Report of lnvestigations 8732

lnfluence of Selected Additives

and CaO:Si0
2
Ratio
on High-Temperature Strength
of MgO Refractories
By Nancy S. Raymon
UNITED STATES DEPARTMENT OF INTERIOR
James G. Watt, Secretary
BUREAU OF MINES
Robert C. Horton, Director

Research at the Tuscaloosa Research Center is carried out under a of agreement between the
Bureau of Mines, U.S. of lhe lnterior, and the of Alabama.
publ cation has been cataloged as follows :
Raymon, ( <tncy '.)
o f c: aO: i02
o f
o f I Uni red of
r i or, 1\ur eau o f Mines ; 8732)
a l rc fe re n cs.
of 110. : 28. 23:87 .3
Magnc 3. 4.
a l s ll. Serie s: H.cport of
Bure>t u o f Mi11 cs) ; 8732.
U43 t8. 26] 622 72\ R2-H00 2 4
CONTENTS
Abstract....................................................................... 1
Introduction................................................................... 2
Tes t procedures. . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Sample preparation.................... . . . . . . . . . . . . . . . . . . . . . . 2
Modulus of rupture tests 3
Factorially designed experiment........................................... 3
Results and discussion......................................................... 4
Initial screening tests 4
Factorially designed experiment........................................... 5
Conclus ions. . . . . . . 8
TABLES
1. Source, location, and chemical composition of periclase materials used in
2.
3.
4.
5.
6.
initial screening tests
Factorial program variables
Chemical composition of periclase materials used in factorially designed
3
3
experiments.............................................................. 4
Effect of oxide additions on hot MOR values of three commercial periclase
grains at 1,550 C
Effect of oxide additions on hot MOR values of 11 commercial periclase
grains at 1,550 C
Analysis of variance data reported as F-ratios
4
6
7
INFLUENCE OF SELECTED AND CaO:Si0
2
HIGH-TEMPERATURE
STRENGTH OF MgO REFRACTORIES
By Noncy S. Roymon 1
ABSTRACT
The Bureau of Mines the effect of controlled additions of
selected metal oxides, as well as the adjustment of the calcia-to-silica
ratio on the high-temperature strength of refractory-grade periclase.
Increases in the hot flexural strength of some periclase materials in
the range of threefold to fourfold were obtained with additions of Zr0
2
and by adjustment of the CaO:Si0
2
ratio to the 2.5 to 3.0 Re-
sults show that for each periclase refractory raw material, there exists
a combination of of Zr0
2
addition and an adjustment to the
CaO:Si0
2
ratio that optimizes the hot flexural strength of each of
these materials. Data also indicate that the hot strengths can
be attributed to the high-temperature secondary phases formed between
the different of periclase impurities and the result-
ing in intergranular high-temperature bond strength.
1Metallurgist, formerly with Research Center, Bureau of Mines,
loosa, Ala.; now resides in Blacksburg, va.
2
INTRODUCTION
The refractories industry has an impact
on all steelmaking processes, as well as
on the production of aluminum, glass,
copper, cement, and other commodities.
With the emphasis today on the impact of
engineering materials on increasing pro-
a need exists to the
high-temperature performance of refrac-
tory lining materials. The refractory
properties of domestic raw materials and
products must be optimized to meet im-
performance demands that re-
sulted from new processing
in hydrometallurgical and pyrometallurgi-
cal operations. It is especially im-
portant to identify substitutes for the
imported ore that is used in the
production of basic refractories.
The refractory industry uses 16 pct of
the total chromite consumed in the United
States.2 The steel industry is by far
the largest single consumer of refrac-
tories, utilizing 60 pct of the
total tonnage produced annually.3 The
steelmaking furnaces predominantly use
basic linings produced from MgO in the
of dead-burned grain and chromite.
Although there are adequate resources
of MgO in the world today, espe-
cially the synthetic MgO from
seawaters and brines, the United States
has no significant domestic chrome ore
resource, so that all of the chromite
consumed in the United States is
imported.4
As part of the Bureau of Mines' mission
to encourage and assist the
