Thin Solid Films, 45 ( 1977) 309-3 19

0 Elsevier Sequoia S.A., Lausanne-Printed in the Netherlands 309

SOME COMPARATIVE PROPERTIES OF LAVES- AND CARBIDE-

STRENGTHENED COATINGS DEPOSITED BY PLASMA OR
DETONATION GUN*

M. 0. PRICE, T. A. WOLFLA AND R. C. TUCKER, JR.

Union Carbide Corporation, Linde Division, Coatings Service Department, Indianapolis, Ind. 46224
(U.S.A.)
(Received March 31, 1977; accepted April 8, 1977)

The microstructures and mechanical properties of a series of plasma and

detonation coatings of cobalt and nickel alloys with molybdenum, chromium and
silicon were characterized. Two of the coatings were strengthened almost entirely by
Laves’ phase precipitation while the other two were strengthened by a combination
of carbide and Laves’ phases. Limited heat treatment studies indicated that the as-
deposited structures are supersaturated solutions and further precipitation, parti-
cularly of Laves’ phases, occurs at elevated temperatures. The elastic moduli and
moduli of rupture of the coatings were determined using a ring compression
technique. These data were compared with the strain-to-failure data obtained in an
expanding ring test. One of the detonation gun coatings with a combination of
Laves and carbide strengthening was found to have an unusually high modulus of
rupture and strain-to-fracture. The corrosion resistance of the materials in room
temperature and boiling solutions of hydrochloric acid, sodium hydroxide, nitric
acid and sulphuric acid was also determined.

1. INTRODUCTION

Many wear-resistant materials are based on the use of hard particles in a

metallic matrix. Tungsten, chromium and titanium carbides have been used most
frequently, but other carbides have been used, as ‘well as oxides and nitrides. In the
last few years a new class of materials, Tribaloys alloys, relying on the Laves phases
for wear resistance has been introduced and has been widely evaluated as a cast,
powder metallurgy and plasma-deposited material’. The Laves phases are softer
than most of the more common carbides, oxides and nitrides but reportedly offer
good wear resistance without causing significant wear of the mating surfaces. They
are also noted for their compatibility with bare or anodized aluminum, self-mating
wear resistance, service in conditions of little or no lubrication and corrosion
resistance.
This paper characterizes some of the mechanical, wear and corrosion

*Paper presented at the International Conference on Metallurgical Coatings, San Francisco, California,
U.S.A., March 28-April 1, 1977.
@Registered trademark of E. I. duPont and Co., Inc.
310 M. O. P R I C E , T. A. W O L F L A , R. C. T U C K E R , JR.

properties of several plasma and detonation gun (D-gun) coatings produced from
Tribaloy powders. Plasma and D-gun coating processes are well known, and the
properties of the general classes of metallic, cermet and ceramic coatings have been
described elsewhere z. The intent of the work reported here was to provide general
guidelines for the selection and use of several specific coatings of Tribaloy alloys.
Therefore the wear and corrosion test results have been compared with several other
types of coatings. It should be fully recognized, however, that exact prediction of
service life cannot be made from laboratory tests.

2. D E S C R I P T I O N OF T H E C O A T I N G S

All of the coatings to be described were made with Tribaloy powders using
standard Union Carbide plasma torches or detonation guns. Table I contains the
nominal compositions 1 of the alloys and the specific powder and coating analyses of

TABLE I
C O M P O S I T I O N OF P O W D E R S A N D C O A T I N G S

Co Ni Mo Cr Si 0 C

LDT-100 Nominal I 55 -- 35 -- 10
(D-gun) Powder 56.6 -- NA a -- 9.72 0.13 0.08
Coating 53.9 -- NA -- 8.75 0.31 0.80

LDT-400 Nominal 62 -- 28 8 2
(D-gun) Powder 60.1 -- NA 7.94 2.26 0.15 0.08
Coating 58.3 -- NA 6.29 1.86 0.18 1.60

