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Unconventional Binders in Refractory Concretes for Cement Plant Use

Chris Macey
Member, IEEE
Resco Products Inc.
2 Penn Center West, Suite 430
Pittsburgh, PA 15276 USA
chris.macey@rescoproducts.com

Abstract The physical properties of three 60% alumina monolithic refractories with different types of binders were
evaluated to determine optimum conditions of use and product selection for several applications within the cement
pyroprocessing train.

Index Terms abrasion resistance alkali colloidal silica refractory bonds compressive strength

I. INTRODUCTION

Refractory concretes (castables and gun mixes) are overwhelming favorites for maintenance of refractory linings
in North American cement plant preheaters and coolers. Refractory concretes provide high quality, durable linings
that can reduce installation time especially when large volumes of refractory need to be installed.

Since their employment in the construction and maintenance of preheater linings dating back to the 1970s,
refractory concretes have traditionally contained calcium-aluminate cements as the binder. Similar to Portland
cement, alumina cements are activated with water. These concretes typically feature good strength development
within 24 hours of installation, however, great care needs to be taken in drying out these linings, and frequently dry-
outs for linings can extend several days.

It is often desirable to dress an existing lining during a maintenance outage by application of a refractory veneer
using dry-gunite methods. Typically calcium aluminate-bonded concretes do not adhere well to existing linings, and
veneer materials will more likely use a chemical binder, as chemically set refractories tend to have much greater
adherence. Chemically-bonded monolithic refractories have an additional advantage of shorter drying times than
alumina cement-bonded mixes.

A third technology has emerged for refractory concretes utilizing nano-particle sized colloidal silica (C/S) as a
binder. This binder reduces the drying time for the refractory body as well as allows the potential for bonding to
existing refractory.

II. THE NATURE OF THE REFRACTORY BONDS

A. Alumina cements. Like Portland cement, alumina cements contain several mineral phases that react with
water. Only about a one-fourth of the tempering water is necessary to hydrate the alumina cement, the remainder is
present in the mix just for flow. When mixed with water, calcium aluminate cements undergo hydration in a
manner similar to Portland cements. The hydrated cement phases precipitate out of the water solution and cause
solidification of the mass. As the hydrate crystals form and grow, strength develops as the crystals interlace and
bind together.

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During the initial dry-out, the majority of the water in the alumina cement-bonded concrete is the simple
unbound water that evolves at or above the boiling point of water, 212F (100C). The hydration reaction products
of alumina cements include a varied array of phases. The hydration waters of the phases CAH10, C2AH8 and C3AH6
evolve between 212F and 752F (400C). In addition if the cement cures at a relatively low temperature, CAH10
and alumina hydrate, AH3, can form in a gel phase that has low permeability, which requires controlled lengthy dry-
out procedures.

In the year 2000, a specific modification of an alumina-cement bonded concrete was developed and brought to
the market. This product-type incorporated a variety of novel features including a very low cement content to
permit the refractory body to sustain a quicker initial dry-out using process-generated heat. Typically this type of
refractory has been employed to both reduce dry-out time and allow safe dry-outs in vessels where controlling a dry-
out schedule is difficult. This type of refractory concrete is referred to in this paper as a Modified Alumina Cement-
bonded Concrete (MACC).

B. Chemical bonds. The chemical bond of choice in many alumina-silica refractories is the phosphate bond.
Ultimately the reaction product of a phosphate binder and an alumina-bearing refractory is aluminum ortho-
phosphate (AlPO4). Water serves as the solvent for the phosphate chemical and allows attachment of the phosphate
anion to the aluminum cation. The chemical bond forms between 400F (204C) and 500F (260C). A hydrous
phase results and is essentially dehydrated at about 950F (530C).

The aluminum ortho-phosphate bond is strong, can be alkali resistant and is considered a non-crystalline bond.
In practicality, chemically-bonded refractories show little susceptibility to dry-out issues. In this paper, this type of
refractory will be referred to as a Phosphate Chemically-Bonded Concrete (PCBC).

