SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA

Preprint 12-013
A SUCCESSFULLY SERVICE TESTED HARD IRON WITH SUPERIOR ABRASION AND CORROSION RESISTANCE IS
AVAILABLE FOR THE MINERAL PROCESSING INDUSTRY.
G. A. Calboreanu, ARW & Sons Inc, Denver, CO

ABSTRACT

respectively 13-m versus 5-m the denuded zone width of proeutectic chromium carbide.

One way of cost reduction is attained when using materials with

improved erosion corrosion resistance. For many years hard irons
successfully answered the Mining Operation needs however
application ranges were limited due to the low chemical resistance of
such alloys. Corrosion resistance of any hard iron increases when
microscopically homogenizing chromium and generating passivation
conditions throughout and between all metallographic phases.
Chromium distribution of the new material called Max10 was
analyzed with EDS energy dispersive spectroscopy. At critical
depleted chromium carbide matrix interfaces chromium increased to
31.72% which is well within passivation levels.
Generally the corrosion resistance of high chromium hard irons
provided by Metal Casting Industry is limited to 0.5% sulfuric acid and
28 PPM ionic chlorides. Such restrains increased when using Max10 to
2.0% sulfuric acid and 100 PPM ionic chlorides.
Max10 contains 35% carbide volume fraction, has excellent
corrosion resistance within pH = 1.15 13.6 while fracture toughness
under plain - strain conditions and Mode I opening is KIC = 20
1/2
KSI.(inch) . Wear rate was calculated with the pin-on-disk apparatus
using a diamond indenter per ASTM G99 recommendation.

Photo 1. Optical microscope view of 25% Cr hard iron etched with

40% hydrochloric acid.
The matrix depletion in chromium along chromium carbide
matrix interfaces takes place through solid state diffusion reactions
which sustains chromium migration toward chromium carbides and
increase their chromium content. Under the circumstances passivation
conditions are diminished especially around the clustered chromium
carbides of eutectic cells.

After years of research, experimentation and implementation the

Max10 castings were service installed in slurry pumps and mixing
equipment. In some applications the life time of slurry pumps
manufactured in Max10 tripled versus previously used materials.
DEVELOPMENT PROGRAM
The development program had two major steps. First one was
completed when passivation conditions were reached by
homogenizing chromium distribution especially at the chromium
carbides matrix interfaces. The phase equilibrium, solubilities and
thermodynamics of constituents defined by the ternary phase diagram
iron chromium carbon proved helpful.
During the second development step the following physical and
mechanical properties were successfully tested:

Corrosion resistance in phosphoric acid, sulfuric acid and

ionic chloride environments;
Wear rate calculated per ASTM G99; [1]
Optimizing the chromium carbide distribution, tensile
strength, elongation, hardness and fracture toughness; [2],
[3]

HOMOGENIZING CHROMIUM AT MICROSCOPIC LEVEL

Photo 1 is a SEM microstructure view of 25% Cr hard iron per
ASTM A532 Standard specification for abrasive resistant cast iron
Class III Type A. [4]

Figure 1. Cr, C and Si concentration distribution between two

chromium carbides within the eutectic cell. [5]

Arrow A points to pro-eutectic chromium carbide, Arrow B

shows part of chromium carbide eutectic cell, Arrow C identifies two
out of many secondary chromium carbides of different shape and sizes
while Arrow D points to the chromium depleted zones which are also
called denuded zones. Due to the higher chromium carbide
concentration of eutectic cells the chromium depletion zone is larger

The comparative distribution data and the superior chromium

content of Max10 at the matrix chromium carbide interface are
shown in Table 1 and they were established with EDS Energy
Dispersive Spectroscopy.

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
Table 1. Microstructural chromium distribution.
Material

Max10

25 Cr%
Hard Iron

Location
Matrix
Eut. Carbide
Interface
Matrix
Eut. Carbide
Interface

EDS analyses
% Cr
% Fe
15.9
84.0
62.9
37.0
68.28
31.72
15.5
54.0
13.6

The large difference in chromium between the chromium carbides

and adjacent matrix generate different electrode potentials and
microscopic galvanic cells are developed which further enhance the
corrosion attack of the matrix.
Using well controlled manufacturing processes the chromium
migration in Max10 was diminished which consequently increased the
matrix chromium content at the carbide matrix interface to 31.72%.
Basically the denuded zones were eliminated. The chromium content
of Max10 at the carbide matrix interface is 2.33 fold higher than the
chromium contained in the denuded zone of 25% Cr.