LPT-700 Nominal -- 50 32 15 3
(plasma) Powder -- 48.2 NA 15.02 2.95 0.176 < 0.01
Coating -- NA NA 14.2 2.85 0.61 0.014

LPT-800 Nominal 52 -- 28 17 3
(plasma) Powder Balance -- NA 16.96 3.04 0.23 <0.01
Coating Balance -- NA 16.06 2.80 0.49 0.05

LDT-800 Nominal 52 -- 28 17 3
(D-gun) Powder Balance -- NA 16.89 3.21 0,224 <0,01
Coating Balance -- NA 15.64 2.92 0.32 0.06

a NA, not analyzed.

T A B L E II
DENSITY A N D H A R D N E S S OF C O A T I N G S

Density Hardness

(g c m - ~) ( ~o o f cast)

LDT-100 7.56 84 850 VPN~o o

LDT-400 8.1 90 750 VPNxo o
LPT-700 7.58 87 470 VPNIoo
LPT-800 7.51 87 500 VPNIo o
LDT-800 8.0 93 750 VPN3o o
LAVES- AND CARBIDE-STRENGTHENED COATINGS 311

the various materials discussed here. The measured densities (ASTM B328-73) and
a calculated percentage of full density based on cast Tribaloy 1 alloys are shown in
Table II.
The D-gun operating parameters used were essentially inert for LDT-800,
somewhat carburizing for LDT-100 and strongly carburizing for LDT-400. As a
result, LDT-100 and LTD-400 have a combination of Laves phase and carbide
strengthening. LDT-100, as shown in Fig. 1, reveals a very dense coating with little
or no particle boundary oxidation. The etched microstructure shows clusters of
Laves' phase particles, but apparently a significant amount of Si remains in

(a)

(b)
Fig. 1. (a) LDT-100 as-coated microsection, as-polished. (Magnification, 140 x .) (b) LDT-100 as-
coated microsection showing a cluster of Laves' phase (arrow) and the lamellar structure, etched,
differential interference contrast (DIC). (Magnification, 840 x .)
 312 M.O. PRICE, T. A. WOLFLA, R, C. TUCKER, JR.

metastable solid solution since the amount of visible Laves phase is far less than that
predicted 1. The microstructure of LDT-800 is in general similar to that of LDT-100
if the difference in chemistry between LDT-100 and LDT-800 is taken into account.
On heat treatment a uniform dispersion of Laves' phase particles is formed, in both
LDT-100 and LDT-800, as shown in Fig. 2 for LDT-800.

Fig. 2. LDT-800microstructure after 4 h at 1080°C in vacuum, etched, DIC. (Magnification, 840 x .)

In LDT-400 comparatively large carbides form during coating (Fig. 3) as

would be expected from the carburizing deposition condition and from the presence
of chromium. Laves' phase formation seems somewhat inhibited but after heat

Fig, 3(a).
LAVES- AND CARBIDE-STRENGTHENED COATINGS 313

(b)

Fig. 3. (a) LDT°400 as-coated microsection, as-polished. (Magnification, 140 x.) (b) LDT-400 as-
coated microstructure showing carbide particles (arrow) and the lamellar structure, etched, DIC.
(Magnification, 840 x ,)

treatment appears similar in distribution to that in LDT-100 and LDT-800 (Fig. 4).
It should be noted that the heat treatment was arbitrarily chosen and was not
optimized for improving mechanical properties or any other purpose. As can be
seen in Figs. 2 and 4, it was high enough to cause complete recrystallization. Some
increase in density was also measured.

Fig. 4. LDT-400 microstructure after 4 h at 1080 °C in vacuum, etched, DIC. (Magnification, 840 x .)
314 M.O. PRICE, T. A. WOLFLA, R. C. TUCKER, JR.

