Wear, 32 (1975) 279 - 289 279

0 Elsevier Sequoia S.A., Lsusanne - Printed in the Netherlands

NEW MATERIALS HESITANT TO WEAR AND CORROSION TO

1000 “c*

R. D. SCHMIDT and D. P. FERRISS

E. I. Du Pant de Nemours Co.. Inc., Wil~in~~o~, Delaware (U.S.A.)
(Received September 24,1974)

Summary

An unusual combination of wear and corrosion resistance has been

developed in cobalt and nickel base alloys known as Tribaloy** intermetallic
materials, These two-phase alloys depend on the unique properties of a Laves
intermetallic phase to resist wear under poor or unlubricated conditions
from cryogenic temperatures to about 1000 “C. The constituent elements
are partitioned so that both the Laves inte~et~li~ and the solid solution
phases have generally good resistance to corrosion also. At higher chromium
content the corrosion resistance is excellent in most environments.
Parts can be fabricated by powder metallurgy, plasma spray coating,
casting or hardfacing. Several wear tests are used to demonstrate the qualities
of Tribaloy. Wear resistance was excellent at 25”, 315”, 650” and 980 “C in
air. Another wear test compares several Tribaloy compositions with other
commercial, corrosion resistant alloys in 5% hydrochloric acid. Some
examples of applications are described.

Introduction

In general terms a sliding wear system consists of two solid materials,

under load, in motion relative to each other in a chemical environment.
Usually the environment is a lubricant whose function is to maintain a vis-
cous shear layer between the two solids so that they do not touch each other,
or touch very intermittently. This condition minimizes surface damage or
recession, called wear. Frequently, a lubricant is not possible. Some seals or
bearings must operate at temperatures well above the functional range of
lubricants. Pump parts sometimes must use the process fluid for whatever
lubricating value it has. In textile or food machinery a lubricant is a con-
taminant. This paper discusses wear systems between metals whose environ-
ments are non-lubricating, poorly lubricating or chemically aggressive.

*Paper presented at the 8th Plansee Seminar on Refractory and Wear Resistant
Materials, Reutte, Tyrol, 27 - 30 May, 1974.
**Registered trade name.
280

The wear mechanisms which apply to these systems are most convenient-
ly categorized as follows:
adhesive - the cold welding of high spots across the bearing interface,
followed by fracture and fragmentation which create wear debris and promote
abrasive wear. Friction is high and variable. The end result is gross cold
welding or galling.
abrasive --- either wear debris or particles from the environment lodge
between the surfaces and plow, score and remove metal so that surfaces
recede.
chemical - electrochemical or general attack on one or more surfaces
causes surface damage and/or recession. Commonly, solid-to-solid contact
will void passive layers which normally make a surface resistant to a chemical
environment.
These mechanisms may superpose and accelerate wear.
The conventional means of dealing with unlubricated wear systems is
L-.
cu.
make one side babbitt or bronze and design to allow recession,
use very hard metals or WC/Co and precision grind mating parts,
use carbon/graphite and/or solid lubricants.
All these methods suffer from being awkward, impractical or expensive. The
need, therefore, is for wear couples which:
do not cold weld across the interface,
have high shear strength (hardness) to resist plastic deformation,
have corrosion resistance which is intrinsic and not dependent on a
passive layer,
can accommodate local stresses by short range plastic deformation and/
or machining by micro-fragmentation,
are fabricable in a variety of shapes and sizes.
The alloys described in this paper have demonstrated an unusual capacity to
satisfy these characteristics.
LOAD

STRAIN GAGE

TEST PINS

Fig. 1. Rotary thrust tester. Normal load = 162 kg/cm2, maximum load = up to 630
kg/cm2, surface speed = 68.5 to 183 cm/s.
 281

Background of the development

Some years ago a goal was set to devise metals systems which would
have low friction and resist wear in non-lubricating environments. A rotary
thrust tester, Fig. 1, was used to screen hundreds of metal pairs. Figure 2
shows the surface of nearly ideal performance: negligible wear recession
under high load and velocity conditions (PV = 1070 kg/cm2 X m/s) in an
ester. Similar performance was obtained in unleaded gasoline. The key
metallurgical factor was the identification of alloys containing a ternary
intermetallic compound known as a Laves phase in a eutectic matrix with a
solid solution having compatible properties and low coherency with many
mating materials, especially steel. These alloys have been registered in the
U.S. under the trademark Tribaloy.

Sliding direction
,

t Original surface preparation

marks

Fig. 2. Surface of PM (50% T-100 + 50% Cu) after rotary thrust wear test. P = 620 kg/cm2
65 h, PV = 1070 kg m/cm2 s., in ester. (X 50)

Metallurgical description of Tribaloy

The nominal compositions of current alloys of Tribaloy are:

282

TABLE I

Elemental composition (Wt.%)

Co Ni MO Si Cr

Tribaloy 100 55 -- 35 10 -
Tribaloy 400 62 - 28 2 8
Tribaloy 700 - 50 32 3 15
Tribatoy 800 52 - 28 3 17

Carbon is less than 0.08%.