C. Silica bonding. For this type of bond to form, silica molecules coat the refractory components in the castable
and form a network. The silica particles are supplied in a water suspension and have a size in the range of 1 to 5
nanometers. Hydroxyl groups are present on the surface of the silica particles. At approximately 302F (150C),
water desorbs from the silica. Silanol (-Si-OH) groups dehydrate at temperatures up to about 1220F (660C). In
the refractory, however, there are no hydration reaction products, and these concretes also have very low
susceptibility to dry-out issues. The silica particles are highly dispersed, and the silica network adsorbs onto an
existing refractory substrate as easily as on the refractory aggregate components of the concrete. This concrete will
be referred to as a Silica-Bonded Concrete (SBC) in this paper.

III. ADVANTAGES OF CONCRETES OF EACH BOND TYPE

The three 60% alumina refractory concrete types that have abbreviated dry-out schedules were selected for
evaluation to determine optimal conditions for use.

Modified Alumina Cement Concretes (MACC) is a newer castable technology that has been used over the past
decade and allows a quicker dry-out than traditional low-cement castables. MACCs feature good strength
formations even after curing and before drying (see Table 1). With this technology, heating for the initial dry-out
can begin as soon as the material has taken its initial set and does not require the traditional 24 hour cure
characteristic for a low-cement castable. The amount of alumina cement is relatively low for the MACC refractory
resulting in a low lime (CaO) content, and the overall refractoriness of the matrix is high. These MACC materials
are easily formulated for mechanized pumping to cast in place and for shotcrete installation, or for gunite
application. In shotcrete or gunite applications, these materials have good set times and allow for trimming the lining
after application. MACC materials are not designed to adhere to existing refractory.

A typical initial heating rate for MACC concrete in a one-component lining is to increase temperature by 100F
(56C) per hour per hour to service temperature, compared to a rate of 50F (28F) per hour with several
temperature holds for traditional low-cement castables.

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Phosphate Chemically-bonded Concretes (PCBC) set fairly rapidly. These concretes feature very good
abrasion resistance, moderate alkali resistance and also have a moderately expensive cost structure because of some
of the high purity ingredients. The normal casting grade refractory may not permit mechanized installation,
although a gunite-grade material is readily available. The chemically-bonded concrete is suitable for use in
preheater vessels.

A recommended initial heating rate for PCBC materials is similar to the Modified Alumina Cement Concretes
(MACC), with temperature increases of 100F (56C) per hour to operating conditions. It should be noted that this
type of monolithic refractory has been used for hot gunning with success, so the PCBC is relatively insensitive to the
speed of dry-out.

Silica-bonded Concretes (SBC) are a two component system of a dry mix and a liquid binder. They feature
rapid setting upon installation, although ultimate strength remained lower than in the two other types of concretes
throughout the range of heating. For a primary lining of an SBC, a suggested heating rate is to raise temperature
50F (28C) per hour to 400F (205C), hold at 400F for one hour per inch of thickness, and then raise to
operating temperature at 100F (56C) per hour. Note that the colloidal silica liquid binder must not freeze, as
freezing will cause the silica particles to fall out of suspension.

IV. LABORATORY TEST RESULTS

In order to evaluate the relative advantages of each bond type, samples of 60% alumina castables were batched
in the laboratory, mixed with water and allowed to set. Initially physical properties for bulk density, compressive
strength and abrasion resistance were determined. Table 1 (below) lists common physical properties for samples of
the three types of refractory concretes using standard ASTM methods. Bulk density (pounds per cubic foot, pcf) is
measured after heating to 1500F (816C). Compressive strength, also called cold crushing strength (CCS), was
measured in the green state after 24 hour cure at room temperature, after drying to 220F (104C), after heating to
600F (316C) and after heating to 1500F.

Refractory Binder Density Cold Crushing Strength (CCS)

after Green after after after
Heating (undried) Drying Heating Heating
to 1500F (psi) to 220F to 600F to 1500F
(pcf) (psi) (psi) (psi)

MACC Cement 152 4,390 9,060 8,560 12,200

PCBC Chemical 150 3,250 8,660 10,200 9,800
SBC C/S 155 1,420 4,720 4,820 6,460

Table 1. Physical properties of 60% alumina castables using the three binders

The cement-bonded refractory, MACC, exhibited the highest strengths in nearly all tests. The MACC
refractorys strength more than doubled after drying. After heating to 600F (316C), the MACC sample showed a
small loss in strength, likely due to the dehydration of some of the cement phases, but increased in strength after
heating to 1500F (816C).