Photo 2. SEM view of the corrosion pattern developed on the tested

0
0
Max10 sample surface in 60% phosphoric acid at 220 F (104 C).
EDS Area 1 identifies the matrix, EDS Area 2 shows clustered
eutectic chromium carbides while EDS Area 3 shows the matrix
chromium carbide interface. The F Arrows show the corrosive attack
inflicted into the matrix at chromium carbide matrix interface.

Within the matrix a smaller chromium migration occurs at the

matrix secondary carbide interfaces nevertheless it diminishes the
corrosion resistance around secondary carbides as well. Eliminating or
reducing the amount of fine cuboids crystallized M23C6 secondary
carbides improves the corrosion resistance of any high chromium hard
iron

Sulfuric Acid and pH Range

The following were the testing parameters:

TESTING THE CORROSION RESISTANCE OF MAX10

Sulfuric acid concentration: 2%;

0
0
Testing temperature: 158 F (70 C);
Testing time: 72 hours;

The corrosion rate was 17 MPY which according to the NACE

ranking is very good.

Phosphoric Acid
Most of time phosphate rocks have high amounts of quartz, ferric
oxide and harmful corrosive erosive contaminants. In such
operations Max10 is very much needed.

Photos 3, 4, 5 and 6. SEM views at different magnifications of the

0
0
Max10 sample surface tested in 2% sulfuric acid at 158 F (70 C) and
the pH meter used during experimentation.
The corroded surface of Max10 sample displays relatively small
sized and uniform distributed corrosion pits. Some pits are empty while
others have a ragged appearance. Arrow G and H show at lower
and higher magnification the largest identified corrosion pit. The matrix
located between the eutectic chromium carbides corroded away.
Without the surrounding matrix the chromium carbides are unsupported and mechanically break down producing an empty hole.
Inclined carbides break in bending and faster rate see Arrow I. The
pH meter used during the sulfuric acid corrosion test indicates pH =
0.68.

Figure 2. NACE published compounded Iso corrosion chart of

phosphoric acid.
The temperature - acid concentration domains in Figure 2 identify
materials having corrosion rates smaller than 20 MPY. During the
Max10 corrosion test in phosphoric acid very severe testing
0
parameters were selected respectively 60% phosphoric acid at 220 F
0
(104 C) see Arrow E. After 72 testing hours the corrosion rate of
Max10 was 31.6 MPY which is slightly higher than A20, slightly lower
than Duplex Stainless Steel and significantly lower than 316 SS.

pH [OH ] = 14 pH [H ]
-

pH [OH ] = 14 0.68 = 13.32

(1a)
(1b)

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
-

Equation 1a and 1b show the alkalinity calculation. [OH ] is the

+
hydroxyl ion while [H ] measures acidity. Conservatively the operating
pH range of Max10 is pH = 1.15 13.3
Ionic chlorides
Ionic chlorides are extremely corrosive due to their molecular
instability. Most of time they just contaminate pumping fluids
nonetheless if present they inflict major corrosion damage.
Ferric chloride one of the most corrosive ionic chlorides was used
during this test. The following were the testing parameters:

The base solution was 60% phosphoric acid at 150 F (66 C).
In such solution Max10 is completely inert;
Through stoichiometric calculation the ferric chloride addition
provided 100 PPM ionic chloride;
Testing time 192 hours while testing results are shown in
Table 2.
Photos 9, 10 and 11. Viewing the pin-on-disk wear apparatus and the
arm holding the pyramidal shaped Rockwell C testing diamond
indenter see Arrow N.

Table 2. Corrosion test results

Testing time
[hours]
72
120
Total: 192

Corrosion rate
[MPY]
29.92
5.36
14.57

After 72 testing hours the corrosion rate was 29.92 MPY however
after additional 120 testing hours the corrosion rate dropped to 5.36
MPY which proves that Max10 passivated. The average corrosion rate
is 14.57 MPY which is ranked very good.
275 m

Figures 3 and 4. Representing two wear testing stages when using an

alumina ball.

Table 3. Pin-on-disk testing parameters

#
Parameter
1
RPM
2
Testing time
3
Testing temperature
4
Mean wear groove diameter
5
Sliding length per RPM
6
Total sliding length
7
Static load
8
Sample roughness

K
Photo 7.

Photo 8.

Photos 7 and 8. SEM views of the Max10 corroded surface in 100

PPM ionic chlorides containing solution.
Corrosion occurred in one very selective location see Arrow J
and K. Most likely a sample surface porosity produced micro-galvanic
conditions which induced a 275-m diameter pit. Comparatively the
corrosion rate of 316 SS in 100 PPM ionic chloride is 40 MPY while the
hard iron with the best corrosion resistance presently produced by the
Metal Casting Industry withstands only 28 PPM ionic chlorides.

Values
80
2 hours
0
72 F
15.875 mm
49.848 mm
478.54 m
1,063 g or 10.425 Newton
0.20 0.12 m

WEAR TESTING
Photo 9 shows the pin-on-disk wear testing apparatus used to
evaluate the wear resistance of Max10. Arrow M points to the 1- inch
x 1- inch x 0.25- inch thick test sample pinned on the 80 RPM rotating
table. During testing the contact point between the sample and the
indenter is constantly flushed with water.
Usually the pin-on-disk wear test is accomplished with a 0.25-inch
diameter alumina ball which progressively breaks into the sample
surface producing the wear track seen in Figure 4. However an
alumina ball wouldnt penetrate into hard irons therefore it was
replaced with a diamond indenter.

Figure 5 and Photo 12. Schematic view of the wear forces acting on
the Max10 sample and the cyclic material pile up in the wear groove.
When compressive stresses are unable to push the front pile the
diamond indenter jumps over the pile developing cyclic material pile
ups see Arrow O in Photo 12.

The wear testing parameters are seen in Table 3.

Under the combined action of static load and rotational movement
the diamond indenter breaks right away into the Max10 material.
During testing the material located in front of the indenter is
compressed while pulling stresses act behind the indenter see Fig. 5.

Table 4 shows the wear rate of Max10 and 25% Cr hard iron soft
annealed, machined and hardened. Despite the 415 HBN hardness of
Max10 versus 620 HBN hardness of 25% Cr their wear rates are

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
uniaxial overload conditions and support the 1% tested elongation
see Arrow P in Photo 14.

nearly identical. The 35% carbide volume fraction of Max10

compensated for the lower hardness.
Table 4. Comparative wear test results
Testing results
Initial
Final
Weight Volume
Material
Wear rate
weight weight
Loss
loss
3
[mm /N/mm]
3
[g]
[g]
[mg]
[mm ]
-5
Max10
28.9680 28.9586
9.4
1.175
23.55x10
25% Cr
softened,
-5
29.2109 29.2014
9.5
1.1855
23.76x10
machined and
hardened
OPTIMIZING THE CHROMIUM CARBIDE DISTRIBUTION, TENSILE
STRENGTH, ELONGATION, HARDNESS AND FRACTURE
TOUGHNESS.
Optimizing the Chromium Carbide Distribution
Photo 13 is an optical microscopic view of Max10 showing that
majority of chromium carbides solidified into rosette eutectic cells.
The 35% carbide volume fraction was calculated with an Image
Analyses System.
Through controlled kinetic reactions the hexagonal crystallized
M7C3 chromium carbides have uniform, size and distribution while the
formation of harmful M23C6 secondary carbides is avoided. The longest
chromium carbide seen in Photo 13 is 50-m which is an acceptable
size. The hardness of M7C3 chromium carbide is 1,400 1,600 HV and
they have better wear and corrosion resistance than other carbides.

Photo 14. SEM view of cup con ductile features found on the
fractured tensile specimen surface.
The hardness range of Max10 is 400 460 HBN and was tested
with New Age Shear Pin and 3,000 kgf Brinell apparatus.
Fracture Toughness
The fracture toughness established by KIVM per ASTM E1304 is a
relative slow advancing steady crack initiated at the tip of the very
sharp Chevron point and propagates as seen with Arrow R in Photo
16.

Photos 15 and 16. Max10 fracture toughness tested sample

Arrow S in Photo 15 points to the grip slot in which closed grips
are simultaneously fit.
Subscript I means mode one opening, V means Chevron notch
while M indicates that maximum force occurs at critical length. The
specimen configuration is S L. It specifies that testing sample is
pulled in the short transverse direction while crack growths
longitudinally.

Photo 13. Optical microstructure of Max10.

Tensile Strength, Elongation and Hardness
The testing specimen was machined from a 6-inch long keel block
poured per ASTM A781. [6] Testing was accomplished with 0.5-inch
diameter pulling test per ASTM A370 while test results are seen in
Table 5.
Table 5. Mechanical properties of Max10
Tensile strength
Mechanical properties of
[PSI]
Max10
63,500

KIVM = x PM / B x(W)
*

Elongation
[%]
1.00

PM
B
W
W/B

Max10 likewise all hard irons have equal tensile and yield
strength. Although the specimen fractured without necking Max10 had
1.00% measured elongation. This beneficial result is somewhere
unique because hard irons are without any elongation. The cup con
ductile features on the specimen fractured surface are formed under

1/2

(2)

= 28.22 minimum stress intensity factor per Table 3 of

ASTM E1304;
= 852 lb the maximum test force;
= 0.998-inch the specimen thickness;
= 1.449-inch the specimen length;
= 1.45 the dimensional requirement of ASTM E1304
being satisfied;
1/2

The test result was KIVM = 20 KSIx(inch)

validity test conditions respectively:

and fulfills the four

The crack plane deviation is less than 0.04B;

The fractured surface is without defects;

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA

On the contrary the Max10 impeller and pump case seen in

Photo 20 and 21 have excellent appearance 10 service months. Only a
few isolated shallow defects are noticed. Arrow U indicates the cut
water damage. The pump was reassembled and functioned additional
two months increasing the total service life to 12 months.

The specimen dimensions are within the ASTM E1304

requirements;
1/2
B > 1.25 (KQVM / y) ;

Because KQVM = KIVM indicates that Max10 has isotropic properties

due to uniform size, shape and distribution of chromium carbides. This
is an exceptional achievement for any hard iron.

With Max10 pumps the service life tripled.

Table 6. Fracture toughness values listed by ASTM E1304.

Specimen Yield strength
1/2
Material
KIVM KSI(inch)
orientation
KSI (MPa)
2024
LT
52.4 (361)
50.8 (55.9)
Aluminum
SL
42.7 (294)
35.3 (38.8)
7075-T651
LT
78.7 (543)
31.3 (34.4)
A l um i num
SL
67.8 (468)
20.7 (22.8)
Grade 250
LT
230.8 (1592)
90.6 (99.7)
Maraging steel
S-L
229.6 (1583)
79.1 (87.0)
Grade 300
LT
274.0 (1890)
49.9 (53.9)
Maraging steel
SL
288.0 (1986)
47.3 (52.0)
6A1 4V
LT
131.5 (907)
103.9 (114.3)
Titanium
S-L
122.8 (847)
95.2 (104.7)

Photos 18 and 19. The pump case and impeller failed in less than
four months when poured with a different material then Max10.

Table 6 published by ASTM E1304 page 7 shows the fracture

toughness of different alloys. The lowest fracture toughness of three
1/2
dissimilar aluminum materials is 20.7 KSIx(inch) and is similar with
the fracture toughness of Max10.
MACHINABILITY
To manually drill and tap pipe threads with a drill press is the most
difficult machining operation of hard irons nonetheless they were
successfully accomplished in Max10.
Photos 20 and 21. After 10 months of service the Max10 impeller
and pump case look extremely good.
Mixing Blades
The riser seen with Arrow X in Photo 22 nearly emptied itself by
compensating the casting solidification shrinkage.

Photo 17. Flawless NPT20 pipe threads machined in Max10 using

one cut only see Arrow R.
Photo 22. Riser showing casting solidification shrinkage issues.

During hundreds of machining operation Max10 never cracked.

Usually the volumetric solidification contraction of hard irons is 4

5.5%. Max10 very much exceeded these values and new foundry
engineering rules were established.

SERVICE PERFORMANCE
Pumps
The severe corrosion erosion conditions of a 24 / 7 operation
damaged rapidly the pump components of all previously used
materials. Photo 18 shows a severely damaged pump case poured
from a different material then Max10. Arrow S points to the damaging
spiral wear pattern which in a few locations broke through the pump
case volute. Arrow T in Photo 19 shows the remnants of an
impeller.

CONCLUDING REMARKS
1.

In real life the S3 frame 1 and 2 slurry pumps build in Max10

tripled the service performance. The service life in a 24 / 7
operation increased from four months to twelve months.
Such performance was obtained by homogenizing the
Max10 chromium distribution at microscopic levels.

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
2.

The chromium content at the chromium carbides matrix

interfaces increased to 31.72% and assured passivation
conditions while the unfavorable M23C6 secondary carbides
were eliminated.

3.

The M7C3 chromium carbides have uniform size, shape and

distribution which conferred Max10 isotropic properties. This
significant achievement elevated all physical and mechanical
properties.
ACKNOWLEDGEMENT

Sincere thanks to Gordan Nordyke, Superintendent, of Western

Foundries Inc in Longmont, CO. With Gordans Foundry Engineering
skills Max10 was successfully implemented.
REFERENCES
1.

ASTM G99 Standard test method for wear testing with pin-ondisk apparatus.

2.

ASTM A370 Standard test methods

mechanical testing of steel products.

3.

ASTM E1304 Standard test method for plane strain (Chevron

notch) fracture toughness of metallic materials.

4.

ASTM A532 Standard specification for abrasion resistant cast

irons.

5.

Dupin et al: AFS Transaction 90 page 711.

6.

ASTM A781 Standard specification for castings, steel and alloy

common requirement for general use.

and

definitions

for

Copyright 2012 by SME