Structurally, the alloys contain 35% to 70% by volume (nearly the same
as by weight) Laves phase, MgZn,-type, a close-packed hexagonal crystal.
The composition is typically between CoMoSi and CosMo,Si inasmuch as
the atom ratios are continuously variable between these two stoichiometric
limits’- 3. The c/a ratio is 1.62, in the range for which low friction is pre-
dicted by Buckley and Johnson*. Chromium partitions itself about l/3 in
the Laves phase and 2/3 in the solid solution, contributing significantly to
the corrosion resistance of both phases. Figure 3 shows the etched structure
of T-400.

Fig. 3. Microstructure of cast T-400; primary hexagonal Laves phase in eutectic with
softer solid solution. Marble’s etch. Oblique illumination. (X 750)

Carbon is kept low so that carbides will not form in preference to the
Laves phase. Structural cobalt base alloys without carbon have not previously
been commercial. All the alloys are hyper-eutectic. The eutectic temperature
 283

is about 1230 “C and the Laves phase melts at about 1560 “C. Pertinent
hardnesses of cast alloys are:
Laves phase 1000 to 1300 HV
Solid solution 300 to 800 HV
Overall : T-400, T-800 54 to 60 HRC
T-700 42 to 48 HRC
At 1200 HV, the Laves phase is harder than the bulk hardness of the
hardest tool steel but is much softer than WC, Also,, TiC and other such
compounds commonly identified as wear resistant. Such materials tend to
wear away their mating surfaces unless surface finish is very fine and mating
geometry is very carefully prepared at high cost. In a matrix of the much
softer solid solution alloy, the structure of Tribaloy resists adhesive wear. At
the same time micro-machining processes can operate to accommodate high
stresses between mating parts. When the accommodation has been accom-
plished, further wear ceases and the two surfaces move with no tendency to
adhere. Figure 2 is an outstanding example of this. Note that the wear track
is actually smoother, more precisely defined than the test surface was prior
to the test.
The structure of Tribaloy is stable from cryogenic temperatures to just
below the eutectic temperature where some grain and phase growth does
occur. Consequently, the alloys are essentially not heat treatable. This
stability is useful for applications when temperature cycles over a wide range
as in refrigeration systems and aircraft. Another advantage is that Tribaloy
can be machined with ordinary tungsten carbide tools. Thread tapping is
difficult but all other machining methods produce excellent surfaces. Grinding
and lapping can be done with alumina or silicon carbide abrasives. Diamond
grinding is not necessary or recommended.

Properties

The mechanical and physical properties of T-400 are listed in Table II.
Essentially, the alloys have the density of copper or nickel, have high bearing
and fracture strengths but are nonductile. Impact energy is about the same as
WC + 10% to 15% Co. Toughness can be improved very significantly by
powder metallurgical processing as described later. Alloy T-100 is weakly
ferromagnetic and T-400 even less so. Alloys T-700 and T-800 are para-
magnetic.
A major difference among the several alloys of Tribaloy is their
corrosion resistance. Table III shows corrosion rates uersus those of some
common, commercial alloys which are designed for corrosion resistance and
are typically poor in wear resistance. Especially T-400, T-700 and T-800,
therefore, are described as alloys resistant to both corrosion and wear over
broad temperature and environmental ranges. This combination makes the
alloys unique in their properties.
284

TABLE II
Typical properties of Tribaloy 400
(for investment castings unless otherwise indicated)

Melting range 1230” - 1590 “C

Thermal conductivity 32 watts/m “C
Coef. of thermal expansion
25” to 500 “C 12.6 x lo+ per “C
25” to 1000 “C 15.1 X lo+ per “C
Density 9.0 gm/cm3
Tensile strength
25 “C 7000 kg/cm2
815 “C 6300 kg/cm2
Compressive strength
cast 19,000 kg/cm2
P/Md* 28,000 kg/cm2
Transverse rupture strength
cast 13,800 kg/cm’
P/Md* 16,500 k#/cm2
Modulus of elasticity 2.4 x 10 kg/cm2
Charpy impact strength
(unnotched)
cast 4 joules
P/Md* 7 joules
Hardness, Rockwell C
cast and H/F 52 - 58
P/Md* 58 - 60

*Powder hot consolidated to 99% to 100% dense.

