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Plastic molding refractory mixes based on highly concentrated ceramic binding

suspensions of high alumina fireclay

Article  in  Refractories and Industrial Ceramics · January 2007

DOI: 10.1007/s11148-007-0028-2

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Refractories and Industrial Ceramics Vol. 48, No. 1, 2007

PLASTIC MOLDING REFRACTORY MIXES BASED ON

HIGHLY CONCENTRATED CERAMIC BINDING SUSPENSIONS
OF HIGH ALUMINA FIRECLAY

V. A. Doroganov,1 E. I. Evtushenko,1 and Yu. E. Pivinskii1

Translated from Novye Ogneupory, No. 3, pp. 120 – 125, March, 2007.

Original article submitted November 30, 2006.

Refractory mixes of high alumina composition are developed for plastic molding. The mixes are distinguished
from more traditional ones by a low clay content (by a factor of 3 – 5) due to introduction into the mix compo-
sition of highly concentrated ceramic binding suspension based on high alumina fireclay that promotes an im-
provement in the basic physicomechanical properties of articles made from these mixes.

It is generally known that there is a modern tendency to
increase the relative proportion of the production and require-
ment for unmolded refractories and the balance of them [1].
Abroad there is very successful application of plastic refrac-
tory mixes both for making monolithic linings and for repair-
ing them. It is well known [2 – 4] that production of refrac-
tory air-hardening plastic mixes of aluminosilicate composi-
tion predominate. According to data in [4] the Al2O3 content
within them is 27 – 90%, and for SiO2 it is 6 – 67%. Whereas
the filler used in these mixes is fireclay, fractionated bauxite
or corundum, clay is used predominantly as a binder. As a re-
sult of the fact that the clay content in these mixes is very
significant their linear shrinkage during drying reaches
1 – 1.4%, and 2.2% after heat treatment at 1100ºC [4].
The mechanical properties of these mixes both after drying
and after heat treatment are relatively low. For a plastic mix
from Plibrico with an Al2O3 content of 27 – 52% the ultimate
strength in compression after drying and heat treatment at
1100ºC is 4 – 7 and 14 – 16 MPa respectively [5]; open po-
rosity for the mixes after heat treatment is very marked
(23 – 30%).
In view of this in the present work the task is set of de-
veloping refractory plastic mixes that compared with known
mixes could be characterized by increased constancy of vo-
lume, density, and mechanical strength. The problem was re-
solved by using for the binder system plastic mixes of com-
plex ceramic binder consisting of highly concentrated ce-
ramic binder suspensions (HCBS) of the appropriate refrac-
1
V. G. Shukhov Belgorod State Technical University, Limited
Liability Company (OOO) NVF KERAMBET-OGNEUPOR,
Russia.
tory material (for example aluminosilicate-fireclay or bauxite)
and the optimum plastifying addition, i.e. refractory clay.
This should provide an increase in concentration and a re-
duction of the water required for these mixes (since HCBS of
acid and acid-amphoteric composition exhibit a low moisture
content [1]) and shrinkage. In addition, for binder systems
based on HCBS there is typically a marked increase in
strength after low-temperature heat treatment [6]. It should
be noted that the problem of plastifying HCBS of quartz
sand [7] or bauxite [8] with refractory clay has been suc-
cessfully realized as applied to a refractory mix formed by
static compaction or pneumo(vibro)molding.
Whereas in previous work for a ceramic binder and ce-
ramic concrete [6 – 9, 10] a detailed study has been made of
rheological properties of the dispersed systems (original
HCBS, filled suspension) in the flowing state, in this case the
task has been set of obtaining refractory mixes not flowing,
but of plastic (solid phase) consistency [11]. In studying the
properties of the materials created subsequent analysis is
necessary for three types of modified dispersed systems: 1 is
a suspension (paste, mix) based on plastic refractory
clay-plastifier; 2 is modified binders consisting of HCBS
inert material plastified with refractory clay, i.e. a refractory
mix matrix system; 3 is finished mix with binder and refrac-
tory filler, i.e. the final product. The first two types of these
dispersed systems have already been studied in detail
[12 – 16], and therefore the present work was devoted to pre-
paring and studying plastic refractory mixes (filled with re-
fractory filler).
Traditionally the method plastic molding is based on in-
troducing into the composition of the molding mixture natu-

63
1083-4877/07/4801-0063 © 2007 Springer Science+Business Media, Inc.
64 V. A. Doroganov et al.

