace), 6, 8,
15
Bismuth, 5, 13, 15, 26, 36
Blast furnace slag (B,F. slag), 3, 4, 9,
14,21,23
Boron, 5, 12, 26, 35
Berates, 12
as mineralizers, 12
Bromine, 5, 6, 7, 17, 19, 26, 36
bromine alinite, 19
c
Cadmium, 4, 5,6,7, 8,20,25, 26, 37
effect on cement setting/strength,
25
effect on melt viscosity, 21
in CKD, 25
volatility, 12, 25
Calcium, 2, 3, 11
Carbon, 2, 13,26, 35
Cement kiln dust (CKD), 9, 13, 19, 22,
23, 24, 25
Cerium (Cc), 4, 26
effect on alite hydration, 26
Chlorine, 2, 5, 6, 7, 17, 19,25, 26, 35
chlorine alinite, 19
chlorine build-ups, 18
chlorine-cycle, 19
sources, 19
Chromium, 4, 5, 6, 7,8, 15,20,21,22,
23, 26, 37
burning conditions vs oxidation
states of chromium, 22
chromate, 22
effect on hydration, 22, 23
in clinker 20, 22, 23, 26
stabilizer for l?-C2S, 22
trivalent chromium (Cr+3) and
hexavalent chromium (cr+13),22
Cobalt, 5, 19, 20,23, 26, 36
in clinker, 20
Copper, 1, 5, 20, 21,24,26, 37
as C$3 accelerator, 24
CUO vs CU20 on alite stabilization,
24
in clinker, 20
D
DRE (destructions and removal
efficiency), 2
E
Erbium (Er), 25
F
Fluorine, 5, 6, 7, 14, 17, 18, 26, 36
Fluorides, 17, 18
as mineralizers/fluxes, 17, 18
C& accelerator, 18
emissions, 18
Fly ash, source of minor elements,
3,4,5,9,11,12,13,14,17,
19, 22,22,24
G
Gadolinium (Gal), 25,26
Gallium, 5, 12, 26, 35
Germanium, 5, 13,26, 35
calcium germanate, 13
calcium germanate hydrate, 13
Group 1,5, 7, 35
Group 11,5, 11, 35
Group Ill, 5, 12, 35
Group IV, 5, 13, 35
Group V, 5, 13, 36
Group Vl, 5, 15, 36
Group Vll, 5, 17, 36
Group Vlll, 20,36
H
Helium, 20,26, 36
Hydrogen, 7, 35
I
Iridium, 5, 12,26, 35
lodine, 5, 6, 7, 17,20,26, 36
K
Krypton, 20, 26, 36
L
Langbeinite (calcium Iangbeinite), 9, 16
Lanthanides (rare earlhs), 25
Lanthanum, 25, 36
clinker accelerator, 26
effect on belite hydration, 26
Lead, 4, 5,6, 7, 8, 12, 13,26, 35
effect on hydration, 13,
as retarder, 13
in CKD, 13
volatility, 12
Lesser elements, 3
Lithium, 5, 7, 8,26, 35
ASR reducer, 8
mineralizer, 8
Lubricating oils (waste oils), 1, 5, 13, 23
Lutetium (Lu), 26
M
Magnesium, 3,4, 5, 11,26, 35
Major Elements, 2
Manganese 5,20,21,23,26, 37
alite formation, 23
calcium alumino manganite, 24
effect on free lime, 23, 24
substitution in C&, 20, 23
Mercury, 5, 6, 7, 8, 13,20,25, 26,37
volatility, 25
Minor elements (see also trace
elements), 1, 2, 4, 5, 6, 7, 26
as mineralizers, 10
in clinker, 8
relative volatility, 12
sources 4, 5, 6, 7
auxiliary materials (fly ash,
blast furnace slag), 6
fuel (coal, used oil), 7
raw meal (limestone, clay/
shale), 6
summary of effects, 35-37
38
Index
Molybdenum, 23,26, 37
N
Neodymium (Nd), 25,26
effect on alite hydration, 26
effect on silicate formation, 25, 26
Neon, 20,26,36
Nickel, 5,6,7, 8, 10, 12,20,21,24,26,
37
as alite stabilizer, 24,
effect on settingtstrength, 23
in CKD, 24
in clinker, 20
mineralizing effect, 10
Niobium, 20,22, 26, 37
Nitrogen, 1,2, 5, 13, 14,26,35
fuel nitrogen, 14
thermal nitrogen, 14
NO,, 2, 14
0
Oxygen, 15,26, 36
oxidation conditions, 22, 23
P
PCBS (Polychlorinated biphenyls), 2
Periodic table, 7
Phosphates, 13, 14
chloroapatite, 14
fluoroapatite, 14,20