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The phosphate-bonded casting mix, PCBC, developed good strength in the green state, and like the cement-
bonded material, more than doubled in strength after drying. On further heating to 600F (316C), strength showed
additional improvement. The PCBC refractory had essentially the same strength after heat treatment at 1500F
(816C) as after heating to 600F (316C). These data are consistent with the phosphate bonds complete formation
by 600F.

The silica-bonded refractory (SBC) exhibited low strength in the green state. Strength of the SBC increased
significantly after drying, and after heating to 1500F (816C), although ultimate strength was still less than that of
the MACC and PCBC. Cold crushing strength for the SBC is approximately half that of the MACC refractory, even
after heating to 1500F (816C).

Abrasion resistance is indicative of a refractory concretes resistance to a scraping or scratching medium.

Abrasion loss is measured at room temperature using the ASTM C-704 procedure typically after heating the sample
to 1500F (816C). In the ASTM C-704 test, 1,000 grams silicon carbide grit abrades the sample at room
temperature and the volume lost (in ccs) is reported. A low number (less volume abraded) indicates better abrasion
resistance.

Abrasion resistance was tested on the three refractory types in the green state after curing, after drying to 220F
(104C), after drying and heating to 600F (316C), to 1500F (816C) and to 2200F (1204C). Generally it was
found that abrasion resistance trended with cold crushing strength (CCS). The MACC and the PCBC exhibited
similar abrasion resistance after heating to the various temperatures. For the SBC, abrasion resistance is fair, at best,
in the lower temperature ranges and improved as the temperature of heat treatment increased.

Refractory Binder ASTM C-704 Abrasion Test (cc, loss)

after after after
after drying heating heating heating
to 220F to 600F to 1500F to 2200F

MACC Cement 6.7 9.2 5.3 5.2

PCBC Chemical 12.2 9.9 6.1 8.8
SBC C/S 22.3 20.6 9.1 5.6

Table 2. Abrasion resistance of the refractory types after heating to various temperatures

In addition to physical property tests, other application-related tests were conducted to evaluate the suitability of
each refractory bonding system in other operating conditions.

Alkali resistance is a topic of interest to cement plant operators. Sometimes the cooler lining and linings in
vessels in the lower preheater can be susceptible to reaction with alkali, primarily potash (K 2O). Alkali reactions
with alumino-silicate refractories are expansive in nature, as the products of reaction with alkali are significantly
larger in volume than the original refractory. The expansion can cause disruption of the refractory bonding matrix
and lead to cracking and spalling.

One method used by the refractory industry to evaluate alkali resistance is a simple cup test. In this test, a
refractory sample is made that contains a 40-mm diameter by 40-mm deep hole. The cup sample is dried at 230F
(110C) and fired in a kiln to 2192F (1200C) for five hours and cooled. Potassium carbonate (K2CO3) is packed
into the hole of the refractory cup. A refractory lid is cemented into place over the charged cup. The cup is then
fired to 2012F (1100C) for five hours and then cooled. The specimen is cut into halves and visually examined.

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Cracks indicate alkali reactions and give the sample an unsatisfactory rating. The samples must also have a
penetration no greater than 3-mm in order to receive a satisfactory rating.

Fig 1 and 2. MACC and PCBC refractories show good alkali resistance with no cracking.

Fig 3. Colloidal silica-bonded refractory also exhibits strong alkali resistance.

In appearance, all three refractory bond types had equivalent alkali resistance, with none of the sample cups
exhibiting cracking, and all three received a satisfactory rating.

Refractory Binder ALKALI CUP TEST

Cracking Penetration (mm) Rating

MACC Cement No <1 Sat

PCBC Chemical No <1 Sat
SBC C/S No 0 Sat

Table 3. Alkali cup test results for the three refractory types

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Another property of interest is the adherence of the refractory material to an existing refractory substrate.
Measuring adherence to an existing refractory is difficult and can be variable. A non-standard test has been devised
to measure this property based on the Modulus of Rupture (MOR) test for flexural strength. MOR bars of a
conventional castable refractory are cast and dried. The bars are broken in typical MOR fashion, and a broken half
bar is re-inserted into the MOR bar molds. The candidate refractory is then cast into the remaining portion of the
bar mold cavity of the bar. The candidate refractory is allowed to set, and the jointed bar is then removed from the
mold and fired to 1500F (816C). After cooling, the jointed bar is again broken in the MOR fashion. The MOR
pressure is then recorded as the adherence strength.

