Chapter

VII

Principles of Corrosion Resistance: Hot Gases and Dusts

ATMOSPHERIC

PENETRATION

AND CONDENSATION

Refractory sidewalls, roofs, ducting, heat exchangers, and muffles exemplify exposures to hot gases and dusts. Kiln and steam boiler linings likewise entail corrosive atmospheric exposures without a liquid bath at the same time. Among the vessel descriptions in Chapter III, zoning tables are included which make distinctions between refractory exposure to liquid (e.g., slag or glass) below and predominantly to gases and dusts above. It is quite common that a change in refractory specification occurs near that boundary. Both similarities and differences exist between atmospheric and liquid-phase corrosion. Entrained particulate matter will be taken up last. A distinction must be made between dust and fog; we shall treat the latter briefly as an extension of the former.

Gas Penetration by Diffusion Through Pores

There are striking parallels between corrosive-gas penetration into a porous refractory and reactive-gas penetration into a porous, surface-active solid catalyst. It is unprofitable here to seek quantitative solutions. But for qualitative use a simple equation can be adapted from the catalyst literature 274 relating gas diffusion kinetics to the characteristics of connected porosity. This equation applies to unidirectional steady-state diffusion in a flat porous wall of thickness Z, at some fixed temperature T: @- (Db * EdP/z)(-dp/dz) 255
.

256 Handbook of Industrial RefractoriesTechnology Here, ais the flux of the diffusing species in mols per unit wall area per unit time. l&, is the bulk value of the diffusivity of that gas in some host gas at that T, and Gd is the suitably-averaged value of a function G,, which gives the actual diffusivity in a pore of diameter d: D, = D, . G.,. This function Gd is non-linear, but decreases from a value of unity for large pores to about Gd0~ d in small pores, where it may range from 10-l to 10-s or so. Then it goes steeply to zero for molecularly-small pores.274 P is the volume fraction of connected porosity, or 0.01 times the volume percent apparent porosity;9 and z is the tortuosity factor, related to the devious diffusion paths through a porous medium but somewhat more intricate than fhaf.274 Common values of s range between about 2 and 5, ordinarily increasing somewhat with decreasing porosity. The derivative dp/dz is itself negative; p is the partial pressure of the diffusing species, highest at the working face of the refractory
(i.e., at z = 0) and tending toward zero with increasing depth due to consumption of that species by corrosive reaction. The derivative dp/dz is not constant with z (hence neither is cp),but we need not be concerned with its evaluation for present purposes. It suffices here to observe how CD varies with porosity and with average pore size. The flux m0 at L = 0 is of course proportional to the volume rate of gas penetration; there is no linear advance of a front as was observed previously for liquids. Q, is, however, equal to the integrated steady-state gas consumption rate per unit area in the interior of the wall. From the equation above and the given descriptions of its terms, 9, varies (a) about proportionately with the apparent porosity, and (b) though not linearly, in ositive correlation .+ with the average pore diameter as determined by cp

These are qualitatively the same relationships as were shown under Porosity and Pore Sizing in Chapter VI for liquid penetration by mass flow -- though matters of wetting and non-wetting are absent here. There are some aspects of gas corrosion which can alter the pore characteristics with time, as will be discussed presently. These and the gradient dT/dz across a refractory wall disclose the above isothermal equation to be an oversimplification; but its correlations are valid. There are also close similarities between gas penetration of crevices, cracks, and microcracks and the penetration of these same features by liquids, again excepting any dependency here on wetting. Two phenomena distinguish corrosive gas diffusion into refractories from liquid penetration. One is that the driving force for the former at steady state is the pressure gradient due to consumption of the gas by reaction. On that account, it is reasonable to characterize gas penetration broadly as less rapid in mass terms than that of wetting liquids. The other distinction is that reaction does not

Principles of Corrosion Resistance: Hot Gases and Dusts

257

necessarily commence at the hot face. On both accounts the depth of penetration by gases can be much greater in some circumstances than that by liqui&.70,81,82,108,275,276 Heat-Exchanger Profiles

