SURFACE HARDENING OF COPPER ALLOYS WITH LASER IRRADIATION

V. N. Dubnyakov

UDC 621.9.048.7:669.35

The majority of rubbing pairs operating under extreme conditions are made of tin bronzes
as the result of the fact that the high contact pressures occurring in service lead to galling
and seizing.
The use of these materials provides a positive gradient of mechanical properties
across the depth and reduces the tendency toward seizing.
The service of rubbing pairs under extreme conditions leads to significant losses of ~
nonferrous metal as the result of wear of them.
In addition, in a number of rubbing contacts
of machines under moving conditions copper alloys do not prevent galling and seizing.
In
connection with this it becomes necessary to increase the mechanical properties, particularly
the microhardness of the surface layers of tin bronzes.
One of the promising methods of
reducing losses to friction and wear of copper alloys is obtaining of a metastable condition
of the surface layers [1-3] by laser treatment.
An investigation of the alloys in the metastable condition showed [4, 5] that laser hardening makes it possible to sharply increase the
tribotechnical characteristics of the parts of mechanisms and machines.
The purpose of this work is an investigation of the structure and physical and mechanical
properties of tin bronzes (Table I [i]) after the action of laser irradiation.
To evaluate the properties of the metal of the zones of laser treatment cylindrical
samples with a diameter of 24 mm and a length of I00 mm, the working surfaces of which were
ground to a finish of R~ = 0.25 Dm and cleaned with alcohol, were prepared.
Then the samples
were laser treated with a Spectro Physics 973 continuous CO2-1aser with an output power of 2.5
kW and a width of the path of 3 mm without overlapping of the zones of treatment.
For comparison hardening was also done on a Kvant-16 pulsed solid-state laser with different energy
densities, a spot diam. of 2 mm, and a coefficient of overlapping of the zones of treatment
of 0.5. A cobalt salt-base absorbent was applied to the samples and they were placed so that
the beam struck the surface of the metal horizontally.
The laser-treated samples of tin bronzes were cut across the traces of interaction of
the irradiation with the metal with a Diskotom diamond saw. A coolant with a corrosion
inhibitor was supplied to the cutting zone. After this the cut-off portion of the treated
metal was pressed into mounting powder.
The prepared specimens were ground by the wet method
on a Planopol-2 polishing machine with subsequent ultrasonic cleaning after each stage of
grinding.
The final stage included polishing with diamond paste (d = i Dm) and etching in a
5% solution of FeCI 3 in HCI.
The microstructure of the specimens was investigated on a light
microscope.
The microhardnesses of the heat-affected zones were measured with a load of 0.5 N on
specimens layer-by-layer each 30 Dm from the surface into the zone of treatment with four or
five measurements on a Leitz Durimet-2 microhardness tester.
The original structure of BrOTsS4-4-2.5 bronze (according to the Cu-Sn-Zn system phase
diagram) consists of crystals of copper-base ~-solid solution (fcc lattice).
The lead present
in the alloy is practically insoluble in the ~- and B-phases of Cu-Zn and Cu-Sn alloys.
In the original condition BrOF6.5-0.15 bronze (after working and annealing) had a structure of ~-'phase with an average grain size of d = 30 Dm. The structure of BrOFI0-1, which
was used in the as-cast condition, consisted of ~-phase, =+Cu3P eutectic, and a small quantity
of ~ + 6 (Cu31Sn 8) eutectoid.
The microstructure of the surface of BrOF6.5-0.15 bronze irradiated by continuous irradiation with a power of i000 W, a rate of movement of the beam of 20 n~n/sec, and a beam diameter
of 3 mm is shown in Fig. i. In the area of interaction of the material with the beam two
Moscow Area Branch of the State Union Tractor Scientific-Research Institute.
Translated
from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 9, pp. 52-56, September, 1987.

0026-0673/87/0910-0699512.50

1988 Plenum Publishing Corporation

699

Fig. i. Hardened zone on BrOF6.5-0.15 alloy.

ment with a continuous laser.

Treat-

zones may be distinguished, the fused and the heat affected (Fig. 2a, b). In the heat affected
zone dispersed particles of Cu3P phosphide are precipitated from the e-solid solution (Fig.
2a). An analysis of the microstructure of the zone of fusion showed (Fig. 2b) that nonequilibrium crystallization occurred in it and a double eutectic (~+Cu~P) crystallized together with
=-phase in the interdendritic space.
Similar structural changes are observed in the hardened zone of BrOFI0-1 bronze.
It
should be noted that changes in the structure of the surface layer of these alloys were seen
only under conditions of laser irradiation leading to fusion of the surface of the samples.
An analysis of the equilibrium phase diagram shows that the ~-solid solution crystallizes
under conditions of slow cooling.
An increase in the cooling rate of the ~-solid solution
leads to the formation of the ~+Cu3P double eutectic and an insignificant quantity of ~ + 6
(Cu31Sn 8) eutectoid, which causes a change in the physical and mechanical properties of the
hardened zone. As the result of this a pulsed quantum-mechanical oscillator providing high
cooling rates of the irradiated material as the result of the short action of powerful radiation was used.
Treatment of BrOTsS4-4-2.5 b r o n z e w i t h pulsed laser radiation led to the formation of a
hardened zone differing in structure from that obtained in irradiation with a continuous
laser. A significant difference in microstructure is observed in the zone of fusion, where
grain refinement occurred as the result of growth of new (columnar) crystals of ~-phase.
It
has been established that cracks penetrating into the original material pass through the zone
of fusion of BrOTsS4-4-2.5 bronze treated by pulsed radiation perpendicular to the surface.
Cracks propagate through lead inclusions located directly at the surface.
This may be explained
explained by the fact that the coefficients of thermal expansion of lead and ~-phase are
different.
In laser beam heating strong thermal stresses, the relaxation of which occurs
in a very thin layer as the result of the high temperature gradient, which leads to cracking
of the material, occur.
The structure of the zone of treatment by pulsed laser radiation of BrOFI0-1 bronze is
shown in Fig. 2c. The hardened zone consists of columnar crystals oriented perpendicular to
the surface.
Some of the dendrites do not have a directed character of crystallization, which
is observed in areas of overlapping of the zones of laser irradiation treatment.
As noted above, the cooling rate of the fusion zone determines its physicochemical properties.
The relationship of the cooling rate Vcool of this zone to the radiation pulse power
was determined from the results of measurement of the dendriticparameter for BrOFI0-1 bronze.
In the original condition the average distance between the axes of the secondary dendrites of
the ~-phase h d = 26.3 ~m while in the radiation treated zone h d = 2.5-3.2 Dm, that is, an order
of magnitude less.
Consequently, taking into consideration the relationship d2vcool = const
[6] for a given material, it may be noted that the cooling rate in the laser fused layer is
two orders of magnitude greater than in casting.
An increase in cooling rate causes refinement
of the structure of the hardened material and this leads to an increase in hardness of the
zones of treatment.
The hardness of the tin bronzes in relation to the power of continuous
laser irradiation (rate of movement of the sample 20 mm/sec) is shown in Table 2. It may be
seen that in treatment with irradiation with a power of 500 W and less recovery processes
leading to a decrease in hardness occur in the bronzes.
An increase in the power of irradiation from 500 to I000 W causes an increase in cooling rate, as the result of which refinement
of the structure and an increase in hardness occur.
The optimum cooling rate is obtained in
hardening with irradiation with a power of i000 W, at which a structure is formed having the
maximum hardness, 1.5 times greater than the original.
The depth of the zone after irradia-

700

TABLE 1

Alloy

Chemical

Sn

Zn

Pb

BrOTsS4-2.5
BK)TsSS-5- 5
BrDF6.5- 0.15

B~)FIO-I

3,0...5,0

4,5...6,0
6,0...7,0
9,5...10,5

3,0...5,0

1,5...3,5

4,0...6,0 / 4,0.. ,6,0

0,1...0.25
0,95...1,!

*Remainder copper.
tion treatment with a power of i000 W is also 1.5 times greater than after irradiation with a
power of 500 W. The hardness of BrOF6.5-0.15 and BrOFI0-1 bronzes is an order of magnitude
higher than the HV of BrOTsS4-4-2.5 and BrOTsSS-5-5 alloys.
An analysis of the character of
change in microhardness of the zones treated by continuous laser irradiation showed that
a decrease in cooling time promotes the formation of a structure with higher physical and
mechanical properties.
An increase in cooling rate of copper alloys in laser treatment is
possible as the result of input of a larger quantity of energy and a decrease in the time
of interaction of the laser irradiation with the metal.
A pulsed quantum source of energy,
which provided a short interaction of the laser irradiation with. the metal, was used for
realization of these conditions.
The hardness of the nonferrous alloys obtained in pulsed laser irradiation treatment
for 6-7 msec is given in Table 3. The mechanical properties of an alloy treated with a pulse
oscillator depend upon the energy of irradiation.
For example, in BrOTsS4-4-2.5 bronze treated
with radiation with an energy of I0 and 12 J processes of recrystallization occur, as the
result of which a reduction in hardness of 14-27 HV is observed.
Such a rule is not maintained
with an increase in irradiation energy, which is indicated by the increase in hardness of the
treated zones with a pulse energy of 16 J and more.
This is caused by refinement of the structure as the result of fusion and crystallization under conditions of high cooling rates.
BrOF6.5-0.15 alloy has a similar character of change in hardness.
The structure obtained in treatment of BrOFI0-1 bronze and the character of change in
its hardness differ from these parameters of the other investigated alloys.
With an increase
in radiation pulse energy an insignificant decrease in hardness is observed.
The hardness
of the areas with a eutectic + eutectoid structure drops while the hardness of the ~-phase
does not change (Table 4). In addition the dimensions of the dendrites do not change.
In
the original as-cast structure as the result of dendritic segregation the axes of the dendrites
are enriched with the more refractory component (copper) and depleted of the lower melting one
(tin).
In the interdendritic space, on the other hand, an increased tin content is observed.
In laser treatment the tin content is equalized (its content in the eutectic drops) and consequently the hardness decreases insignificantly in comparison with the hardness of the original material.
The abrasive wear resistance of the hardened zone of the bronzes was evaluated by the
method of scratching of the surface with a diamond pyramid.
The volume of metal removed was
calculated from the track of the scratch (Fig. 3). The action of the diamond pyramid may be
conditionally assumed to consist of two stages, indentation to a certain depth and scratching
through, which primarily determines the processes of deformation.
In a quantitative sense
the first stage is characterized by the hardness of the metal while the second is determined
by the intensity of occurrence of the martensite transformation and controls the wear (volume
of metal removed).
The character of resistance to abrasive wear is determined by the nature
of the alloy (Fig. 3). In laser treatment of BrOTsS4-4-2.5 bronze an increase in abrasive
wear resistance of the surface layers is observed, most sharply after treatment by irradiation
in a narrow range of powers of 450-500 W. The determining factor in the abrasive wear resistance of the hardened structure is not hardness but the intensity of structural transformations
during deformation.
The results of the relationship of the displaced volume in scratching of
the hardened zone to irradiation power make it possible to determine the microstructure of
BrOF6.5-0.15 alloy with the maximum wear resistance.
To such a structure corresponds higher
plasticity as the result of relaxation of internal stresses in further transformations during
deformation.
It should be noted that an increase in irradiation power to i000 W leads to the
formation of a packing of atoms providing an increase in plasticity and consequently in wear
resistance (by 1.5 times).

701

TABLE 2
Hardness HV after irradiation with a power ofsW

Alloy

B~)Ts4-4- 2.5

Bg)TsSS- 5- 5
~05-i0.1
5

Explanat ion.

lOS

11o
120
129

700

500
91 (--)
87 (--)
llO(--)
118 ( - - )

In parentheses

142
130
143
155

800

(12)
(15)
(50)
(90)

I51
143
160
163

(18)
(15)
(230)
(220)

10O0

162 (25)

157 (30)
177 (450)
181 (510)

is the depth of hardening in )am.

TABLE 3
Hardness HV after irradiation with a pulse energy of, J

Alloy
B~OTsS4- 4- 2.5
BlOF6.5- 0,.15
B~)FIO-1

Explanation.

l0

12

16

21

27

108
120
129

81 (6)
85 ( - - )
129 (140)

94 (15)
90 ( - - )
130(140)

123 (20)
107 (--)
120 (180)

125 (190)

153 (25)
160 (9o)

192 (25)
220 (130)
136(190)

In parentheses

is the depth of hardening in ~m.

TABLE 4
d enin~

paar
ses

H~lrdness J-/V after lr~d$afion

w~tn a pulse energy or, j

0110

!6

21

120

125

126

240 204 264 208 207

216

129

Euteetic y
eutectoid

129

130

27

Fig. 2. Microstructures of the heat-affected zone (a) and of the

zone of fusion (b) of BrOF6.5-0.15 alloy and the hardened zone of
BrOFIO-I alloy (c) after treatment: a, b) by continuous laser
irradiation with a power of i000 W and a rate of 20 mm/sec; c) by
pulsed irradiation with an energy of i0 J and a coefficient of
overlapping of 0.5.

702

Tn3m 3

F'IOi

V.IO~ m m
37,5

F
t

3X5

11

28
I
T!

13,5

a5

i_

500

700

900 ~ k W

80

40

q, k W / e ~q2

Fig 3. Relationship of the displaced volume of metal in

scratching of bronze specimens to the power of the continuous laser irradiation with a rate of treatment of 20
mm/sec (a) and to the density of the pulsed laser irradiation (b): i) BrOTsS4-4-2.5; 2) BrOF6.5-0.15; 3) BrOFI0-1.
The abrasive wear resistance of the investigated alloys treated with pulsed laser irradiation is shown in Fig. 3b. For BrOTsS4-4-2.5 and BrOF6.5-0.15 bronzes treatment with a power
density of pulsed irradiation of more than 6"104 W/cm 2 promotes the formation of a microstructure with an increased abrasive wear resistance. The optimum packing of the atoms of the
hardened structure of BrOFI0-1 alloy providing a 1.5 times increase in wear resistance in comparison with that for untreated material is formed under the action of laser irradiation with
a power density of 6.5"104 W/cm 2. From the results presented it may be seen that laser treatment of copper alloys promotes the formation in the hardened zone of a metastable phase with
increased mechanical properties.
The use of laser treatment for hardening of rubbing parts of copper alloys makes it
possible to increase the life of parts of machines and mechanisms.
Conclusions.
i. Laser treatment Of tin bronzes leads to the formation of a metastable
structure with high wear resistance.
2. The maximum hardness (220 HV) of the hardened zones of tin bronzes is obtained in
pulsed laser treatment with fusion.
LITERATURE CITED
i.
2.

3.
4.
5.

6.

V. N. Dubnyakov, S. F. Pulim, and T. E. Proskurina, "The influence of a concentrated

energy source on the properties of copper alloys," Elektron. Obrab., No. 6, 30-34 (1984).
V. N. Dubnyakov, S. F. Pulim, and T. E. Proskurina, "Increasing the wear resistance of
nonferrous alloys by laser irradiation," in: Technical Control of the Tribotechnical
Characteristics of Machine Assemblies [in Russian], Sevastopol' (1983), pp. 144-146.
V. N. