You are on page 1of 5

Modification of the Bogue calculation

H. F. W. Taylor*
UNIVERSITY OF ABERDEEN: DEPARTMENT OF CHEMISTRY

The Bogue calculation gives low results for alite and It has often been stated that the Bogue calculation
inaccurate ones for the other phases in Portland cement gives inaccurate results because equilibrium is not
clinkers, largely because the compositions of the phases maintained during cooling of the clinker, but this is
differ markedly from those of the unsubstituted com- only partly correct. Even if equilibrium was main-
pounds which it assumes to be present. For a wide range tained, all four major phases would contain sub-
of rapidly cooled clinkers produced in modern plants, stituent ions. The basic reason for the inaccuracy is
the compositions of the phases are sufficiently constant that the phases do not have the compositions that are
to justify ~ use, with minor modifications, of average assumed; the absence of equilibrium during cooling
values based on X-ray microanalyses, instead of those of merely modifies their compositions.
the unsubstituted compounds. On this basis, a procedure
is described which, like the Bogue calculation, is essen-
Theoretical requirements for a correct
tially a solution offour linear simultaneous equations. A
method for estimating the contents of sulphate com- calculation
ponents from the bulk composition is also described. For a calculation of phase composition from bulk
These procedures together yield a mass balance table analysis to give correct results, the following data
showing how the oxide components, both major and would be required:
minor, are distributed among the major and minor
(a) A bulk chemical analysis free from errors. This
phases. Limitations, modifications, extensions to special
types of Portland cement and a test of the procedure for implicitly assumes that any necessary corrections
the major phases are described. (e.g. to an AI 2 0 3 content determined by the classi-
cal wet method) are applied.
(b) Data, similarly free from errors, concerning the
Introduction amounts of any of the four major components
The Bogue calculation was a major advance in that are not present in any of the four major
cement chemistry, but its limitations are becoming phases. This is a routine feature of the Bogue
increasingly apparent, and there is wide agreement calculation in the case of free lime, but, even for a
today that it tends strongly to underestimate alite clinker, it is also necessary to know, for example,
contents. In a study of 39 clinkers, Kristmann l found how much CaO, if any, is present in sulphate
that the content of alite found by reflected light micro- phases and, if modern analytical methods are
scopy was always higher than that given by the Bogue used, the contents of oxide components (normally
calculation, the mean discrepancy being 8%. Odler assumed to be Si0 2 and A1 20 3 ) present in the
et al. 2 found that alite contents from either microscopy insoluble residue.-
(c) The compositions of each of the four major
or quantitative X-ray diffraction analysis (QXDA)
were always higher than those from the Bogue calcu- phases. If any is variable, a weighted mean must
lation, and Gutteridge 3 reached a similar conclusion be used. This situation arises from such causes as
using QXDA. The results of a co-operative study on zoning in alite or ferrite, or the presence of both
six clinkers in a number of laboratories, reported by cubic and orthorhombic aluminate. Belite presents
Aldridge,4 showed alite contents from microscopy to a special problem, because of the presence of other
be higher than those given by the Bogue calculation in phases exsolved between the lamellae. s In the
the great majority of cases. present state of knowledge, it is probably necessary
to use an average value, including the ex solved
material.

"Emeritus Professor, Department of Chemistry, University of In principle, the Bogue calculation is a solution of four
Aberdeen, Meston Walk, Old Aberdeen AB9 2UE, UK. linear sim1,lltaneous equations for four unknowns. For

Advances in Cement Research, 1989, 2, No.6, Apr., 73-77 73

Downloaded by [ UNIV OF TORONTO ENGINEERING LIB] on [31/07/16]. Copyright © ICE Publishing, all rights reserved.
Taylor

Table 1. Typical compositions of phases in Portland cement production clinkers*

Na,O MgO AI,03 SiO, P,O, SO, K,O CaO TiO, Mn,O, FC,03

Alitet 0·1 1·1 1·0 25·2 0·2 0·0 0·1 71·6 0·0 0·0 0·7
Belitet 0·1 0·5 2·1 31·5 0·2 0·1 0·9 63·5 0·2 0·0 0·9
Aluminate§ 1·0 1-4 31·3 3·7 0·0 0·0 0·7 56·6 0·2 0·0 5·1
Ferritell 0·1 3·0 21·9 3·6 0·0 0·0 0·2 47·5 1·6 0·7 21·4
Aluminate~ 0·6 1·2 28·9 4·3 0·0 0·0 4·0 53·9 0·5 0·0 6·6
Aluminate" 0-4 1·0 33·8 4·6 0·0 0·0 0·5 58·1 0·6 0·0 1·0
Ferritett 0·1 2·8 15·2 3·5 0·0 0·0 0·2 46·0 1·7 0·7 29·8

" Weight percentages.


t For a clinker with 1·65% MgO and 2·8% Fe,O,. More generally, % MgO = 0·667 x % MgO in clinker, but not> 2·0%; % Fe,03 =
o· 25 x % Fe,03 in clinker, but not > \·1 %; % CaO = 71·6 ~ \-4 x (% MgO in alite ~ 1·1). The composition should be normalized
to a total of 100%.
t S03 higher in clinkers of high S03/(Na,O + K,O) ratio.
§ Cubic polymorph, normal in clinkers of low alkali content and AI,O,/Fe,03 weight ratio ;s 3.
II Normal composition in clinkers with AI,03/Fe,03 weight ratio;::: \·5.
"I Orthorhombic or pseudo-tetragonal polymorphs, found in clinkers high in alkalis; Na/K ratio varies with that of the clinker.
""Tentative composition for high Al component in white cement clinkers.
ttTentative composition for high Fe component in sulphate resisting clinkers.

each of the four major oxide components, there is an an AR of 1·5~3·0, are reasonably well established, and
equation of the form can possibly be used without serious error over a
wider range of AR between about I and 4, but the
(I)
others are based on very limited data. For alite, the
where the summation is over the four major phases, aij composition is assumed to be related to the MgO and
is the weight fraction of oxide component i in phase j, Fe 20 3 contents of the clinker.6.8.10.16 Other such
Xj is the weight percentage of phase j in the clinker and correlations have been reported, but were not used
hi is the percentage of oxide component i in the clinker, because they were considered either too uncertain or
after deducting any contributions from phases other insufficiently important.
than the four major ones. [n these terms, the errors in
the Bogue calculation arise mainly because incorrect
Example of a calculation
values are used for the coefficients aij, and sometimes
also from failure to apply all the necessary corrections The calculation in the form described below can be
to the right-hand sides hi' If the coefficients were free carried out without using any data other than the bulk
from error, and all the other conditions noted above chemical analysis (as defined above) and the content
were satisfied, this procedure would necessarily give of free lime. Its limitations, and modifications that are
correct results. possible if additional data are available, are described
later. The calculation, which is illustrated by an
example, also yields a mass balance table showing the
Practical solution distribution of oxide components, both major and
The compositions of the individual phases are minor, among phases.
best determined by X-ray microanalysis. [t is plainly
impracticable to use this as a routine method for Input data
determining quantitative phase composition. How- Consider the case of a clinker having the bulk
ever, for modern, rapidly cooled clinkers with an chemical composition shown in Table 2, determined
AR * between about 1·5 and 3·0, the variations in using X-ray fluorescence.
the compositions of the phases are small compared
with the differences between their average values and Corrections to the input data
the compositions of the pure compounds. Following From the CaO content, deduct free lime and any
Yamaguchi and Takagi6 and Harrison et al.,7 average CaO equivalent to CO 2 , In the absence of data,
values may therefore be used. This will introduce some assume 0·3% of insoluble residue and that this is
errors, but these are almost certain to be smaller than composed of Si0 2 , 67%, and A1 2 0 3 , 33%. The quan-
those inherent in the Bogue calculation. tity of CaO present in sulphate phases can be esti-
Table I includes typical compositions of the four mated from the bulk analysis by a method described
major phases, based on a critical examination of data later. Except with clinkers high in S03 and low in
from a number of sources.6-1~ The first four com- alkalis, this correction is probably rarely significant
positions, which apply to a majority of clinkers with from the standpoint of calculating the quantitative
phase composition, but it is needed if a mass balance
*AR (alumina ratio) is the weight ratio of AI,03 to Fe,03' table is to be obtained, and is easily made. In the

74 Advances in Cement Research, 1989, 2, No.6

Downloaded by [ UNIV OF TORONTO ENGINEERING LIB] on [31/07/16]. Copyright © ICE Publishing, all rights reserved.
Modification of the Bogue calculation

Table 2_ Bulk chemical composition of the clinker used as an example*

Oxides Na 2 0 MgO AI 2 0 J Si0 2 P 2 O, SOl K2 0 CaO Ti0 2 Mn,O, Fe,Ol Loss Total

Percentage
by weight 0-21 2-0 5-4 22-0 0-20 0-46 0-51 65-7 0-17 0-09 2-8 0-5 100-0

'Free lime 0-9%; CO 2 nil.

present case, it gives a value of 0-03%, equivalent to X2 -3-724144b l + 1O-29531b 2 + 5-343733b 3


0-07% of CaS04_ The same calculation also gives
estimated contents of K 2 S04 (0-69%) and Na 2 S04 + 1-065700b4 = 14-4 (7)
(0-18%)_ After applying these corrections, the con-
tents of A1 20 3, Si0 2 and CaO are 5-3%, 21-8% and X3 0-117872b l - 0-369269b 2 + 3-669829b 3
64-8%, respectively_
Correct the alite composition in accordance with - 3-955085b4 = 8-0 (8)
the MgO content of the clinker, as shown in the note
to Table 1. This gives contents of 1-3% MgO, 71-3% X4 - 0-023 283b[ - 0-055861 b2 - 0-867256b,
CaO and 0-7% Fe203 in the alite_
For a cement, if the content and composition of the + 5-621492h 4 = 8-4 (9)
gypsum are known, appropriate additional corrections The Bogue calculation, if the same corrections are
may readily be made_ If they are not, it is necessary to applied to the input data, gives C 3 S, 58-6%; C 2 S,
assume that some arbitrary quantity of S03, such as 18-3%; C 3A, 9-3%; C 4 AF, 8-5%_ Equations (6)-(9)
0-5%, is present in the clinker and to deduct a quantity
may be used to calculate the percentages of the four
of CaO equivalent to the remainder. For a cement major phases in any clinker or cement for which those
containing a calcite filler, no special difficulty arises phases have approximately the same compositions as
provided the calcite is sufficiently pure and the CO 2
in the present example_ Variations in the MgO content
content of the cement is known, but with other fillers, of the clinker have little effect on the calculated con-
serious problems may arise in any attempt to calculate tents of aluminate and ferrite, but a greater effect on
quantitative phase composition from bulk analysis_
those of the alite and belite, because they imply vari-
Solution of the equations ations in the CaO content of the alite_ For a clinker
with the same contents of the major oxide components
Continuing with the example given, the equations as in the above example but with 1-0% of MgO, the
to be solved are calculated content of alite is 63-6% and that of belite
0-713x l + 0-635x2 + 0-566x 3 + 0-475x4 is 16-5%_ For one with 3-0% or more of MgO, the
corresponding values are 68-9% and 12-0%_
= b l = 64-8 (2)
Estimation of sulphate components
0-252xl + 0-315x2 + 0-037x3 + 0-036x4
The following empirical procedure is based on the
= b 2 = 21-8 (3) experimental data of Pollitt and Brown,2o with which
it gives results generally in good agreement. The
O-OlOxl + 0-021x2 + 0-313x 3 + 0-219x4 following symbols are used: K = total K 20; N =
total Na 20, S = total SO,; K s ' N" C" SS = K 20,
= b 3 = 5-3 (4) Na 2 0, CaO and SO, present as sulphates_ All quan-
tities are in moles per 100 g of clinker.
0-007xl + 0-009X2 + 0-051x3 + 0-214x4
Step 1_ Calculate the ratios R = S/(K + N) and
= b4 = 2-8 (5) k = KIN.