R e t u r n i n g to T a b l e I, it is evident that p r o p e r p l a s m a d e p o s i t i o n causes only

insignificant changes in c o m p o s i t i o n for LPT-800, a n d similar results w o u l d be
expected for LPT-700. F i g u r e 5 illustrates the clean m i c r o s t r u c t u r e that was typical
o f the coatings used for this study. As with the D - g u n coatings, the a s - d e p o s i t e d
s t r u c t u r e is m e t a s t a b l e a n d heat t r e a t m e n t allows further L a v e s ' phase pre-
cipitation.

(a)

(b)

Fig. 5. (a) LPT-800 as-coated microstructure showing the fine Laves' phase precipitate in a fully melted
particle (light, arrow) and an incompletely melted large particle (dark, arrow), etched, DIC.
(Magnification, 840 x .) (b) LPT-800 microstructure after 4 h at 1080°C in vacuum, etched, DIC.
(Magnification, 840 x .)
LAVES- AND CARBIDE-STRENGTHENED COATINGS 315

3. MECHANICAL PROPERTIES

As usual, the tensile bond strength (ASTM C-633 modified to a thinner

coating) of all of the D-gun coatings exceeded that of the epoxy used in the test, i.e. it
was greater than about 10 000 lbf in - 2 for a coating 0.010 in thick on 1018 steel. The
bond strength for LPT-700 exceeded 5200 lbf in- 2 and that for LPT-800 exceeded
8500 lbfin-2. Data on the hardness of the coatings in cross section are contained in
Table II.
The compression of free-standing rings of each coating was used to determine
the moduli of rupture and elasticity and the strain-to-failure of each coating (Table
Ili). The rings were about 1 in in inside diameter, ½in wide and either 0.010 or 0.020
in thick. It should be noted that the elastic modulus increased with coating thickness
(probably as a result of the specimen geometry) and that the strain-to-fracture
decreased (probably as a result of increasing residual stress and specimen geometry)
for each coating.
The compressive strength and elastic modulus of LPT-800 were determined
both parall.el and perpendicular to the coating surface by machining 0.2 in x 0.2
in x 0.65 in specimens out of a coating 0.75 in thick. As shown in Table IV, there is
no significant directional dependence of the ultimate strength, but the elastic
modulus is higher parallel to the surface than it is perpendicular to it. The failure
mode was almost completely brittle. It was difficult to distinguish between the
appearances of the fractured surfaces in the two directions.

4. WEAR PERFORMANCE

The wear performance o f the coating was determined using an Alpha (LFW-1)
block-on-ring test. The test procedures have been described elsewhere 3. In these
tests the block was coated and run against a 4620 steel ring with a surface hardness
o f R~ 58-63. The results shown in Table V are the average of two or three tests run at
a speed o f 33 cm s- 1 for 593 m in Mil H5606A hydraulic fluid (a poor lubricant). D-
gun and plasma W C - C o coatings are included for comparison.
In Mil H5606A hydraulic fluid at 136 or 204 kg loads, LDT- 100, LPT-700 and
LPT-800 wore at a higher rate than did the tungsten-carbide-based coatings, but
they caused less wear of the mating steel. Under a 272 kg load, LDT-100 and LPT-
800 both wore at a higher rate than the tungsten carbide coatings, as at the lower
loads, but the LPT-800 caused as much wear of the mating steel as did the tungsten
carbide coatings. LDT-400 appeared to be comparable with the D-gun tungsten
carbide coating (it should be noted that LDT-400 contains some carbides).
Although a direct comparison cannot be made, the wear scar volume of the LDT-
400 at 272 kgis about one-fifth o f that reported 1 for a different type of plasma T-400
in Stoddard's solution which is also a poor lubricant. The dynamic coefficients of
friction for all the L D T coatings fell in the range 0.12-0.15. Using 30 weight motor
oil as a lubricant, plasma and D-gun LPT-700, LPT-800 and LDT-800 all
performed quite well (Table VI).
TABLE III
MECHANICAL PROPERTIES OF THE COATINGS