The scenario implicit in the above is of a wall whose working face is bathed by a rapid-flowing gas parallel to it and of sensibly constant composition: typical for furnace and kiln walls and roofs and fairly close for ducts. Still another relationship in the catalyst field can be borrowed for heat exchangers. Here the gas flows progressively

over a large refractory surface in packed tower configuration. At each level in the tower part of the corrosive component of the gas moves into the porosity of the solid and is consumed, and the remaining part passes along to the next level. The partial pressure p0 of that component (0 for outside the solid) thus falls with the distance or height, h, traversed by the gas through the tower, commencing wherever the corrosion process begins.
Equations relating pO to h in an analogous catalyst bed or tower are roughly exponential in form at constant temperature, but depend on the kinetic order of the consuming reaction.277 A simple isothermal equation for kinetic order of unity is adapted for use here as:

Po2= pal exp [WhVkl

where h2 > h,, h, is the height at which gas consumption begins, po, is initial, po2prevails at height h2, and k is a constant. Again it is not profitable to seek quantitative solutions: matters of kinetic order, of boundary-layer mass transfer coefficients, and of actual temperature variation with h and time interfere. It suffices to infer that corrosion of the refractory heat-exchanger packing or checkerwork is intensely concentrated close to height h, and then falls off in quasi-exponential fashion with increasing h. Field evidence of this is in hand for h, = 0 in glass checker bricks removed after service:278 severe damage was sustained in the topmost foot or so of a downflow tower.
Permeation Rates

The permeability of a porous refractory to gases is also sometimes of interest, in connection with leakage through a wall to

the exterior or opposite side. Cases in point are a muffle, or a kiln or retort wall that is not encased in steel. If part of the gas reacts with the solid, equations can be developed to handle the simultaneous processes but are specific to each given case. The case of nonreactive gases can be treated more generally.

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The simplest permeation equation is of the same form as that for diffusion: Cp = (DG,P/z)( - dp/dz) . But here Dr becomes, at steady state, an averaged permeation coefficient for the gas components present. Its most important dependency is on the gas viscosity, which is a function of composition, pressure, and temperature. The other terms in the equation are as defined above. Some fractionation by molecular weight occurs, which we are ignoring here. In simple permeation, dp/dz is constant with z and can be replaced by (p,-pJ/Z. Here, p. is the exit value and p,,the entrant (or, initial) value of the total pressure of the permeating gas, and Z is again the wall thickness. In common situations there is enough sweeping of the exterior or exit side of the wall that pB may be taken as zero. This simple model has obvious limitations with respect to real systems: but the separate effects of p, P, Gd and r on CD remain about as shown. The conclusion for permeability is thus sensibly the same as for diffusion: gas leakage as well as diffusion through a refractory wall is diminished by decreasing its apparent porosity and pore size; and (though rarely practical) by increasing the wall thickness. An important pertinence of the above equation in the reverse sense is in computing the pressure drop, p,,-perin porous diffusers, used e.g. for 020r Ar blowing of steelmaking vessels (Chapter Ill). Those opencelled refractory-materials have large porosities and large pore sizes, whereby both Gd and 2 approach unity; and the use of a singlecomponent gas simplifies the determination and use of Dr. Then 0 = -DP.A~/Z. An alternative isothermal permeability equation, entirely compatible with the above but used in a standard measurement method of ASTM,9 is:
WA = (K/$(Ap/L)
.

Here Q/A is the gas flow or permeation rate in cm3 (measured under standard conditions) per second per cm* of specimen cross-section; II is the gas viscosity in centipoise; AP/L (L equivalent to our Z) is the absolute pressure drop through the specimen in atm./cm; and K, the coefficient of permeability, is in darcys. The darcy is a unit of permeability such that K = 1 darcy when Q/A, q, and dp/L are all unity. This equation and its terms will be commonly found in the engineering literature of permeation; but it omits the relations of permeability to porosity and pore size given by our preceding

Principles of Corrosion Resistance: Hot Gases and Dusts

259

equation in O. It is thus less informative as to microstructure. The coefficients K/T) and D are clearly equivalent; but they are by no means numerically equal, as their units differ.