These equations are readily solved on a microcom- Step 2_ Calculate Ss as follows


puter using any standard method for matrix inversion, if R :( 0-8, Ss = S
such as the Gauss-Jordan method_ 19 The result in the if 0-8 < R :( 2-0, Ss = [1-0-0-25(R-0-8)]S
present case is contained in equations (6)-(9), where if R > 2-0, Ss = 0-7S_
X I -X4 are the respective percentages of alite, belite, Step 3_ Calculate Ks and Ns as follows
aluminate and ferrite in the clinker if R :( 0-8 and k < 3-67, Ks = 1-12RK and Ns
XI = 4-641200b l - 8-838681b 2 - 7-094597b 3 0-56RN
if R > 0-8 and k < 3-67, Ks = 0-9K and Ns
- 1-554488b4 = 66-1 (6) 0-45N

Advances in Cement Research, 1989, 2, No_ 6 75

Downloaded by [ UNIV OF TORONTO ENGINEERING LIB] on [31/07/16]. Copyright © ICE Publishing, all rights reserved.
Taylor

Table 3. Mass balance table for the clinker used as an example*

Na,O MgO AI,O, SiO, P,Os SO) K,O CaO TiO, Mn,03 Fe,O) Loss Total

Alite 0·1 0·9 0·7 16·8 0·1 0·0 0·1 47-4 0·0 0·0 0'5 0·0 66-4
Belite 0·0 0·1 0·3 4·5 0·0 0·0 0·1 9·2 0·0 0·0 0·1 0·0 IH
Aluminate 0·1 0·1 2·5 0·3 0·0 0·0 0·1 4·5 0·0 0·0 0-4 0·0 8·0
Ferrite 0·0 0·3 1·9 0·3 0·0 0·0 0·0 4·0 0·1 0·1 1·8 0·0 8·5
Free lime 0·0 0·0 0·0 0·0 0·0 0·0 0·0 0·9 0·0 0·0 0·0 0·0 0·9
Periclase 0·0 0·7 0·0 0·0 0·0 0·0 0·0 0·0 0·0 0·0 0·0 0·0 0·7
K, S04 0·0 0·0 0·0 0·0 0·0 0·3 0-4 0·0 0·0 0·0 0·0 0·0 0·7
Na,SO. 0·1 0·0 0·0 0·0 0·0 0·1 0·0 0·0 0·0 0·0 0·0 0·0 0·2
CaSO. 0·0 0·0 0·0 0·0 0·0 0'0 0·0 0·0 0·0 0·0 0·0 0·0 0·1
Other 0·0 0'0 0·1 0·2 0·0 0'0 -0'1 0·0 0·0 0·0 0'0 0·5 0·6

Total 0·2 2'0 5-4 22·1 0·2 0'5 0·5 66·0 0·2 0·1 2·8 0·5 100·5

*Percentages on the ignited weight. Discrepancies in totals arise from rounding. 'Other' phases (calculated by difference) comprise insoluble
residue, loss and residuals arising from errors in assumed compositions.

if k ~ 3'67, proceed as above but multiply each sulphate phases are given as single salt components,
result by the factor (K + N)/(1'12K + 0'56N); but in fact often occur as the double sulphates,
this ensures that (Ns + Ks) ~ Ss-the critical value aphthitalite, calcium langbeinite or, in cements,
of 3·67 for k is equal to (1-0' 56)/(1'12-1). syngenite.
Step 4. Calculate Cs = Ss - Ks - N,.
Limitations and modifications
If the contents of water soluble Na10 and K10 are
known, it is only necessary to calculate Ks and Ns from Application of the main procedure described above
them, to calculate R, and to carry out steps 2 and 4. to a clinker having an AR below about 1·0 will give a
From K" Ns and C" the weight percentages of the negative content of aluminate. Such clinkers indeed
corresponding sulphates are easily obtained. contain little or no aluminate, and the ferrite in them
is higher in iron than for clinkers of higher AR. The
aluminate may be replaced in the calculation by the
Calculation of a mass balance table
high Fe ferrite composition given in Table I. The
Using the weight percentages of the major phases calculation will then give positive values for all four
and sulphate components, and the compositions constituents, together with a predicted ferrite com-
assumed for the phases, a mass balance table is readily position represented by the weighted mean of the
calculated (Table 3). It is assumed that any MgO not two that are used. A similar situation exists with
present in the major phases occurs as periclase. The clinkers of AR higher than about 4, when the high Al

Table 4. Comparison of observed and calculated phase compositions*

Phase Character of Number of cases calculated by


calculated value
Bogue Modified Bogue
method method

Alite High a 6
Reasonable 8 25
Low 31 8
Belite High 21 12
Reasonable 15 20
Low 3 7
Aluminate High 26 (13) 16 (6)
Reasonable \3 (26) 21 (30)
Low 0 (0) 2 (3)
Ferrite High 2 (0) 8 (I)
Reasonable 28 (21) 29 (19)
Low 9 (18) 2 (19)

*Experimental data from reference I, for 39 clinkers. Alite and belite were determined by light
microscopy, and aluminate and ferrite by QXDA, with values using the results of a combined
microscopy-QXDA method given in parentheses. 'High' and 'low' denote differences between
calculated and observed values exceeding 5% absolute for alite and belite, or 2·5% for
aluminate and ferrite, 'reasonable' denoting agreement within these limits.

76 Advances in Cement Research, 1989,2, No.6

Downloaded by [ UNIV OF TORONTO ENGINEERING LIB] on [31/07/16]. Copyright © ICE Publishing, all rights reserved.
Modification of the Bogue calculation

aluminate composition may be used in place of ferrite. 5. CHAN C.-J. et al. Analytical electron microscopic studies of
The validity of the method for white cements that have doped dicalcium silicates. J. Am. Cerarn. Soc., 1988, 71,
713-719.
been quenched in water is, however, uncertain, as
6. YAMAGUCHI G. and TAKAGI S. The analysis of Portland cement
these can contain glass. 17 clinker. Proc. 5th Int. Syrnp. Chern. Cern., Tokyo, 1968,
Many clinkers high in alkali contain orthorhombic Vol. I, 181-225.
or pseudo-tetragonal aluminate in place of, or as well 7. HARRISSON A. M. et al. Electron-optical analyses of the phases

as, the cubic variety. Where this situation is known or in a Portland cement clinker, with some observations on the
calculations of quantitative phase composition. Cern. Coner.
suspected, more accurate results can probably be
Res., 1985, 15, 775-780.
obtained by replacing the composition of the cubic 8. TERRIER P. Contribution of analysis by means of an electron
aluminate in the calculation by that given in Table I microprobe to the cement chemistry. Proc. 5th Int. Syrnp.
for orthorhombic aluminate, or by a weighted mean of Chern. Cern., Tokyo, 1968, Vol. 2, 278-287.
the two. The orthorhombic aluminate composition 9. REGOURD M. and GUINIER A. The crystal chemistry of the
constituents of Portland cement clinker. Proc. 6th Int. Congr.
given in Table I is appropriate to a clinker of high
Chern. Cern., Moscoii', 1974, Vol. I, 25-51. (Russian with
KINa ratio. For one in which this ratio is lower, a English preprint.)
composition higher in Na and lower in K would prob- 10, KRISTMANN M. Portland cement clinker: mineralogical and
ably be more appropriate. chemical investigations. Part II. Electron microprobe analysis.
The applicability of any of the ferrite and aluminate Cern. Concr. Res., 1978,8,93-102.
II. GHOSE A. and BARNES P. Electron microprobe analysis of
compositions in Table I to slowly cooled clinkers is
Portland cement clinkers. Cern. Coner. Res., 1979,9, 747-755.
doubtful. X-ray diffraction evidence shows that the 12. GHOSE A. Electron-microscope investigations on Portland
ferrite composition depends on cooling rate,21.22 and cement and its hydration characteristics. University of
this is probably true also of the aluminate, but there London, PhD thesis, 1980, 124-135.
are no reliable data on the relationship between cool- 13. BOiKOVA A. I. et al. On the composition of cement minerals.
Proc. 7th Int. Congr. Chern. Cern., Paris, 1980, Vol. 4, 183-
ing rate and composition for these phases. Major
185.
modifications would also be needed for clinkers made 14. SARKAR S. L. and ROY D. M. Quantitative phase delineation of
under reducing conditions. four American clinkers by SEM-EDS. Proc. 6th Int. Con!
Cern. Microsc., Alhuquerque, 1984, 37-46.
15. UCHIKAWA H. et al. Influence of character of clinker on the

