13 Adel Nofal PDF
13 Adel Nofal PDF
13 Adel Nofal PDF
❖ These alloyed white irons provide the best combination of toughness and
abrasion resistance attainable among the white cast irons.
❖ In an idealized cube of high Cr-white iron, the randomly oriented rods of carbide
embedded in the metallic matrix are shown.
INTRODUCTION
❖ The 25% Cr or 28% Cr white irons, which may contain other alloying
additions of molybdenum and/or nickel up to 1.5%.
i) Chromium
❖ With small castings such as grinding balls, which can be shaken out of the
molds white still hot, air cooling from the shakeout temperature will produce
the desired martensitic structure even when the nickel content is as low as
2.7%.
❖ On the other hand, an excessively high nickel content (more than about 6.5%)
will so stabilize the austenite that little martensite, if any, can be formed in
castings of any size.
❖ Ni-Hard IV is often specified for pumps and other equipment used for handling
abrasive slurries because of its combination of relatively good strength,
toughness, and abrasion resistance.
❖ Nickel contents higher than this range tend to excessively stabilize the
austenite, leading to austenite retention.
iii) A special grade, class I type C, has been developed for producing
grinding balls and slugs. Here the nickel-chromium alloy composition has
been adapted for chill casting and specialized sand casting processes.
❖ The class I type D (Ni-Hard 4) alloy is a
modified nickel-chromium iron that
contains higher levels of chromium,
ranging from 7 to 11% and increased
levels of nickel, ranging from 5 to 7%.
❖ Class I type D, Ni-Hard type 4, has a higher level of strength and toughness and
is therefore used for the more severe applications that justify its added alloy
costs. It is commonly used for pump volutes handling abrasive slurries and coal
pulverizer table segments and tires.
❖ The class I type C alloy (Ni-Hard 3) is specially designed for the production of
grinding balls. This grade is both sand cast and chill cast. Chill casting has the
advantage of lower alloy cost, and, more important, provides a 15 to 30%
improvement for 8 h at 260 to 315C.
Examples of Ni-Hard Castings
❖ They are usually considered the hardest of all grades of white cast irons.
❖ Compared to the lower-alloy nickel-chromium white irons, the eutectic carbides are harder
and can be heat treated to achieve castings of higher hardness.
❖ Molybdenum, as well as nickel and copper when needed, is added to prevent pearlite and to
ensure maximum hardness.
❖ The high-chromium irons (class III of ASTM A532). These general-purpose irons, also
called 25% Cr and 28% Cr irons, contain 23 to 28% Cr with up to 1.5% Mo.
❖ To prevent pearlite and attain maximum hardness, molybdenum is added in all but the
lightest-cast sections.
❖ Although the maximum attainable hardness is not as high as in the class II chromium-
molybdenum white irons, these alloys are selected when resistance to corrosion is
also desired.
❖ Class I and II high-chromium white irons are superior in abrasion resistance and
are used effectively in impellers and volutes in slurry pumps, classifier wear
shoes, brick molds, impeller blades and liners for shot blasting equipment, and
refiner disks in pulp refiners.
❖ In many applications they withstand heavy impact loading, such as from impact
hammers, roller segments and ring segments in coal grinding mills, feed-end
lifter bars and mill liners in ball mills for hard-rock mining, pulverizer rolls, and
rolling mill rolls.
Examples of High Cr Cast Iron for Abrasion Resistance Castings
❖ Fully austenitic matrix structures provide the best resistance to corrosion, but
some reduction in abrasion resistance must be expected.
❖ Because of castability and cost, high-chromium white iron castings can often be
used for complex and intricate parts in high-temperature applications at
considerable savings compared to stainless steel.
❖ The carbon content of these alloys ranges from 1 to 2%. The choice of an exact
composition is critical to the prevention of -phase formation at intermediate
temperatures and at the same time avoids the ferrite-to-austenite transformation
during thermal cycling, which leads to distortion and cracking.
❖ Typical applications include recuperator tubes; breaker bars and trays in sinter
furnaces; grates, burner nozzles, and other furnace parts; glass bottle molds;
and valve seats for combustion engines.
Examples of High Cr Cast Iron for High Temp. Resistance Castings
Valve Seats
Burner Nozzles
MICROSTRUCTURES OF HIGH-Cr IRONS
❖ Although relatively soft, can give satisfactory abrasive wear performance, due to
pronounced work hardening in service.
Carbides
❖ For castings that will be heat treated, the desired mold-cooled structure is
often pearlite. This softer structure will facilitate removal of gates and risers
and minimize the transformational and thermal stresses that cause cracking.
❖ The pearlitic structure will also shorten the response to heat treatment.
❖ The heat treatment requires an air quench from the austenitizing temperature.
Faster cooling rates should not be used, because the casting can develop
cracks due to high thermal and/or stresses.
❖ Thus, the alloy must have sufficient hardenability to allow air hardening.
However, overalloying with manganese, nickel, and copper promotes retained
austenite, which detracts from resistance to abrasion and spalling.
❖ Pearlite will always occur when alloying is insufficient to inhibit its formation.
❖ Most of the chromium is tied up in the chromium carbides, so other alloying
relatively low-cost material will have adequate wear resistance, higher-cost
material will have measurably superior wear resistance.
❖ The ratio of wear rate to replacement cost should be evaluated. This ratio can
be an effective means of evaluating the most economical use of materials.
❖ Because these volume changes may not occur simultaneously in each part of
the casting, they tend to set up residual stresses, which may be very high and
may therefore cause the casting to crack in the foundry or in service.
❖ The nickel-chromium martensitic white irons, containing up to about 7% Ni and 11% Cr,
usually put into service after only a low-temperature heat treatment at 230 to 290C to
temper the martensite and to increase toughness.
❖ If retained austenite is present and the iron therefore has less than optimum hardness, a
subzero treatment down to liquid nitrogen temperature can be employed to transform
much of the retained austenite to martensite.
❖ Subzero treatment substantially raises the hardness, often as much as 100 Brinell points.
❖ Following subzero treatment, the castings are almost always tempered at 230 to 260C.
❖ However, high-temperature treatments are usually less desirable than subzero treatments,
because the former are more costly and more likely to induce cracking due to
transformation stresses.
iii) The high-chromium martensitic white irons (>12% Cr)
❖ The high-chromium martensitic white irons (>12% Cr) must be subjected to a high-
temperature heat treatment to develop full hardness. They can be annealed to soften
them for machining, then hardened to develop the required abrasion resistance.
❖ The usual reaustenitizing temperature for high-temperature irons ranges from about
950C for a 15Cr-Mo iron to about 1065C for a 27% Cr iron.
❖ This lowers the amount of carbon dissolved in the austenite to a level that permits
transformation to martensite during cooling to room temperature.
❖ Air quenching is usually used, although small, simply shaped castings can be
quenched in oil or molten salt without producing quench cracks.
❖ In low-chromium white irons, rapid solidification will also reduce any tendency
toward formation of graphite. The presence of graphite severely degrades
abrasion resistance.
❖ Chills in the mold can be used to promote directional solidification and therefore
reduce shrinkage cavities in the casting.
❖ This reversal of the continuous phase in the structure tends to increase the
fracture toughness of white irons, but only those irons that have a hypoeutectic
or eutectic carbon equivalent.
❖ All hypereutectic white irons are relatively brittle and are seldom used
commercially.
Structure of sand-cast white iron. Composition: 3.5TC-0.4Si-0.8Mn-16.0Cr-3.0Ni. Structure shows M7C3 carbides in a
matrix of austenite containing small amounts of pearlite and martensite.
❖ After a white iron casting has solidified and begins to cool to room temperature,
the carbide phase may decompose into graphite plus ferrite or austenite.
ii) As the austenite cools further, through the range of 700 to 540C, it tends to
transform to pearlite. This transformation can be suppressed, however, by
rapid cooling and/or by the use of pearlite-suppressing elements in the iron.
Nickel, manganese, and copper are the principal pearlite-suppressing
elements.
iii) Upon cooling to below about 540C, the austenite may transform to bainite or
martensite, thus producing martensitic white iron, which is currently the most
widely used type of abrasion-resistant white iron.
Martensitic white irons usually contain some retained austenite, which is not
considered objectionable unless it exceeds about 15%.
❖ Silicon is also used to enhance the hardening response when the castings are
cooled below ambient temperature.
Structure developed by the heat treatment of a high-chromium iron. Specimen from a chute liner 50 mm thick,
containing 2.6% total carbon, 1.5% Si, 1.1% Mn, 14.3% Cr, and 3.0% Mo, reheated to 1040 to 1065C and air
cooled. Structure is M7C3 eutectic carbides in a matrix of martensite and fine spheroidized M3C carbides.
❖ Hardness is the principal property of white iron that is routinely determined and
reported. Other (nonstandard) tests to determine strength, impact resistance,
and fracture toughness are sometimes employed by individual users,
producers, or laboratories. Because of the difficulty of preparing test
specimens, especially from heavy-section castings, these nonstandard tests
are seldom used for routine quality control.
❖ Two exceptions are the tumbling-breakage test and the ball-on-ball impact
spalling test, which have been routinely used by certain producers for testing
grinding balls.
❖ Minimum hardness values for pearlitic white irons are 321 HB for the low-
carbon grade and 400 HB for the high-carbon grade. A chill-cast high-carbon
2% Cr white iron may reach a hardness of about 600 HB.
❖ A typical hardness range for a sand-cast high-carbon grade is about 450 to 550
HB.
❖ The minimum hardness specified for the hardened (heat-treated) class II
castings is well below the average expected hardness.
❖ These irons, when fully hardened so that they are free from high-temperature
products of austenite transformation, will have hardness values ranging from
about 800 to 950 HV (depending on retained austenite content). The 800 to 950
HV range is equivalent to 700 to 790 HB or 62.5 to 67.5 HRC.
❖ For optimum abrasion resistance of the class I irons in Table 1, the minimum
Brinell hardness, as measured with a tungsten carbide ball or converted from
HV or HRC values, should be 700 HB.
❖ Hardness conversions for white irons are
somewhat different from the published data
for steel. The next table lists data for two
classes of white irons: high-chromium irons
and nickel-chromium irons. Because of
inherent variations in structure for many
cast irons, hardness conversion must be
made cautiously. For example, Brinell
hardness tests are more consistent and
reliable for coarse structures such as those
typical of heavy sections.
❖ Limited data indicate that the yield strengths of white irons are about 90% of their
tensile strengths.
❖ Because of the near-zero ductility of white irons, the usefulness of tensile test
data for design or quality assurance is limited.
❖ Values of transverse strength, deflection, and toughness for as-cast test bars should
be considered very general; the wide spread of these data emphasizes that
properties depend on a marked degree on composition and the conditions under
which the castings were produced.
Typical mechanical properties of alloyed white irons
❖ Chromium-molybdenum white cast irons are well known for their good abrasion
resistance. Abrasion is a type of wear that occurs under the relative movement of
a hard body (e.g. mineral or work-hardened wear particle) and the softer surface
of a mating material.
❖ In the abrasive process, the hard body may be fractured and the softer surface
will be cracked and/or deformed, and the material will be removed from the
surface, resulting in a measurable volume loss.
❖ Mining and earthmoving equipment must withstand severe service stresses and
loading rates, so industrial applications of white cast irons under abrasive
conditions are frequently limited by their toughness.
❖ Carbon content was varied from 1.4 to 3.9% and chromium content was varied
from 11.6 to 25.7%. Slight variations in copper content were also made. The
matrix microstructures that were employed included predominantly austenitic
structures and predominantly martensitic structures.
❖ In addition, one composition of white iron (heat No. 63) was subjected to 30
different heat treatment to define the effect of matrix microstructure on dynamic
fracture toughness and abrasion resistance. The following figure summarizes
these heat treatments.
K.-H. Zum Gahr and D.V. Doane, Optimizing Fracture Toughness and Abrasion
Resistance in White Cast Irons, Metall. Trans. A, Vol 11, 1980, p613-620.
Summary of heat treatments carried out
on Heat 63.
❖ Dynamic fracture toughness decreased linearly to a first approximation with
increasing volume of carbides.
❖ The K1d values were found to be lower in the martensitic condition than in the
austenitic condition at the same carbide volume.
❖ As carbide volumes increased above 30%, however, abrasive wear loss increased
with both matrix structures.
❖ The bulk hardness of the white cast irons measured on surfaces of rubber wheel
test specimens increased with increasing carbide volume linearly to first
approximation.
Abrasive wear volume loss and hardness as a function of volume of massive carbides. (a)
Austenitic irons (as-cast, stress-relieved 2h at 200C). (b) Martensitic irons (castings heat
treated 5h at 900C, air quenched, refrigerated twice at -78C, stress-relieved 2h at 200C).
❖ A predominantly austenitic matrix ❖ Different structures with the same
resulted in the highest dynamic K1d value can show large differences
fracture toughness. in hardness, and, conversely, K1d
values can vary substantially at the
❖ Predominantly austenitic as-cast same hardness.
structures, stress-relieved
between 200 and 400C for 2 h,
exhibited good dynamic fracture
toughness values.
❖ Austenitic structures are the only choice, however if high dynamic fracture
toughness is required.
❖ Martensitic matrices resulted in much higher abrasive wear resistance, but they
can be used only where moderate K1d values can be used.
❖ Careful selection of heat treatment (data points 17 and 51) provided both good
wear resistance and reasonable fracture toughness.