ral plastic ceramic materials (clay, kaolin, bentonite) that to prepare refractories with high operating indices. However,
play the role of a binder and enter into the composition of the in a number of cases in preparing articles of complex confi-
plastifying addition required in order to give the molding guration or large articles use of even these pressures is prob-
mix certain viscoplastic properties. Molding of plastic mixes lematical. Therefore the aim of the present work is to de-
is accomplished in charges with increased moisture content velop and study refractory mixes intended for plastic mold-
that may reach 25 – 27%; here the molding pressure is ing, accomplished with a low pressing pressure (< 10 MPa).
1 – 2 MPa. Using a mix with a lower moisture content From a production point of view a distinguishing feature of
(16 – 18%) the required molding pressure (in relation to the these mixes from previous ones [17] consists of the fact that
molding mixture composition) increases considerably, i.e. up the clay component is introduced into the charge not in the
to 5 – 7 and even up to 10 MPa. form of a suspension, but as a dry finely-ground powder.
Previously [17] refractory mixes have been studied of re- In addition, these mixes are distinguished by high plasticity
duced moisture content based on plastified HCBS, by means and moisture content. Molding of experimental specimens in
of which with sufficiently low molding pressure (10 – 30 MPa) this case is accomplished by free pressing (extrusion).
it is possible to prepare materials with improved physico- High alumina fireclay produced by OAO Semilusk Re-
mechanical properties. Use of these mixes makes it possible fractory Plant (OAO SOZ) was used as the filler whose com-
position is given in Table 1. As applied to the plastic molding
method the optimum size fraction was chosen for a three-
TABLE 1. Grain Size Composition of the Test Filler fraction filler according to two parameters: by the packing
factor K 1pa [6] to compaction and by the packing K 2pa after
Composition Content, %, fraction, mm compaction. The molding pressure was chosen proceeding
number 0.1 – 0.5 0.5 – 2.5 2.5 – 5.0 from the force that a normal plastic molding press develops
1 100 — — (2 MPa).
2 — 100 — In the diagram for the change in K 1pa and K 2pa , shown in
3 — — 100 Fig. 1, it follows that for a polyfractional filler composition
4 20 20 60 these factors are higher than for a monofractional composi-
5 40 20 40 tion. The maximum packing factor before (0.58) and after
6 60 20 20 compaction (0.59) occurs for composition 4 (see Table 1),
7 20 40 40 and here DKpa is 0.01. The maximum value of DKpa (0.03) is
8 20 60 20 typical for composition 6 (see Table 1), which points to its
9 40 40 20 good compacting capacity compared with composition 4.
Thus, high values of K 1pa and K 2pa do not always correspond
to the optimum filler size fraction, and therefore in choosing
1 the optimum composition it is also necessary to consider the
Kpa
a difference between these factors. Taking account of the re-
0.575
sults obtained the optimum filler size fraction is for composi-
0.550 tion 6 that has a high value of DKpa.
0.525 On the basis of the optimum size fraction selected for
0.500 filler refractory mixes were studied intended for plastic
0.475
molding with a different binder content mb and clay compo-
nent within it. The binder used was a mixed system consist-
0.450
ing of HCBS based on high alumina fireclay produced by
0.425 OAO SOZ, that has been studied already in detail [15, 17]
0.400 and clay grade LT0. For comparative evaluation of the differ-
2
Kpa ent operating characteristics of mixes their moisture content
b
was within narrow limits (11 – 12%). Compositions of the
0.55 test plastic mixes are presented in Table 2. Plastic mixes
were prepared by the following regime: filler of the optimum
0.50 composition was previously mixed with finely-ground clay,
and then HCBS of high alumina clay was added to the mix-
0.45
ture, after this the mix was moistened to a content of
11 – 12%. In order to average the moisture content through-
0.40
1 2 3 4 5 6 7 8 9 out the whole volume and stabilize the structural and me-
Composition number chanical properties of the mix it was stored for 24 h in a de-
Fig. 1. Diagrams of the change in K 1pa for compaction (a) and siccator without access to atmospheric air.
K 2pa (b ) after compaction of filler in relation to its size fraction Before molding specimens in a conical Rebinder
(composition number from Table 1). plastometer by a known procedure [18] values of plastic
Plastic Molding Refractory Mixes Based on Highly Concentrated Ceramic Binding Suspensions 65