of the Nation's mineral resources and to
identify domestic substitute materials,
exploratory were conducted
on the effects of on the hot
strength of periclase raw materials. The
studies in this report
screening tests to identify
potentially promising metal oxide
Selection was predominantly
based on the effects of these oxides on
the sintering of MgO, as reported by Lay-
den and McQuarrie.S They hypothesized
that to certain limits additions of Fe
and Mn ions enter the MgO crystal lattice
and promote sintering, while additions
of other ions such as Ti, Zr, and Ta
aid sintering by unidentifiable mechan-
isms. The main effects and interaction
effects of metal oxides and CaO:Si0
2
(C/S) ratios on high-temperature flexural
strength of the refractory-grade 1-1g0 were
determined through factorially designed
experiments.
TEST PROCEDURES
Sample Preparation
The materials were
commercial-grade, dead-burned periclase
grains that are used in the production of
basic refractories. The samples were
either from seawater, lake and
well brines, or natural magnesite and
came from Israel, Japan, or the United
States. Partial chemical analyses in-
cluding the C/S ratios of the 11
2Peterson, c. Chromium. BuMines
Minerals Yearbook 1980, v. 1, 1981.
3oickson, u.s. Refractories
Industry--A Progress Report. Industrial
Miner., 148, 1980, 59.
materials used in the initial screening
tests are in table 1. The follow-
ing reagent-grade oxides were evaluated
as CaO, Fe
2
o
3
, MnO, Sc
2
o
3
,
Si0
2
, Ta
2
o
5
, Ti0
2
, Zro
2
These oxides
were chosen because of their high melting
points and because the cation atomic
radii are similar to that of MgO,
allowing solid solution development at
high temperatures.
4work cited in footnote 2.
SLayden, G. and c.
Effect of Minor Additions on
MgO. J. Am. Ceram. Soc.,
1959, 89-92.
McQuarrie.
Sintering of
v. 2, 2,
3
TABLE 1. - Source, location, and chemical composition of periclase materials
used in initial screening tests
Source and sample Location
number MgO
Brine:
Israel 99.2
........ United States 97.6
do 94.5
........... do 93.7
Magnesite: do .... 92.2
Seawater:
S-1 Japan 97.6
S-2 do 96.4
S-3 . ......... United States 96.2
S-4 ............ do 94.5
S-5 . ........ do 93.5
S-6 ......... ... Israel 93.3
ND Not detected.
The as-received periclase grain materi-
als were crushed, then ground to pass
through a 200-mesh sieve in a tungsten
carbide-lined vibratory mill. The dif-
ferent metallic oxides in the form of
minus 325-mesh, reagent-grade powders
were added to the ground periclase mate-
rial. After thoroughly mixing the dry
components, the admixtures were isostat-
ically pressed to 20,000 psi and subse-
quently fired to 1,600 C in an electric
furnace with molydisilicide heating ele-
ments. adjust the C/S ratio of sam-
ples, either CaO or was added. The
heating rate was 200 C/hr followed by a
a soaking time of 1 hr. The fired
materials were reground to pass 200 mesh
and pressed at 2,000 psi into 3/8- by
1- by 2-in briquets. These were fired to
1,600 C in the previously described man-
ner and cut into 1/4- by 1/4- by 2-in
samples for modulus of rupture (MOR)
testing.
Modulus of Rupture Tests
The MOR
1,550 c.
apparatus
described
tests were performed
The specially designed
and testing procedure
in a previous publication.6
at
MOR
are
6McLendon, J. s. Raymon, and
Heystek. Relationship of Mineralogical
and Chemical Composition of Refractory
Periclases to Modulus of Rupture at
1,500 to 1,600 c. BuMines RI 8386,
1979, 18
Chemical analyses, wt-pct
CaO Si0
2
Alz03 Bz03
Fe
2
o
3
C/S
0.68 0.10 0.04 ND 0.08 6.8
.63 .90 .23 0.09 .18 .7
2.40 .90 .26 .09 .19 2.7
2.80 1.90 .26 .03 .25 1.5
2.90 1. 70 .34 .02 .82 1.7
.53 .60 .26 .03 .53 .9
.90 2.10 .26 .01 .27 .4
1.10 .80 .34 .06 .45 1.4
1.10 1.90 .38 .23 .70 .4
1.20 2.70 .34 .19 .56 .4
1.20 3.30 .26 .33 .54 .4
Factorially Designed Experiment
establish the interaction effects of
oxide additions and C/S ratio adjust-
ments, single replicates of 3- by 3- by
4-factorial experiments of completely
random design were performed. Table 2
shows the levels at which each factor was
examined. Finely ground (85 pct minus
200-mesh) domestic periclase raw materi-
als were obtained for these tests.
TABLE 2. - Factorial program variables
Factor Level
1 2 3 4