Test of the calculation for major phases early hydration process and rheological property of cement
paste. Cern. Coner. Res., 1985,15,561-572.
Table 4 shows the results of a test using Kristmann's 16. BOiKOVA A. I. Chemical composition of raw materials as the

data. I Agreement is reasonable for all four phases, main factor responsible for the composition, structure and
properties of clinker phases. Proc. 8th Int. Congr. Chern.
with no significant bias in either direction for alite or
Cern., Rio de Janeiro, 1986, Vol. I, 19-33.
belite. The method possibly tends to give high results 17. BOiKOVA A. I. et al. Chemical composition of phases and
for aluminate; one cannot tell whether bias exists with phase relations in unbleached and bleached clinkers. Proc. 8th
ferrite, owing to inadequate agreement between the Int. Congr. Chern. Cern., Rio de Janeiro, 1986, Vol. 2, 243-
results of the two experimental methods used. Similar 248.
18. HARRISSON A. M. et al. An examination of some pure and
levels of agreement have been obtained in tests on
composite Portland cement pastes using scanning electron
a wide range of cements, using experimental data microscopy with X-ray analytical capability. Proc. 8th In!.
obtained using QXDA 3 and kindly supplied by Dr Congr. Chern. Cern., Rio de Janeiro, 1986, Vol. 4, 170-175.
W. A. Gutteridge of the British Cement Association. 19. NORRIS A. C. Computational Chemistry. John Wiley, Chiches-
ter, 1981.
20. POLLITT H. W. W. and BROWN A. W. The distribution of
alkalis in Portland cement clinker. Proc. 5th Int. Syrnp. Chern.
Cern" Tokyo, 1968, Vol. 1,322-333.
References 21. MIY AZA WA K. and TOMITA K. On the color change of Portland
I. KRISTMANN M. Portland cement clinker: mineralogical and cement. Proc. 5th Int. Syrnp. Chern. Cern., Tokyo, 1968,
chemical investigations. Part I. Microscopy, X-ray fluor- Vol. 1,252-261.
escence and X-ray diffraction. Cern. Concr. Res., 1977, 7, 22. aNa M. and NAGASHIMA N. Effect of cooling conditions of
649-658. clinker on strength of cement. Proc. 6th Int. Congr. Chern.
2. ODLER I. et al. Mineralogical and oxidic composition of indus- Cern" Moscow, 1974, Vol. I, 170-173. (Russian with English
trial Portland cement clinkers. Zernent-Kalk-Gips, 1981,34, preprint.)
445-449.
3. GUTTERIDGE W. A. Quantitative X-ray powder diffraction in
the study of some cementive materials. Proc. Brit. Cerarn.
Soc., 1984, No. 35, 11-23.
4. ALDRIDGE L. P. Accuracy and precision of phase analysis in
Portland cement by Bogue, microscopic and X-ray diffraction Discussion contributions on this Paper should reach the Editor by 2
methods. Cern. Concr. Res., 1982, 12, 381-398. January 1990,

Advances in Cement Research, 1989,2, No.6 77

Downloaded by [ UNIV OF TORONTO ENGINEERING LIB] on [31/07/16]. Copyright © ICE Publishing, all rights reserved.

You might also like