Condensation-Corrosion

by Gases

Interaction Processes. Again for the time being we shall set aside redox reactions in gas corrosion. That done, there remain three possible modes of interaction of a gas with the external and First, if the gas is condensible internal surfaces of a refractory. (referred to as a vapor), in the course of penetration of the porosity
and moving down the temperature gradient in a wall, the gas may literally condense or liquefy progressively. Second, the gas may condense by virtue of dissolving in the refractory; and third, it may
condense by virtue of reacting chemically to form one or more new compounds. These three possible modes, in the order given, are progressively more energetic and rapid and hence are progressively

into a narrow band in the porous solid. The one but impossible for gases is to dissolve components of the refractory directly. For that reason we have called gas-phase corrosion condensation-corrosion, as opposed to the term

more concentrated

mode

open to liquids

dissolufion-corrosion

used for liquids.

Once condensation

has occurred, however, the basic criteria

for liquid corrosion apply. Liquid interaction products are the hallmark of corrosive gases. If liquid products occur, they will be wetting; but their penetration via the porosity will be paced by the gas diffusion and condensation rate, not by capiilarity from an external reservoir. Thus rapid slabbing is absent in gas-exposed refractories. Invasive debonding by liquid interaction products observes the reactivity distinction between refractory matrix and grains as described in Chapter VI. But again this tends to be paced by the gas penetration rate or slow rate of generation of liquid, in the absence of appreciable capillary flow. Even liquid interaction products tend to protect the underlying solid somewhat, however, so that the depth into the refractory at which maximum gas reaction rates occur tends to increase with time. Eventually the depth of alteration becomes large. But in the most aggressive cases, blinding of the hot-face pores with liquid occurs early and the most dramatic alteration is concentrated there. Reaction at depth then becomes paced by diffusion through liquid-filled pores near the hot face. This concentration of liquid products at macroscopic surfaces causes severe local melting by dissolution, especially in crevices. Mortared joints between bricks are particularly vulnerable in this respect, as mortars tend to be more reactive than well-sintered bricks. In contrast with the blinding of pores, low-viscosity liquids condensed

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Handbook of Industrial Refractories Technology

in mortared joints tend to run out of the crevices by gravity, at once carrying out dissolved mortar and exposing the crevices to further condensation. This gravitational flow is most marked in vertical brick joints in sidewalls, and quite generally in roof joints. Attack is most severe with liquids of lowest viscosity, hence with alkalies and chlorides.27e It Is not uncommon for otherwise-sound bricks to fall out of a roof eventually in such service, requiring shutdown for repair to avoid a massive collapse. Temperature is a major factor, both in reaction kinetics and in its effect on liquid viscosity. Sulfur dioxide, usually from combustion, gives good examples of most of the condensation-corrosion patterns found in refractory interiors. Its condensation is essentially the reverse of the Decomposition of Sulfates, discussed under that heading in Chapter II. Unaccompanied by appreciable alkalies, SOPreacts with oxidic refractories in accordance with the Acid-Base Series of Oxides (Chapter VI). Condensation-reaction occurs with CaO in refractories at about 1400% and down; with MgO at about 11 OOOC and down; with A1203 or ZrOpat much lower temperatures, about 600C and down: and inappreciably at all with SiOo. Given the refractory type and a hotface temperature above the appropriate limit, SO, penetrates the porosity but does not condense until (with a negative AT across a wall) that limiting temperature is reached. Refractory alteration in that case occurs well inside a wall instead of at the hot face, while other corrosive gases may attack the latter region. This separation of corrosive reactions has been seen, for example, in oil-fired boiler linings.70~280 When alkali vapors are present with SOpat the same time, e.g. Na,O, the condensation of Na$O,starts at still higher temperatures and overlaps with SO2attack on the refractory. Liquid Na,SO,appears in this case at some 16OOOCand down. Examples are seen in the cement kiln hot zone,108 in coal processing,203 and emphatically in Checkers, it will be glass furnace checkers. 17*,275,27*,278,2*1 recalled, operate over a large AT/Ah and dT/dt as well, so that the spectrum of condensation products is ultimately spread out, including by chromatographic redistribution (i.e., vaporization-recondensation) in cycling.922*12*2 Condensed liquids fill the porosity and engage in debonding of They may experience freeze-thaw cycling, and if the refractory. solidified may create thermal expansion mismatches with the host. The typical consequences are weakening, softening, swelling, and finally even slabbing. 7~~~c*l~~7~~*el~*~ These are additional to the surface-concentrated effects of dripping and brick separation mentioned previously above.