Coating thickness (in) LDT-IO0 LDT-400 LPT-700 LPT-800 LDT-800

0.010 0.020 0.010 0.020 0.010 0.020 0.010 0.020 0.020

Elastic modulusa ( x 106 lbf in- 2)

~b 18.0 27.2 19.5 25.9 8.9 I 1.9 10.3 11.5
s 2.6 1.8 1.6 1.3 1.6 0.9 1.3 2.6
n 6 5 3 2 6 6 5-7 5-7
Modulus of rupture ( x 103 l b f i n - 2)
91.6 82.6 142 132 30 31 24.4 26.1 68
s 9.8 6.7 9.8 0A 1.6 1.4 2.7 1.7 6.2
n 6 5 3 2 6 6 5-7 5-7 4
Strain-to-fracture ( x t0 -3)
calc.¢ 5.2 3.1 7.4 5.1 3.5 2.6 2.4 2.3
meas. 2 6.7 3.8 8.4 -- 5.0 4.0 3.3 3.5 3.5 9
s 1.4 0.7 1.7 --- 1.5 0.5 0.3 0.9 1.0
n 6 5 3 -- 6 6 5-7 5-7 4 m
,.q
a From strain gauges. >
b$, average; s, standard deviation; n, number of tests.
e Calculated from the moduli of elasticity and rupture. ©

t"-'

,..]
LAVES- AND CARBIDE-STRENGTHENED COATINGS 317

T A B L E IV
COMPRESSIVEPROPERTIESOF LPT-800

Parallel to the Perpendicular to

surface the surface

Ultimate strength ( x 10 a Ibfin -2)

~a 143 135
s 16 23
n 9 6

Elastic modulus ( x 106 lbfin -2)

13.5 9.6
s 2.8 1.7
n 9 6

a ~., average; s, standard deviation; n, number of tests.

TABLE V
ALPHA WEARTESTSIN HYDRAULICFLUIDa

Coating Wear scar volume ( × 10 -6 cm 3)

136 kg load 204 kg load 272 kg load

Coated 4620 Coated 4620 Coated 4620

block ring block ring block ring

LDT- 100 33 Gain 54 165 67 190

LDT-400 26 460
LPT-700 50 180 20 178

LPT-800 43 130 36 184 64 426

LW- 1N40 b 14 360 20 410

LW-I IB c 8 240 16 560 42 670
LC-2 d 30 520
Cr e 47 Gain

a Coated blocks run against carburized AIS14620 steel rings with a surface hardness of H R C 58-63 and a
surface finish of 0.20-0.25 ltm centerline average in Mil H5606A hydraulic fluid for 594 m.
b D-gun WC-15Co.
c Plasma WC-12Co.
dplasma Cr3C2-25NiCr.
e Electroplated.
318 M . o . PRICE, T. A. WOLFLA, R. C. TUCKER, JR.

TABLE VI
ALPHA WEARTESTSIN OILa

Coating Wear scar volume ( × 1 0 - 6 c m a)

136 kg load 204 kg load 272 kg load

Coated 4620 Coated 4620 Coated 4620

block ring block ring block ring

LPT-700 25 110 89 390

LPT-800 59 150 11 460
LDT-800 23 40 45 40 38 10
Electroplated
hard Cr 4 30 17 40

a Coated blocks run against carburized AIS14620 steel rings with a surface hardness of HRC 58 63 a n d a
surface finish of 0.20-0.25 pm centerline average in 30 weight motor oil for 594 m at 33 cm s- 1.