strength Pm were determined for the starting molding mix. Thus, the plastic strength of mixes has a governing effect
As follows from Fig. 2, with an increase in clay component on pressure with which the mix is molded freely by extru-
content in the mix there is an increase in plastic strength. sion. As can be seen from Fig. 5, in which the dependence of
There is an increase in the value of Pm for mix compositions Ps.f on Pm is shown for mixes with different binder and clay
with mb = 30%, and the least for compositions with content within them, with an increase in Pm the value of Ps.f
mb = 50%. Thus, an increase in binder content by 20% leads decreases for all compositions, but for a mix with maximum
to a reduction in mix plastic strength by 50 – 60 Pa.
Specimens in the form of cylinders with a diameter and
Pm , Pa
height of 50 mm were prepared using a die of special con- 30
140
struction (Fig. 3). Mix 1, intended for molding, was placed in 40
120
the die 2 between lower 3 and upper 4 punches. Then a force
was applied to the upper punch 4. On reaching a certain pres- 100
50
sure for the start of plastic flow Ps.f, when the mix started to 80
freely force through a special hole for this purpose 5 with a 60
diameter of 15 mm in the die (see Fig. 3), there was no 40
further increase in pressure. This made it possible to con- 20
clude that the value of Ps.f is the optimum pressure for plastic
0
molding. Specimens molded to the required size and the ex- 20 40 60 80 100
cess mix were removed through hole 5. Clay content in the binder, %
Shown in Fig. 4 is the dependence of optimum pressure 80 60 40 20 0
Ps.f on clay and HCBS content in the binder with a different HCBS content in the binder, %
amount of it in the plastic mix. With an increase in clay con- Fig. 2. Dependence of plastic strength Pm on clay content in HCBS
tent in the binder Ps.f decreases in all mix compositions, but in binder plastic mixes with different values of mb (shown on the
the nature of change is somewhat different. The most sharp curves, %).
change in Ps.f occurs in compositions with mb = 40%; in
compositions with mb = 50% with an increase in clay content
to 40% the Ps.f is almost unchanged. It should be noted that 4
with a clay content in the binder of more than 40% there is a
marked difference in the value of Ps.f that is 18 – 20 MPa.

TABLE 2. Composition of Plastic Mixes Made of HCBS Based on

High Alumina Fireclay 2

Composition Binder composition, % 5

1
number HCBS clay
3 Fig. 3. Die for preparing labo-
Mix with mb = 30%*
80 20 ratory specimens.
1¢
2¢ 70 30
3¢ 60 40
Ps.f , MPa
4¢ 50 50
5¢ 0 100 30

Mix with mb = 40% 25 30

6¢ 80 20 20
7¢ 70 30
15 40
8¢ 60 40
9¢ 50 50 10
10¢ 0 100
5 50
Mix with mb = 50%
0
11¢ 80 20 20 40 60 80 100
12¢ 70 30 Clay content in the binder, %
13¢ 60 40 80 60 40 20 0
14¢ 50 50 HCBS content in the binder, %
15¢ 0 100 Fig. 4. Dependence of Ps.f on clay and HCBS content in the binder
* Here and subsequently, filler, %. plastic mix with different values of mb (shown on the curves, %).
66 V. A. Doroganov et al.

content of matrix system (mb = 50%) the nature of the curve compositions (see Table 2) are shown in Fig. 6. An increase
is smoother than for the others. This points to a greater pro- in clay component content and a reduction in the amount of
portion of plastic deformation development in the mix as the HCBS in mixes leads to an increase in Pop by 5 – 6% (see
content of the matrix system increases. Thus, an increase in Fig. 6a ), and here there is also a marked reduction sco for the
clay component in the binder and correspondingly a reduc- material, i.e. by 25 – 40 MPa (see Fig. 6b ). The markedly
tion in the amount of HCBS leads to an increase in the plastic lower sco (up to 15 – 20 MPa) for the composition with
strength of the system and a reduction in pressure required in mb = 50% is due to an increase in the clay component content
order to mold specimens by the plastic method. and as a consequence much greater material porosity.
Results of studying the main physicomechanical proper- It follows from these studies that introduction into the
ties of heat treated specimens based on the experimental
binder composition for refractory mixes of plastic molding
HCBS of high alumina composition improves the operating
Ps.f , MPa
properties of the material (it reduces Pop by 2 – 4% and in-
30 creases sco by 9 – 20 MPa) compared with traditional plastic
30 40 mixes whose binder is only a clay composition. An increased
25 HCBS content in the binder leads to a marked increase in
20
pressure (by almost a factor of ten for some compositions)
required for molding these mixes (see Fig. 5). The optimum
15 mix is one consisting of 60% filler and 40% binder in which
10 the clay component content is 30 – 40% (compositions 7¢, 8¢
5
see Table 2), and converted to the total mixes not exceed
50
16%. With a mix of this composition it presses well with a
0 20 40 60 80 100 120 140 160 low pressure (5 – 7 MPa) and it exhibits quite high operating
Pm , Pa indices.
In previous work [15, 17] the high efficiency of introduc-
Fig. 5. Change in Ps.f and Pm for plastic mixes with an increased
ing into the composition of the matrix system a complex
clay content in them (from 6 to 50%) with different values of mb
(shown on the curves, %). organomineral thinner (COMT) was demonstrated, consist-
ing of superplastifier SB-5 [16] and sodium tripoly-
phosphate, applied to pressing a mix based on plastified clay
Pop, % HCBS of high alumina fireclay. Additions of COMT pro-
motes improvement not only in material molding capacity,
28 50
but also its physicomechanical properties. The authors of the
26 present article have studied the effect of COMT both on the
molding properties of mixes, used for plastic molding, and
24 also the physicomechanical properties of a mineral based on
40 them. The COMT concentration was 0.02% of the suspen-
22
30 sion weight [15].
a
20 The effect of COMT has been studied in composition
sco, MPa with the optimum ratio of binder (40% and filler (50%) with
b
a different content of the clay components in the binder
50 30
(compositions 6¢ –9¢, see Table 2). From analysis of the plas-
40
tic properties of mixes it follows that with introduction into
40 the composition of a COMT binding addition there is a
30
marked (by a factor of five to six) increase in the plastic
strength of the mix (Fig. 7a, curve 1 ) compared with a sys-
20
tem without the addition (Fig. 7a, curve 2 ). This nature of
50 change is reflected in the value of Ps.f (Fig. 7b ): with use of
10
COMT Ps.f decreases markedly (by up to a factor of nine),
20 40 60 80 100 particularly in the range of low concentrations of clay in the
Clay content in the binder, % binder (curve 1 ). This is a consequence of the fact that in the
80 60 40 20 0 system with introduced COMT there is a marked increase in
HCBS content in the binder, % the proportion of slow deformations and the time for true re-
Fig. 6. Dependence of open porosity Pop (a) and ultimate strength laxation, as has been established previously [17]. As a result
in compression sco (b ) for specimens of plastic mixes heat treated at of this conditions are created for minimizing the energy con-
1300ºC on clay and HCBS content in the binder with different va- sumed in molding this mix. It should be noted that for mixes
lues of mb (shown on the curves, %). without added COMT the limiting molding pressure (10 MPa)
Plastic Molding Refractory Mixes Based on Highly Concentrated Ceramic Binding Suspensions 67