Principles of Corrosion Resistance: Hot Gases and Dusts

261

Corrosive Gases. In compiling a summary list of corrosive gases, the Acid-Base Series of Oxides is a good place to start. That Series should be reviewed (Chapter VI). The strongest acids and bases at its extremities are volatile, and these react with the chemically opposite components of the atmosphere and of oxidic refractories. Oxides of nitrogen are infrequently encountered in quantity, but nitrate interaction products are low-melting. SO9and SOSform liquid sulfates in restricted temperature regions, the former by simultaneous oxidation to SO3in the process of condensing. Sulfite products are generally unstable at hot process temperatures. Phosphorus oxide vapors produce relatively high-melting phosphate reaction products (Chapter II), and are generally considered to be noncorrosive on that
account. They are also rarely encountered as gases, usually as minor components of liquid slags. The same is true of B,O,: it is generally met as a component of liquid silicates, infrequently as a free

gas.92 COPis commonly met as a gas, but carbonate reaction products are thermally unstable above about 700-1000C (Chapter II). CO, is frequently an agent of redox corrosion, however. CO, equally commonly met, has no addition reactions with solid oxides and is restricted to redox corrosion alone. Volatile oxides of arsenic are encountered in some nonferrous metal operations, and are corrosive. This recounting covers the top of the Acid-Base Series down to SiOp,below which volatile species generally do not occur. The volatile basic oxides of the Series are the alkalies, K20 and Na,O, and their corresponding hydroxides, KOH and .NaOH. Though encountered as components of process liquids, these are also distilled out as gases in the blast furnace, in glassmaking and Portland cement manufacture, and in other comparably hightemperature processes such as in steel and in the sintering and fusion of refractory oxides and ceramics. Their reaction products with containing refractories are almost always low-melting. Even more volatile and more corrosive than the alkalies are the chlorides. The identity of the chlorides boiled out of an inorganic process liquid depends on the cations that are present; so does the temperature at which vaporization occurs. Alkali chlorides are by no means the most volatile. HCI gas is encountered in acidic systems, and may be accompanied or followed by others as temperature increases. Condensation of chlorides in refractories typically produces liquids, but these products are most often oxychlorides: solutions of refractory oxides (including silicates) in chloride hosts. Chloride ion also dissolves substitutionally in refractory oxides, lowering their melting temperatures. A summary list of corrosive gases and vapors is:

262 Handbook of industrial RefractoriesTechnology Acidic Oxides s:: 1: -79 B.p., OC 47 Basic Oxides Na,O NaOH KOH K,O Big, 1275 1390 1320 (1200) Volatile Chlorides HCI BCIB SiCi, AICI:, SbCi, ZnCip PbCi2 CdCip NiCI;! M9Ct2 NaCi KCI

B;$-,
-84 :: 178

1412 1413 1500

223 732 950 960 973

Process gases are usually accompanied by fogs and dusts of more complex composition: the roster of real corrosive agents is not so simple as this table suggests. Products of combustion, often including coal ash or oil ash, are part of the direct-fired corrosive environment. Countermeasures. Methods of resisting condensationcorrosion by gases are substantially the same as those marshalled against hot process liquids. Even non-wetted refractory compositions are useful, not because wetting is a factor in gas penetration but because a non-wetted surface is also relatively resistant to reaction, whether with a liquid or with its vapor. The reduction of porosity, an achievement mainly of the 1970s and following, has greatly improved gas-phase corrosion resistance. Upper sidewall and roof refractory compositions are usually chosen from the same broad family used to resist the corresponding process liquid. Exceptions are made for the fact that gas-phase corrosion is slower, if less-expensive refractory types can therefore serve adequately long. Other exceptions are made for special situations including gas-fog-dust mixtures, local temperature differences, and local velocity and impingement patterns resulting in abrasion. In general, basic refractories (almost always containing chrome ore) are used where atmospheric exposures are alkaline-to-neutral and hot face temperatures are highest.losll78,203,278,281 The hot zones in copper furnaces and cement kilns and the uncooied sidewalls of electric arc steel furnaces are examples, and the uppermost zone of glass checkers. Where exposures are neutral to acidic and temperatures are highest, high-alumina, zircon, A-Z-S, and muiiite refractory types are employed.2s~s2~275~2sl~282 The use of silica acid refractories in furnace and kiln roofs, once almost

Principles of Corrosion Resistance: Hot Gases and Dusts

263

universal, has given way to these higher-temperature types to such an extent that silica bricks are no longer manufactured in quantity in the U.S.A. Super-duty silica still makes good crowns, however.

As operating temperatures lessen, high-alumina refractory applications expand into alkaline exposures and then give way successively to super-duty, high-duty, and regular fireclay products at
successively lower cost.69g870,2751280-282 A classic example of this progression of usage, from basic to alumina and alumina + mullite

and on to the several grades of fireclay refractories, occurs in tunnel and periodic ceramic-firing kilns as their hot face temperatures decrease from -1850C to 4000C -- depending on the products being fired and the zoning in each different kiln. One reason why the highest-temperature oxidic refractories have lapped successfully into each others environmental domains is that they have become better made -- purer, much less porous, and better bonde&arkheneemore +zorrosion-resistant-acrossthe board. Indeed, there are relatively few corrosive applications today in which only one type of working refractory can survive competitively. This is a good thing: other qualities are required as well, whose specifications vary from one installation to another. Thermal stress resistance, redox cycling resistance, thermal conductivity, hot strength, and abrasion resistance are examples of these other considerations. The process operator has some breadth of choice among the several characteristics that are most critical. Gas Corrosion by Oxidation-Reduction
It is appropriate to close the subject of gas corrosion by returning briefly to redox reactions. Gases are ubiquitous instruments of oxidation and reduction, and their ability to reach over large distances from their point of generation or release adds a spatial dimension to their corrosion phenomena. Most of the reactions described under Redox Alteration in Chapter V involve gaseous reagents; but not all of the gases which may be faced by refractories are catalogued there. First, an important group of condensible vapors is comprised of the volatile chemical elements. These ordinarily appear along with their liquids in smelting or other reducing chemical process operations. They are most likely to be found among the low-melting elements in Figure 11-2. But still others turn up in metallurgy as alloying elements, or elsewhere m chemical and device applications. They too have to be handled hot. A table of twenty more-or-less volatile elements is provided below, in alphabetical order by symbol, giving the m.p. and b.p. of each in OC.11 This table omits the low-melting elements gallium, germanium, indium and tin, all of which boil close to or above 2000C.

264

Handbook of Industrial Refractories Technology Mp.,

-mm

Element

OC

B.p., C 615s 1140 1560 1240 767 670 357 760 1336
1107

Element Na Ll :tr Se Sr Te TI
Zn

M.p., OC 98 34248
113 631 217 800 452 302 420

B.p., OC 880 280 1620

445 1380 688 1150 1390 1460 907

850 271 845 321 -ii 18e26 649

Whether an element in this list will be encountered as a vapor depends on the temperature of a relevant process operation. A gasexposed refractory for the operation may be in the form of a crucible, still, retort, kiln, furnace, or associated plumbing, whose first obligation will be to prohibit vapor leakage. Its second obligation will be to survive reduction and to withstand alteration by the product of oxidation of the metal vapor. Inquiries as to redox reactions must encompass not only refractory major phases, but also their minor and impurity components. Each such inquiry consists of: (a) proposing a valid chemical redox equation and the physical state of each substance therein, including solutions; (b) estimating the chemical activity of each substance; (c) acquiring the AG Or data for each, either from compilations such as the JANAF Table@ or from the literature of the substance; and (d) using the equilibrium thermodynamic techniques given in Chapter V to assess the postulated reaction. It should be noted that, at any temperature between the m.p. and the b.p., a liquid and its vapor at the equilibrium vapor-pressure are equally at standard state, for which the activity a -1. Thus exposure of a refractory either to a liquid or to its saturated vapor is thermodynamically the same. 83 The differences lie in transport mechanisms and kinetics. The second set of gaseous redox reagents encountered by refractories is comprised of the permanent oxidizing and reducing gases. These were incompletely sampled in Chapter V as Redox Reagents in Combustion Atmospheres. The fuller table below presents the most common oxidizing and reducing gases, respectively. Each set is given in approximate order of decreasing thermodynamic power.

Principles of Corrosion Resistance: Hot Gases and Dusts

265

Oxidizing Gases
Et
02

Reducing Gases
[Activ;Fls
3

& Carbon]

HCI CO,

ZH, [Corn::;
2

s2p,

Metal Vapors]

Except for CIp, HCI, and the metal vapors, the reduced products of the oxidizing gases and the oxidized products of the reducing gases are themselves volatile and go back into the local atmosphere after reaction. That is, with these named exceptions the damage done to a refractory by redox corrosion is almost solely the result of valence alteration of the refractory composition itself. Sufficient examples of that damage are given in Chapter V.
Certain of these oxidized and reduced pairs of gases can carry out a further kinetic function in corrosion. This is to supply an alternate path for solid-state reactions which otherwise would soon stop due to parting of their solid-solid interfaces.283 The MgO+C reaction in composite basic refractories, for example, may proceed as,

MO + C + Mg,, + CO,,,,
only until the reagents lose contact. Recall, however, that the atmosphere in the BOF is a CO-CO2mixture which fills the pores of the refractory. Now the sequence,

Mgo + CO(,)+ Mg,,) + COP(,)and

CO,(*) + c + 2 co,, 9

can replace the former solid-solid reaction. The sum of these two is exactly the former equation; and their thermodynamic equivalence to it in terms of the equilibrium p(C02)/p(CO) ratio can be readily demonstrated from the data in Table V.l. All that is necessary is that the gases be confined together in a small space (e.g., pores), reasonably isolated from the external atmosphere. In the blast furnace, the FeO+C reaction is similarly facilitated by CO on a huge scale -- though a liquid-solid mechanism is also in effect there.

Countermeasures. The available methods of controlling or slowing redox corrosion have all been mentioned previously. These include, in addition to limited allowable process modifications of temperature and atmospheric exposure: (1) selection of refractory

266

Handbook of Industrial Refractories Technology

compositions that are resistant to reduction or to oxidation; (2) elimination of oxidizible-reducible minor refractory components or impurities, e.g., Fe,O, and TiO*; and (3) inhibiting the entry of the corrosive gas and exit of gaseous products, e.g., by decreasing porosity and pore size or by glazing or coating of the working face or back face of the refractory. (4) Sacrificial additives have also been

mentioned.

The most difficult and damaging redox environment remains the cyclic one, for example the alternation of refractory exposures to process CO and to ambient air. The most effective defense that has ever been devised is removal of the unnecessary half of this cycle by
the process architect.

DUSTS:

DEPOSITION

AND

ABRASION

Hot process dusts originate in feed materials, but also importantly in the grinding action of moving solids within heated vessels. A further source is evaporation-condensation from process chemicals, while the combustion of inexpensive fuels always yields some dust and may produce soot (carbon dust) in addition. A number of such cases were called out in Chapter Ill. Dusts have two characteristic effects on refractories.
Deposition: Scaling and Caking

Industrial process dusts are often accompanied by fog and by gases which condense on refractories. These accompanying liquids facilitate the gradual accretion of solid particles on the working surfaces. The resulting build-up can be variously a hard scale, or a somewhat porous, lightly-sintered cake, or (typically downstream and cooler) simply a pile of powder. In some less-obvious cases, dust, fog, and condensing gases all fuse together to create an invasive

liquid -- an extension of condensation-corrosion.

Solid build-up on refractory surfaces tends to seal off the porosity and is a deterrent to chemical corrosion. This is often welcomed. In large masonry installations, however, the deposition of hard scale in crevices together with temperature cycling or mechanical flexing can eventually fracture and even dislodge bricks. Since scaling and caking of walls may be unacceptable to a particular process, periodic de-scaling operations may be carried out which themselves are mechanically damaging to the working lining. These operations include the firing of explosive charges and/or projectiles as in rotary kilns, and the use of air chisels or pneumatic hammers as

Principles of Corrosion Resistance: Hot Gases and Dusts in shafts and rotaries, for example. shortening. The net consequence

267

may be life-

Finally, there are a number of geometrical situations in which solid build-up in inaccessible places actually terminates the life of a refractory installation or component. A dramatic example of this has been in glass checkers,*81 whose passageway dimensions have now become much enlarged by re-design to allow for their gradual constriction by caking. The effect of build-up on the transfer of heat from gas to refractory has to be figured in as well, requiring overdesign of the checker height. Scaling, caking, and the accumulation of dust are operational problems which call for operational design adaptations. There is little latitude for refractory compositional countermeasures. In some instances, refractory hot-face glazing in manufacture has provided a smooth surface to minimize dust adhesion. But on the whole this approach can work only where simultaneous chemical corrosion is minor. By contrast, refractory selection does play some defensive role against the second characteristic mode of dust attack: abrasive wear. Abrasive Wear

Lacking protective deposition or build-up, abrasion of the refractory working face by dusts often contributes to wear. This mechanical mode of recession is familiar in all materials wherever solid patticulates are entrained in rapidly-moving fluids. Abrasive wear depends on the impinging particle size, shape, hardness, mass and velocity; on the inertia and viscosity of the entraining fluid; on the presence of intervening films; on the refractory surface geometry and texture; and on the angle of impact. Abrasion is frequently an accompaniment and aggravator of corrosion, as has been mentioned. Its severity is hard to predict; but throats, ports, flues, elbows, valves, angular shapes, surface roughness, and similar sites of high gas velocity or turbulence are most vulnerable. Apart from the streamlining of ducting design and the limited use of glazing for smooth texture, the simple refractory property of most importance in abrasion resistance is hardness. The following table gives room-temperature hardness values from Ref. 11 for most of the crystalline refractory substances listed in Table IV.1, plus one or two others of interest. Within each group (oxides and nonoxides, respectively), these are listed in approximate order of decreasing hardness on the Mohs scale,8 which is a relative scratch-hardness scale from 1 (talc) to 10 (diamond). Where data were not given,11 estimates have been made by analogy and placed in parentheses.

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Handbook of Industrial Refractories Technology

Substance
Corundum Spine1 Zircon
Chrome Spine1 Mullite Dialuminum Silicate Silica (quartz) Forsterite Cordierite
A1203

Mohs Hardness
MgAkzO4 ZrSi04 MgCr&
AW2013

Substance
Silicon Carbide Boron Carbide Titanium Carbide Titanium Nitride Titanium Boride

Mohs Hardness
sic Tic TiN TiBp C gY.)
B4C

A12Si05 Si02

9 7.5-8 7.5-8 (7.5-8) (7.5) 7-7.5

Zirconia Titania (wile)

Magnesia (perfclase)

Zr02 Ti02 WO

Mg2Si04 MwW5Ola

;
7 6.5 6-8.5
8

Carbon (various) Graphite Boron Nitride

There is no known compilation of hardness data at high temperatures. However, each of these substances probably retains its hardness tolerably well up toward its Tammann temperature (Table IV.1). To put these values in perspective, sintered periclase at hardness 6 is used in the charge pad area of basic oxygen steelmaking furnaces, while high-alumina at 9 or Sic at 9.5 does high-wear duty in most other metallurgical furnaces receiving heavy charges of scrap or ingot and ore. Those are severe impact applications, calling critically for matrix toughness in addition to grain hardness. In dust-abrasive exposure, resistance of the matrix to mechanical undermining is also about a8 important as grain hardness; high-purity, high-density, high-fired, high-melting compositions are the most durable. Those are the same characteristics that impart corrosion resistance; so an excellent refractory for the one is likely to be excellent for the other as well. Experience suggests that nitride-bonded Sic may be the number one abrasion-resistant refractory at this time, either cold or hot. But it is not entirely oxidation-proof. Alumina tops the list of oxides in a wide variety of abrasive applications. Yet whether or not chemical debonding of the working face accompanies abrasion, the matrix may well govern refractory selection.ll7~208~224-228

CONCLUSION: CONSTRUCTION

PRINCIPLES

OF WORKING

REFRACTORY

Chapters V-VII together relate the major considerations and material characteristic8 that qualify industrial refractories for duty in corrosive environments. The materials which actually face or enclose those environments are the working refractories. In illustrating the principles of their construction, reference has been made to nearly every chemical and phase composition and every microstructural type

Principles of Corrosion Resistance: Hot Gases and Dusts

269

that is commonly encountered. These concepts of refractory construction have been developed in relation to the phenomena by which products survive or excel. It remains to re-group working refractory products under the classifications used in the industry -such as might be found in a manufacturers catalog. These and some important features of each class will be summarized in Chapter VIII. Another whole category of like materials is comprised of the thermally insulating refractories. Their conditions of use are on the whole much less corrosion-intensive. Insulating refractories will be described and classified in Chapter IX. Then the selection of lining materials for the equipment of Chapter Ill will be addressed, followed in turn by examination of other properties required for use in engineering design.