hydroxyapatite, 14
Phosphorus, 5, 13, 14,26, 37
effect on free lime,14
Potassium (see also alkalies), 7, 8,9,
26, 35
compounds, 9
vapor pressure, 9
Producer gas, 7
R
Rare earths (Ianthanides), 25
RCRA (resources conservation and
recovery act), 4, 6, 8
Rubidium, 7, 11, 26, 35
s
Scandium {SC), 25
Selenium, 5,6,7,8, 17,26,36
in CKD, 17
selenates, 17
volatility, 17
Sewage sludge, 1,14
partial kiln feed, 1
Silicon, 2,3, 13
Silver, 6,7,8,24,26,37
Sodium (see also alkalies), 7,8,9, 10,
26,35
chlorides,9
sulfate,9
Sex,2
Stack emissions gases, 1,2, 13, 14, 17,
19,22,23,24,25,26
Strontium (Sr), 7, 11,26, 35
effect on alite/belite formation, 11
Sulfates, 9, 15, 16, 17
alkali sulfates, 9, 15, 16
effect of burning conditions, 9
effect on clinkering, 15, 16
effect on silica modules (SM), 16,17
Sulfur4, 5,6, 12, 15, 16, 17,26, 35, 36
compound formations, 15, 16
in clinker, 17
pyritic sulfur, 17
sulfur-cycle, 15
Syngenite, 16
T
Tantalum, 20,22
TCLP (toxicity characteristics leaching
procedure), 6,8
Tellurium, 5, 15, 17,26,36
Thallium, 4,5,6,7,8, 12, 13,26, 35
Thenardite, 9
Tin, 5, 13,26,35
Tires, 1,2,4, 5, 13, 19,24
tire derived fuel (TDF), 1, 2
whole tires, tire chips, 1
Titanium, 5,20, 21,26,37
in clinker, 20, 21
Trace elements (see also minor ele-
ments), 1, 2,4, 5, 6, 7, 12, 26
summary of effects, 35-37
Transition elements, 20
in clinker, 20
Tungsten, 20,23,26, 37
effect on alite morphology, 23
u
Uranium (U), 26
v
Vanadium, 5,6,7,20,21,26, 37
effect on alite/belite morphology, 22
effect on clinker grindability, 22
effect on melt viscosity, 21, 22
x
Xenon, 20,26, 36
Y
Ytterbium (Yb), 26
Yttrium, 20,26, 37
z
Zinc, 5,6, 7,20, 21,24,25,26, 37
as mineralizer, 25
retarder, 25
calcium hydroxo zincate, 25
in CKD, 25
in clinker, 20, 24, 25
in tires, 24
in used oil, 24
relative volatity, 12
Zirconium, 20, 21,26, 37
39
Metric conversion table
Following are metric conversions of the measurements used in this text.
They are based in most cases on the International System of Units (S1).
1 in
1 sq in
in
1 Sq ft
1 sq ft per gallon
1 gal
1 kip = 1000 Ibf
1 lb
1 lb per cubic yard
1 psf
1 psi
No. 4 sieve
No. 200 sieve
1 bag of cement (U. S.)
1 bag of cement (Canadian)
1 bag per cubic yard (U. S.)
deg. C
. 25.40 mm
= 645.16 mm2
= 0.3048 m
= 0.0929 m2
= 0.0245 m2/L
= 3.785 L
= 4.446 kN
= 0.4536 kg
= 0.5933 kg/m3
. 4.882 kg/m2
= 0.006895 MPa
. 4.75 mm
= 75 mm
= 94 lb = 42.6 kg
=881b =40kg
= 55.8 kg/m3
= (deg. F - 32)/1.8
40
PALABRAS CLAVE: manufacture, elementos menores, cemento portland, materia prima, elementos de traza
SINOPSIS: En esta revisi6n se reportan 10S efectos de la mayor parte de 10S elementos menores y de traza en la
manufacture y comportamiento de cemento portland. Se ha puesto 6nfasis tanto a 10S elementos que forman parte
de materials naturales tambi6n como a aquellos elementos que resultan del desperdicio en la manufacture de
cemento. Los elementos para 10S cuales se ha obtenido informaci6n detallada, se han tratado de acuerdo con la
tabla peri6dica de elementos. Cuando necesario, las partes vokitiles de 10S elementos tarnbidn se han considerado.