Pm , Pa Pop, %
a
23 2
400
1 22 1
300

21
200

100 2 20
a
0 19
Ps.f , MPa sco, MPa
b b
25 2 55

50 1
20
45 2
15
Pcr 40
10
35
5
1 30
0
20 25 30 35 40 45 50 25
20 25 30 35 40 45 50
Clay content in the binder, %
Clay content in the binder, %
80 75 70 65 60 55 50 80 75 70 65 60 55 50
HCBS content in the binder, % HCBS content in the binder, %
Fig. 7. Dependence of Pm (a) and Ps.f (b ) for plastic mixes with Fig. 8. Dependence of Pop (a) and sco (b ) for specimens heat
added COMT (1 ) and without it (2 ) on clay and HCBS content in treated at 1300°C based on plastic mixes with added COMT (1 ) and
the binder. without it (2 ) on the content of clay and HCBS in the binder.

is observed with introduction to the binder of 30% clay (see
Fig. 7b, curve 2 ). Systems with addition of COMT are cha-
racterized by a markedly reduced (up to 3MPa) value of Ps.f
over the whole concentration range for the clay component
in the binder (see Fig. 7b, curve 1 ).
In molding articles based on plastic mixes with added
COMT there is formation of a more ordered structure with
improved physicomechanical properties, and this is con-
firmed by the dependences shown in Fig. 8. With introduc-
tion of COMT there is a reduction in Pop by 1.5 – 2% and an
increase in sco by 6 – 12 MPa over the whole concentration
range for clay in the binder. The minimum Pop (19.2%) is
achieved for mixes with added COMT with a clay concentra-
tion in the binder of 20% (see Fig. 8a, curve 1 ): here there is
a maximum sco for the material (see Fig. 8b, curve 1 ).
Thus, it been established that with an increase in plastic
strength of mixes intended for plastic molding there is a re-
duction in the optimum pressure required for molding arti-
cles. Use of mixes in whose binder the clay component is
partly replaced by HCBS of high alumina fireclay with
added COMT it is possible to mold mixes of a high alumina
composition with a moisture content of 11 – 12% at a low
pressure (3 MPa). Here finished specimens are characterized
by relatively low open porosity for plastic mixes (19 – 20%)
and quite high ultimate strength in compression (50 – 55 MPa).
The plastic mix composition developed is also distinguished
by a low (compared with traditional plastic mixes) clay con-
tent (20%) in the binder, which converted to the total mix
does not exceed 8%, and it promotes a reduction in the
shrinkage of articles based on it. For plastic mixes produced
by Pilbrico shrinkage at 1300ºC is 1.9 – 2.2% [4], which is
higher by a factor of to six than for the mixes developed
based on HCBS with added COMT (0.3 – 0.6%). These
mixes may be used not only in preparing, for example refrac-
tory articles by a plastic method, but also as ramming mixes,
repair mixes, and in molding large shaped articles.
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