As expected, the PCBC jointed bar had the highest adherence strength, closely followed by the silica-bonded
concrete sample (SBC). The Modified Alumina Cement Concrete (MACC) had the lowest adherence and after
heating to 2200F (1204C), there was no adherence at all to the original broken refractory piece.

Also as expected, the adherence strength of the silica-bonded refractory (SBC) increased as the heat treatment
temperature increased, consistent with the compressive strength characteristics of this material.

Refractory Binder Adherence Test (psi) After Heating to

220F 600F 2200F

MACC Cement 249 134 0

PCBC Chemical 419 130 800
SBC C/S 73 286 610

Table 4. Adherence strength of the refractory materials

V. DISCUSSION

Based on the comparative tests, conclusions can be drawn from the laboratory work regarding the application of
these refractory bonding systems in the cement kiln pyroprocess train.

Primary linings in preheaters and coolers need early physical strength to withstand any abrasion or mechanical
stress. Monolithic refractories bonded with alumina cements provide the best strengths and abrasion resistance, not
only upon setting at room temperature but throughout the working temperature ranges in the clinker cooler or the
preheater.

MACC refractories meet the strength needs and provide the shortest dry-out procedures of alumina cement-
bonded refractories. Primary lining applications for MACC refractories include clinker cooler sidewalls and curbs,
cooler inlet walls, firing hood sidewalls and roofs, tertiary air duct linings, rotary kiln nose rings, feed inlet
chambers and feed shelves, preheater riser duct sidewall linings and cyclone vessel sidewalls and roofs.

Cement-bonded refractories, however, are not useful for application onto primary linings because they do not
bond well to an existing refractory substrate.

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PCBC concretes and gunning mixes are used most frequently to dress, or add thickness, to existing refractory
linings where the remnant thickness of the refractory does not justify removal and replacement, but where additional
operating time can be gained by application of a veneer layer over the refractory. PCBC mixes are able to adhere to
clean existing linings and have been used for many years in the cement industry to extend the life of primary linings.
PCBC materials provide good strength and abrasion resistance as well as superior adherence. PCBC refractories can
be dried out easily compared to conventional low (alumina cement-bonded) castable materials.

Refractories bonded with colloidal silica (SBC) are the newest type of monolithic refractories used in cement
plant preheater and cooler linings. Because strength development in an SBC occurs only after heating, and
especially so in heating to elevated temperatures, the use of SBC refractories for primary linings may be limited. It
is anticipated that refractories bonded with colloidal silica will probably be most useful in extending the life of
primary linings by gunite application of a veneer onto the existing lining surface. SBC gunning mixes apply
smoothly with the mix adhering quite well to the existing refractory substrate (see Figure 4). Colloidal silica-
bonded refractories can also be easily dried out.

As stated earlier, the colloidal silica binder must not be allowed to freeze. This must be recognized as a
drawback for transport of the binder liquid and installation of SBC materials in cold weather.

Fig 4. Colloidal silica-bonded refractories are excellent patch and veneer materials
installed by gunite application and used to extend the service life of primary linings.

As a newer refractory technology available to cement manufacturers, colloidal silica-bonded refractories can be
used for gunite application onto primary refractory linings in cement kiln preheaters, hoods and coolers, augmenting
the more conventional cement-bonded castables and phosphate-bonded patching refractories. Colloidal silica-
bonded refractories can be used in primary linings if low temperature, or early, strength and abrasion resistance are
not critical for the process.

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REFERENCES

1. C. Parr and C. Wohrmeyer, The Advantages of Calcium Aluminate Cement as a Castable Bonding
System, presented at the St. Louis Section Meeting of American Ceramics Society, St. Louis, Missouri, 2006.

2. C. Parr, E. Spreafico, T. Bier and A. Matthieu, Calcium Aluminate Cements (CAC) for Monolithic
Refractories, presented at the First Monolithics Conference, Tehran, Iran, 1997.

3. H. Balter, Reparaturtechniken zur Beseitigung von Feuerfestschaden im Zementofen, ZKG International,

Vol. 52, (4), pp. 182-189.

4. P. Yuan, D. Wu, H. He and Z. Lin, The Hydroxyl Species and Acid Sites on Diatomite Surface: a Combined
IR and Raman Study, Applied Surface Science 227, pp. 30-39.

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