HnO mole-pct 0.25 0.50 ND
Zr0
2
mole-pct 1. 2.0 ND
C/S mole ratio 5 2.0 2.5 3.0
ND Not determined.
Although the periclase materials were
similar to ones used in the initial
screening tests, the chemical composi-
tions of the new shipments of the peri-
clase materials differed from those in
the earlier studies, as shown in table 3.
The samples were renumbered to include a
subscript
Samples were prepared by blending the
85 pct minus 200-mesh periclase with ad-
ditives in a slurry of water. After dry-
ing this mixture, the material was
pressed into 1- by 2- by 1/4-in briquets
and fired for 2 hr in a gas-fired fur-
nace at a temperature of 1,700 C.
4
This higher firing temperature is more
representative of industrial practice
and eliminates the necessity of re-
grinding and refiring the samples. The
sintered slabs
1/4- by 2-in
1,550 c.
were cut into 1/4- by
bars for MOR testing at
TABLE 3. - Chemical composition of periclase materials used
in factorially designed experiments
Sample Analysis, wt-pct
MgO CaO Si0
2
Al203
Fe
2
o
3
C/S
B-2n 95.3 0.61 0.64 0.20 0.11 0.61 1.0
B-3n
95.9 2.30 .56 .13 .02 .40 4.1
M-2n 93.5 3.30 1.30 .44 .02 .64 2.5
S-3n
97.4 .89 .60 .12 .05 .46 1.5
S-4n 93.9 .96 1.80 .41 .13 .68 .5
RESULTS AND DISCUSSION
Initial Screening Tests
Table 4 presents the hot MOR data ob-
tained at 1,550 C for periclase materi-
als and with oxide addi-
tions at levels of 1/4, 1/2, 1, and 2
mole-percent. For the initial evaluation
of the effectiveness of the metal oxide
additives, these three periclase materi-
als were chosen because their MgO
contents ranged broadly from a high of
99.2 to a low of 92.2 pct as shown in
table 1.
TABLE 4. - Effect of oxide additions on hot MOR values
of three commercial periclase grains at 1,550 C
Hot MOR, psi
2.0
Zr0
2
4,500 1,850 2,250 2,650 3,475
Ti0
2
4,500 ND
1 '700
600 650
Ta
2
o
5
4,500 ND 1,600
1 '7 50
2,250
Sc
2
o
3
4,500 ND 675 5,47 5 5,550
Fe
2
o
3
4,500 ND 3,000 2,000 1,275
4,500 ND 6,175 4,625 4,350
SAMPLE 93.7 MgO
Zr0
2
4,610 7,650 8,700 1,125 750
Ti0
2
4,610 1,825 7,550 6,050 125
Ta
2
o
5
4,610 ND 375 200 ND
Sc
2
o
3
4,610 ND ND ND ND
Fe
2
o
3
4,610 ND 1,000 225 725
MnO 4,610 ND 3,650 5,875 2,325
SAMPLE 92.2
Zr0
2
1,800 ND 1,350 725 750
Ti0
2
1,800 ND 350 250 100
Ta
2
o
5
1,800 ND 300 225 350
Sc
2
o
3
1,800 ND 2,725 2,525 ND
Fe
2
o
3
1,800 1,37 5 2,250 750 375
MnO 1,800 ND 1,27 5 1,87 5 1,900
ND Not determined.
In general, the 93.7-pct-MgO periclase,
either doped and undoped, produced sam-
ples of the highest strength. The re-
fractoriness of the periclase grains
apparently is related to the total impur-
ity content, but the type of impurities
may be more important.
Additions of Zr0
2
in amounts of
0.25 mole-pct and 0.50 mole-pct were
found to increase the strength of
periclase sample (93.7 wt-pct
MgO) by 66 pct and 89 pct, respec-
tively. However, additions of Zr0
2
in
amounts above 0.5 mole-pct resulted in
decreased strength for samples
and Additions of Ti0
2
decreased
the strength of periclase samples
and but increased the strength
for sample when added in amounts
between 0.25 and 2.00 mole-pct. Doping
with Ta
2
o
5
decreased the hot strength
for all three samples. Additions of
Sc
2
o
3
increased the strength of peri-
clase sample by about 45.0 pct and
of sample by about 22.0 pct at the
1.0- and 2.0-mole-pct addition; sample
was not evaluated. Additions of
Fe
2
o
3
decreased the strength of samples
and whereas 0.5-mole-pct addi-
tions increased the strength of sample
Additions of MnO appeared to in-
crease hot strength values in several
cases.
The effects of the selected metal oxide
(Zr0
2
, Ti0
2
, and MnO) additions and C/S
ratio adjustments to 2:1 on flexural
strength at 1,550 C on all 11 periclase
materials are shown in table 5. Statis-
tical analyses of the data indicated that
additions of Zr0
2
significantly improved
5
hot strengths of six of the periclase
materials, especially those derived from
seawater, whereas additions of 0.5-
mole-pct MnO improved hot flexural
strengths of two of the periclase
materials. Additions of Ti0
2
resulted in
decreased strength values. As noted in
previous studies,7 adjusting C/S ratios
to 2:1 significantly improved hot MOR
values of most of the refractories.
These studies also demonstrated the dele-
terious effect of high