Fabrication

All alloys can be processed as powders using plasma spray coating or

powder metallurgy. T-400, T-700 and T-800 are castable by investment and
centrifugal methods, and they can be overlayed on base metals by TIG or
oxyacetylene hardfacing. As mentioned above, the alloys are machinable
with carbide tools and can be ground and lapped with non-diamond
abrasives.
Significant advantages are gained by blending Tribaloy with other
powders and making parts by conventional powder metallurgy. The wear
resistance of P/M products of bronze, stainless steel and alloy steel has been
improved to a remarkable degree by the addition of 15% or 20% T-400.
Powders of Tribaloy are not readily compacted by themselves because of
their refractory nature under pressure. However, blends with up to 25%
Tribaloy are compactible. Sintering must be done in vacuum or in a
reducing atmosphere with -40” dew point, similar to stainless steel powder
processing. Done properly, powders sinter very well and one must be careful
not to oversinter some blends which may tend to dissolve the Tribaloy
particles. Sintering temperatures are appropriate to the binder metal recog-
nizing that the 1230 “C!eutectic temperature is an upper limit.
TABLE III
Corrosion rates* for TribaIoy 400, 700 and 800 and selected commercial compositions in several environments
millyear (1 mil = 0.001 in. = 0.0254 mm)

_Oxidizing Non Oxidizing Reducing

.
Chloride No chloride Chlorides No chlorides
10% Ferric** 65% Nitric 85% Phosphoric 3.5% Sodium 50% Acetic 5% Hydro- 45% Formic 10% Sulfuric
chloride acid (150 “F acid (150 “F chloride(250 acid (212 “F chloric acid acid (220 “F acid (215 “F
(Rm. temp.) (66 “C)) (66 “C)) “F (121 “C)) (100 =‘C)***) (150”F(66”C) (104 C)***) (102”C)***)

Tribaloy 400 101 1365 0.3 0.2 N(1) 194 :& 218
Tribaloy 700 84 12 N N N 30 -
Tribaloy 800 9.0 39 N N N 1.5 1.6 34

Commercial
Compositions
Nickel Base Super
Alloys
Hastelloy C 1.0 22 0.3 N N 18 3.1 26
Hastelloy B 102 9860 0.5 0.6 N 10 0.9 2.0
Hastelloy N X000 970 - - - 17 - 22
Nickel Base Alloys
Inconel600 440 28 - 14 123 37 220
Monei 400 >lOOO >50:: 1.0 - 2.8 26 0.8 16
Stainless Steel
Type 316 X000 11 0.5 -_ 2.0 > 500 500 900
Type 304 X000 8.0 1.0 - 300 X000 1700 >5000
Cobalt Alloy
No. 6B 80 8.0 0.3 0.3 N 4100 28 240
Tungsten Carbide/
6% Cobalt - 133 - - - 82 31 160
---
Legend (1) N: Nil corrosion < 0.1 millyear. (2) - : Not tested. * Average of 3 to 5 24-hour periods. ** 5 to 7 days exposure. *** Boiling. :
286

The second advantage of P/M processing of Tribaloy blends is the

practical matter of thermal and mechanical toughness. Although green
strength is lowered by 20% Tribaloy, the sintered part retains toughness at a
very useful level.

Wear tests

General laboratory wear tests are notoriously deficient in their ability

to predict wear resistance in specific applications. However, the relative
performance of materials systems in simplified tests is useful to provide
guidelines for materials selection. Two different tests were used to survey
the wear properties of Tribaloy.
The oscillating slider test, Fig. 4, was used by an independent research
and development org~ization to determine the friction and wear resistance
of Tribaloy up to nearly 1000 “G. The 7.1 mm diam., superalloy pin moved
back and forth 25 mm at up to 30 mm/s under load. The data for a plasma
sprayed and sintered test flat of T-120 are shown in Fig. 5. (T-120 is 80%
T-100 + 20% Ni.)

LOAD

3/8”DIA PIN
a2
M 8

0.2 - ;;~fkd
D Q 35 kg
a 105 kg
A 210 kg
0.1 -

0 I I , I 1
0 5 IO I5 20 25 30

TIME, MINUTES

Fig. 4. Oscillating slider test.

Fig. 5. High temperature tests - coefficient of friction us. time.

Sintering improves both the adhesive and cohesive strength of a plasma

deposited coating. For high temperature applications, the associated
reduction of porosity to near zero is necessary to prevent internal oxidation.
Note that at each temperature and under loads up to 210 kg/cm2 friction
was constant for the 30-min test. Friction coefficient decreased from 0.70
at room temperature to 0.45 at 315 “C under 35 kg/cm2 and to 0.3 at 650”
and 980 “G. Increasing the load to 105 kg/cm2 and 210 kg/cm2 at 980 “G
did not change the coefficient of friction. In all the above tests, neither the
Tribaloy composite coating nor the superalloy pin showed any si~ific~t
damage. It is concluded that the oxides of Tribaloy have the non-galling
properties at high temperature as does the two-phase, clean Tribaloy near
room temperature. Conceivably, one could pre-oxidize the surface for
service at a lower temperature range.
 287

LOAD

ROTATING DRUM

Fig. 6. Rider and drum apparatus.