Los elementos que se han revisado incluyen hidr6geno, sodio, potasio, Iitio, rubidio, cesio, bario, berilio, strodio,
magnesio, boro, galio, indio, talio, carbono, germanio, estafio, plomo, nitr6geno, f6sforo, arsdnico, antimonio,
bismuto, oxigeno, azufre, selenio, telurio, fluoro, cloro, bromo, iodo, helio, neon, argon, kripton, xenon, itrio,
titanio, zirconio, vanadio, niobio, tantalum, cromo, molibdeno, tugsteno, magnaneso, cobalto, niquel, cobre, plata,
zinc, cadmio, mercurio, y 10S lanttiidos.
REFERENCIA: Bhatty, J. I., Role of Minor Elements in Cement Manufacture and Use, Research and Development
Bulletin RD109T, Portland Cement Association [Papel de Ios Elementos Menores en la Manufacture y Uso del
Cemento, Boletin de Investigaci6n y Desarrollo RD109T, Asociaci6n de Cemento Portland], Skokie, Illinois,
U.S.A., 1995.
STICH WORTER: Herstellung, Nebenelemente, Portlandzement, Rohrnaterialien, Spurenelemente
AUSZUG: In dieser ~ersicht wird uber die Wirkung von fast allen stabilen Nebenelementen und Spuren-
elementen auf die Herstellung und Eigenschaften von Portlandzement berichtet. Besondere Berucksichtigung
gilt den Elementen, die in natiirlichen Mineralien sowie in Abfallen vorkommen, die bei der Herstellung von
Portlandzement Verwendung finden. Die Elemente, wofur detallierte Informationen gesammelt wurden, werden
nach ihrer Rangordnung im chemischen Periodensystem besprochen. Wo notig, wird such die Volatilit&en der
Elemente diskutiert. Zu den untersuchten Elementen gehoren Wasserstoff, Natrium, Kalium, Lithium, Rubidium,
Casium, Barium, Beryllium, Strontium, Magnesium, Bor, Gallium, Iridium, Thallium, Kohlenstoff, Germanium,
Zim, Blei, Stickstoff, Phosphor, Arsen, Antimon, Wismut, Sauerstoff, Schwefel, Selen, Tellur, Fluor, Chlor, Brom,
Jod, Helium, Neon, Argon, Krypton, Xenon, Yttrium, Titan, Zirkonium, Vanadium, Niob, Tantalum, Chrom,
Molybdiin, Wolfram, Mangan, Kobalt, Nickel, Kupfer, Silber, Zink, Cadmium, Quecksilber und die Lanthanide.
REFERENZ: Bhatty, J. I., Role of Minor Elements in Cement Manufacture and Use, Research and Development
Bulletin RD109T, Portland Cement Association [Einfluf3 der Nebenelemente bei der Zementherstellung und -
anwendung, Forschungs-und Entwicklungsbulletin RD109T, Portlandzementverband], Skokie, Illinois, U.S.A,
1995.
PCA R&D Serial No. 1990
This publication is intended SOLELY for use by PROFESSIONAL
PERSONNEL who are competent to evaluate the significance and
limitations of the information provided herein, and who will accept
total responsibility for the application of this information. The
Portland Cement Association DISCLAIMS any and all
RESPONSIBILITY and LIABILITY for the accuracy of and the
application of the information contained in this publication to the
full extent permitted by law.
Portland Cement Association 5420 Old OrchardRoad, Skokie, Illinois 60077-1083, (847) 966-6200, Fax (847) 966-9782
m
An organization of cement manufacturers to improve and extend the uses
II
of portland cement and concrete through market development, engineer-
ing, research, education and public affairs work.
Printed in U.S.A.
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