levels on hot
strengt11 of commercial periclases. The
hot strengths in table 5 for periclase
samples S-4, S-5, and S-6, which have the
three highest

contents, were the
three lowest values measured.
Results from this phase of the study
indicated that a C/S ratio and metal
oxide addition combination should be es-
tablished for each individual periclase
material. Of the metallic oxides studied
in this investigation, additions of
MnO and Zr0
2
appeared to be the most
promising.
Factorially Designed Experiment
Analyses of variance as applied to
the results of the factorial experiment
identified main effects and interaction
effects for each of the periclase materi-
als. The concentrations of MnO and Zr0
2
and the C/S ratio were chosen as the fac-
tors, and hot MOR as the response, for
the 4-level factorial experiment design
outlined earlier. Table 6 lists the F-
ratios for each factor and for second
order interactions between factors.
cited in footnote s.
TABLE 5. - Effect of oxide additions on hot MOR values of 11 commerical periclase grains at 1,550 C
Sample S-1 S-2 S-3 S-4 S-5 S-6
Source Israel United United United United Japan Japan United United United Israel
States States States States States States States
MgO wt-pct 99.2 97.6 94.5 93.7 92.2 97.6 96.4 96.2 94.5 93.5 93.3
B
2
o
3
wt-pct 0.09 0.09 0.03 0.02 0.03 0.01 0.06 0.2 0.20 0.3
C/S ratio,
as-received 7 0.7 2.7 1.5 1.7 .9 .4 1.4 0.4 0.4 0.4
MOR, psi:
As-received 4,550 220 6,520 4,610 1,800 490 240 450 210 170 180
Zr0
2
, wt-pct:
5, 730* 5 2,250 220 6,360 860 310 510 250 130 190
1 1,000 370 700 1,220 300 920* 450* 450 300 130 210
2. 1,040 600 6,830 960 750 980* 540* 710* 410* 150 410*
Ti0
2
, wt-pct:
5 330 100 490 490 350 270 130 190 230 50 180
1 360 80 230 140 160 250 280 210 90 60 50
2. . .......... 650 110 125 50 100 260 130 80 120 110 140
MnO, wt-pct:
5 1,040 170 3,650 6,620* 1,275 620* 230 490 220 120 230
1. . .......... 4,950 160 5,480 5,760 1,380 420 210 400 190 140 130
2 ........... 4,350 160 2,325 3,690 1,900 540 160 460 230 130 150
C/S ratio = 2 440 530*
1 '100 2,420 580 2 ,420* 900* 680* 1,190* 710*
*
I
- MOR improvement sign1ficant at 99 pct confidence level (Student s t test).
I
IMiller, and J. Freund. Probability and Statistics for Engineers. Prentice Hall, Englewood Cliffs,
N.J., 1965, 136-39, 168-70.
TABLE 6. - Analysis of data
reported as F-ratios
Sample
B-3n S-4n S-3n B-2n M-2n
Factorl:

0.6 1.1 1.7 0.4 1.8

23.1 .9 50.5 9.08 61.4
c ..... 11.88 7.6 20.07 .04 64.1
1. 4 .4 1.6 .9 .66
AC 1. 4 1.0 1. 3 1.2 1.04
BC 7.14 2.01 19.27 1. 5 115.5
= MnO; = ZrO
2
; c
=
C/S.
The C/S ratio had a significant effect
the hot strength of sample M-2n, the
93.5-pct natural magnesite periclase, so
did the addition of Zr0
2
The interac-
tion of C/S ratio and Zr0
2
had a highly
significant effect on hot strength of
this periclase material, with the most
interaction occurring at Zr0
2
additions of 1.0-mole-pct and a C/S ratio
of 3.
Additions of Zr0
2
also had significant
effect on the hot strength of sample
B-2n, a 95-pct-MgO peri-
clase. Interaction of Zro
2
content and
C/S ratio were found to be insignificant.
This sample contains substantial boron
impurities (0.11-pct

reported
to be extremely deleterious to the
refractory properties of periclase.8 The
C/S ratio adjustment was found to be
for sample S-3n, a 97-
pct-MgO seawater periclase.
The effect of C/S ratio was found to be
significant for sample S-4n, a seawater
periclase containing 94 pct MgO and 0.13
percent

Interactions between fac-

tors were shown to be unimportant. The
BGilpin, c., and D. R. F. Spencer.
New in Dead-Burnt Magnesite
and Dead-Burnt Dolomite. Refrac. J.,
47, 4, April 1972, 4-16.
C/S ratio was found to be
factor in determining hot
sample B-3n, a 96-pct-MgO
from brine.
7
a significant
strength of
periclase de-
Phase identification results (by X-ray
diffraction) in the optimized periclase
materials containing MnO additions,
samples S-3n and B-3n, indicated that
trace amounts of CaMn0
3
,

and a
spinel were present in both of these
specimens .
x-ray diffraction analysis indicated
that CaZr0
3
was present in both samples
containing Zr0
2
additions, samples M-2n
and B-2n. only other secondary phase
in sample M-2n was a trace amount of

Sample B-2n, a high-boron peri-

clase (0.11 pct

contained a minor
amount of cubic Zr0
2
Also detected in
this specimen were trace amounts of mon-
ticellite and merwinite, which may
account for its low hot
strength when compared wi th that of some
of the other doped samples. It has been
well documented that the low melting
points of monticellite (1,487 C) and
merwinite (1,577 C) lead to lower hot
strengths for periclase that contain
these silicates as secondary phases.
Thus, in the case of all periclase mate-
rial, a C/S ratio of at least 2.5 is
desired in order to more refrac-
tory dicalcium silicate that melts at
2,130 C, or tricalcium silicate that
dissociates at 1,900 C. Similarly, ad-
ditions of Zr0
2
resulted in the formation
of CaZr0
3
, a refractory secondary
phase (melting point of 2,340 C).
The only secondary phases identified in
sample S- 4n, another high-boron periclase
(0.13 pct

was

sample
also exhibited less in hot
strength than other doped periclase
materials .
8
CONCLUSIONS
Additions of Zr0
2
and C/S ratio adjust-
ments were determined to be effective in
increasing the hot MOR of calcined peri-
clase grain materials. The most effec-
tive additive tested was Zr0
2
The level
of addition of Zro
2
and the C/S ratio
adjustment required to yield maximum hot
strength varied among periclase refrac-
tory raw materials. In the case of "as-
received" periclase samples having hot
strengths of 1,500 psi or over, the
U S GOVERNMENT PRINfiNG OFFICE:
1982- 605 - 015/97
use of oxide addtions or C/S ratio
adjustments had little positive effect on
hot strength. The factorially designed
experiment was judged to be useful in
evaluating the interaction effects be-
tween factors and in establishing the
combination and levels of factors yield-
ing optimum results. Research to develop
superior full-size brick from domestic
periclase grain materials using these
results methods is continuing
INT.BU OF MINES,PGH., 26445