The wear resistance of Tribaloy in a corrosive environment was

demonstrated using a drum and rider test, Fig. 6. The 7.1 mm wide-face of
a rectangular test block was loaded under 6.8 kg in contact with an 89 mm
diam. drum rotating at 400 r.p.m. in a pool of 5% (absolute) hydrochloric
acid. A one-hour test was adequate to distinguish the behavior of several
systems. In addition to weight loss, each component was rated on its surface
appearance immediately after the test. Ratings were made according to the
following guidelines:
Weight loss Appearance
Excellent < 10mg no visible score marks at 10 X ;
no surface damage or galling
Good <lOO mg a few score marks visible at 10 X;
nil surface damage; no galling
Fair <lOO mg continuous grooving; pits or other
evidence of incipient corrosion; no
galling
Poor >lOO mg signs of galling or transverse micro-
cracks; severe corrosion

Figure 7 summarizes the data. In the Tribaloy tests both the rider and
drum were castings of the same composition. Cobalt alloy 6 was also run
against itself. Other dissimilar metals, having generally good corrosion
resistance, were tested for comparison. Each tested component has its
surface rating indicated at the end of its “weight loss bar” in Fig. 7.
Clearly, cobalt base Tribaloy was outstanding in these tests. There were
no signs of corrosion on the test surfaces and weight loss was low or
moderate. The nickel base Tribaloy showed some corrosion and moderate
weight loss. Cobalt Alloy 6 had moderate weight loss but both surfaces had
signs of galling and corrosion. Cobalt Alloy 6 uersus 316 stainless steel and
uersus Hastelloy C gained weight because of galling. The hard chromium
plate on one drum was stripped off the wear surface during test.
 316 6i’6 II)317w

(P) CoeALT bLl#f 6

CO4ALT ALLOY 6 (P) -IPI

( wt. pan ) Y”

, * ’ ’ ’ I
iOoM6O4OxlOP#6OmtallE.Ql4Oi6O
OF DRUM OF RICER

WEIGHT LOS, mg

Fig. ‘7. Corrosive wear tests with drum and rider apparatus. 1 h in 5% HCI, speed 2.0 m/s
under a load of 6.8 kg.

Applications

Parts and surfaces of Tribaloy are being used in test programs, proto-
types and commercial parts in Europe as well as in the United States. Some
examples will convey the breadth of these applications.
Gear pumps are costly, precision devices which are subject to high
stresses, wear and sometimes corrosion from the process fluid. Cast T-800
has lasted twice as long as its Hastelloy C predecessor in an application where
the nickel base alloy has adequate static corrosion resistance but inadequate
wear resistance. Conversely, no previous known wear resistant alloy had the
required corrosion resistance.
Tribaloy 480 (20% T-400 + 80% 316 stainless steel) has been specified
by a large automotive company for P/M processing of bushings for the
diverter valve in its 1975 automobiles. The motion is unlubricated and is
exposed to temperature in the range 600” to 1050 “C.
A manufacturer of torque converters for snowmobiles has specified
P/M parts of bronze + 15% T-400 in sleeve bearings which are unlub~cat~.
Service life has been 6 times that of the bronze without Tribaloy.
Half the production of a manufacturer’s plug valves for polymer
processing have been plasma spray coated with T-400. The valve operates
against a type 316 or 440 C stainless steel seat. Commercial experience for
over two years has been equivalent to using D-gun applied WC-Co which has
been used for the other half of this company’s production. This company is
now changing to 100% Tribaloy.
Computer tape heads have been plasma coated with a blend of 75%
T-100 + 25% T-400 and processed to a near-mirror finish, Head life has
doubled and tape life has been extended 3 to 5 times over that experienced
with competitive coatings.
A toe bearing submerged in a molten polymer blender was wearing
away on the sleeve side. The conventional Co- 0-W-C alloy hardfacing was
replaced by T-400. Life was increased 300% with concomitant benefits in
production and reduced maintenance.
 289

Acknowledgements

The authors are grateful to C. B. Cameron for general assistance in this

work; to R. E. Murvine who designed the rotary thrust tester and contributed
to fabrication of test parts; and to J. J. Demo who conducted the corrosion
testing.

References

1 E. I. Gladyshevskii and Yu. B. Kuz’ma, Zh. Strukt. Khim., 1 (1) (1960) 66.
2 E. I. Gladyshevskii, Porosh. Met., 4 (10) (1962) 46.
3 R. V. Skolozdra, E. I. Gladysherskii and Ya. P. Yarmolyuk, Izv. Akad. Nauk USSR
Metal., 5 (1966) 148.
4 D. H. Buckley and R. L. Johnson, Trans. ASLE, 9 (1966) 121.