5. CORROSION RESISTANCE

Free-standing cylinders of LPT-700, LPT-800 and LDT-800 were made by

coating aluminum tubes, by machining out most of the aluminum and by dissolving
the remaining aluminum in dilute NaOH. These rings were then immersed in
solutions ofNaOH, HC1, HNO 3 or H2SO4, and the weight change was noted (after
washing and drying) every 7 days for 28 days at room temperature and every day for
7 days in the boiling solutions. The room temperature solutions were changed every
3 days and the boiling solutions daily. Corrosion rates were calculated based on the
projected surface area of the coatings. The results are compared with several other
types of coatings in Table VII. Obviously this type of measurement does not
necessarily reveal the full extent of corrosion damage since selective attack of one or
more phases in the microstructure can cause destruction of the coating without
removing much material, as it does for LDT-800 or LPT-800 in HNO 3.
Furthermore, the creation of a solid corrosion product can result in a weight gain
instead of a weight loss. If either occurs, it is not possible to calculate the depth of
attack by a simple division of the rate in weight per unit area per unit time by the
density. The tests do, however, provide general guidance.

6. DISCUSSION

The properties of plasma and D-gun coatings, even though they are made with
the same alloy powder, can be varied drastically by the choice of coating equipment
and operating parameters. The data presented here certainly do not fully
characterize plasma and D-gun coatings with Tribaloy alloys. They are meant only
to describe partially the particular coatings produced by a given set of parameters
and equipment. The metastable nature of the coating microstructures is not unique;
many coatings exhibit similar phenomena as a result of the very rapid quench rate
associated with this type of deposition. It is different, however, from that of cast or
LAVES- AND CARBIDE-STRENGTHENED COATINGS 319

TABLE VII
AQUEOUS CORROSION RATES (mg dm - 2 d a y - 1) AT 2 2 ° C AND IN BOILING SOLUTIONS

Coating 50 wt. % NaOH 5 wt. % HNO 3 20 wt. % HCI 5 wt. % H~S04

At 22 °C
LPT-700 - 2.7 - 22.5 - 20.5 -20.6
LPT-800 - 6.8 -149.5 - 35.3 - 1.9
LDT-800 + 0.9 - 7.7 - 11.0 - t.9
LW-IN30 a + 0.5 + 13.1 - 9.9 -10.7
WT-I b - 2.5 -497 -469 -13.1
LW-15 c +24.7 + 7.3 - 8.9 -21.2

In boiling solutions
LPT-700 + 57.0 -3120 -2080 - 180
LPT-800 - 613 -3340 -3610 -663
LDT-800 - 1500 -6710 -2180 - 98.8
LW-1N30 - 403 + 45.4 - 180 - 52.5
WT-1 - 2.5 - 610 -2030 -960
LW-15 - 94.1 + 0.6 - 220 -128

a D-gun W C - I 3 C o .
bD-gun ( W , T i ) C - 1 7 N i .
c D-gun WC- 10Co-4Cr.

sintered Tribaloy alloys, and some caution is in order when trying to extrapolate
performance from one to the other. The effects of heat treatment on these coatings
are being studied and may be reported elsewhere.
The mechanical properties of these coatings, particularly LDT-400, are of
interest. The modulus of rupture and the strain-to-failure of this coating are among
the highest known. Thus it may be especially useful in fatigue-sensitive applications
and similar situations. As with any material, the wear and corrosion data indicate
that attention must be paid to the specific environment of the intended application
since universal applicability is not likely. Although the wear resistance of the
coatings with Tribaloy alloys without a carbide dispersion is not equal to that of the
WC-Co coatings, the Tribaloy alloys do cause much less wear of the mating
material. Preliminary results at elevated temperatures imply that these coatings,
particularly the 400, 700 and. 800 series, may have unique wear resistance in the
range of about 400-800 °C.

REFERENCES

1 C . B . Cameron and D . P. Ferriss, Cobalt, 3 ( 1 9 7 4 ) 49.

2 R . C . T u c k e r , J r . , J. Vac. Sci. Technol., 11 ( 1 9 7 4 ) 725.
3 R . C . T u c k e r , J r . , a n d A . E. Miller, in R . G . B a y e r (ed.), Selection and Use of Wear Tests for Metals,
Am. Soc. Test. Mater., Spec. Tech. Publ. 615 ( 1 9 7 6 ) 68.