❖ These heat treatments involved air quenching from high temperatures, followed
by tempering at 200C.
Abrasive wear resistance vs. fracture toughness for Heat 63. The wear resistance is
expressed as the reciprocal of volume loss (V).
SPALLING RESISTANCE
❖ A study of spalling due to impact of high-chromium
white cast iron grinding ball media shows the
advantage of careful control of heat treatment. In this
test, balls were impacted against each other until they
broke or lost 100 g by spalling. The tests were
conducted in the ball-on-ball impact-spalling testing
machine. The white irons tested had chemical
compositions in the following range:
R. Blickensderter, J.H. Tylczek, and J. Dodd, The Effect of Heat Treatment on Spalling
of a Cr-Mo White Cast Iron, Wear of Materials, American Society of Mechanical
Engineers, 1983, p. 471-476.
Ball-on-ball impact-spalling test machine. In this test, 75 mm diam. white iron grinding
balls are dropped about 3.5 m to produce multiple impacts on the balls at the base of the
curved tube. The energy of the first impact is 54 J. The energy of subsequent impacts
decreases to about 5 J at the last impact.
❖ The balls were given the heat treatments identified in the following table.
❖ R1850 balls were improved by Spalling life of variously heat-treated white iron grinding
tempering. The longest 100 g life, balls. Life is number of impacts to produce 100 g loss.
127,900 impacts, resulted from
the 540C tempering treatment.
References
1. G. Laird II, Some Comments on White Cast Iron Microstructures and Wear
Properties, Trans. AFS, Vol 1993, p 497-504.
2. F. Maratray and A. Poulalion, “Study of the Hardness of the Martensitic
Structures in High-Chromium Ferrous Alloys and the Control and
Transformation of Retained Austenite:, Publication M-399E, Climax,
Molybdenum Co., 1984.
3. J. Dodd and J.L. Parks, “Factors Affecting the Production and Performance of
Thick Section High Chromium-Molybdenum Alloy Iron Castings: Publication
M383, AMAX, Inc.
Selected References
❖ All nickel-chromium white iron castings are given a stress-relief heat treatment
because, properly made, they have a martensitic matrix structure, as-cast.
❖ Tempering is performed between 205 to 260C for at least 4 h. This tempers the
martensite, relieves some of the transformation stresses, and increases the
strength and impact toughness by 50 to 80%.
❖ In the heat treatment of any white cast iron, care must be taken to avoid cracking
by thermal shock. Never place the castings in a hot furnace or otherwise subject
them to rapid heating or cooling. The risk of cracking increases with the
complexity of the casting shape and section thickness.
High-Temperature Heat Treatment
❖ In the past, hardening of the class I type D alloy, Ni-Hard 4 was performed by
supercritical heat treatment when as-cast hardness was insufficient.
❖ Refrigeration hat treatment is the more commonly practiced remedy for low
hardness today.
Refrigeration Treatments
❖ To achieve a hardness of 550 HB,
it is necessary that the as-cast
austenite-martensite present.
When martensite content is
increased to 80 to 90%, however,
hardness values exceed 650 HB.
❖ Too high a temperature increases the stability of the austenite, and the
higher amount of retained austenite reduces hardness.
❖ For castings that are fully pearlitic prior to heat treatment, the holding time at
temperature can be reduced.
Quenching
❖ Air quenching (vigorous fan cooling) the castings from the austenitizing
temperature to below the pearlite temperature range (that is, between 550
and 600C is highly recommended.
❖ Complex and heavy-section castings are often placed back into a furnace at
550 to 600C uniform temperature is reached within the castings.
❖ Typical tempering temperatures range from 480 to 540C and times range
from 8 to 12 h. Excess time or temperature results in softening and a drastic
reduction in abrasion resistance.
❖ Lower hardness can often be achieved with full annealing whereby castings
are heated in the range 955 to 1010C, followed by slow cooling to 760C and
holding this temperature for 10 to 50 h, depending on composition.
❖ Annealing does not affect the primary carbides or the potential for
subsequent hardening.
❖ The information in this article is largely taken from R.B. Gundlach and D.V.
Doane, Heat Treating of High-Alloy Irons, Heat Treating, Vol. 4, ASM
Handbook, 1991, p 697-708.
References
1. J. Dodd and J.L. Parks, “Factors Affecting the Production and Performance of
Thick Section High Chromium-Molybdenum Alloy Iron Castings”, Publication
M-383, AMAX.
2. W.W. Cias, Austenite Transformation Kinetics and Hardenability of Heat
Treated 17.5%Cr White Cast Irons, Trans. AFS, 1974, p. 317-328.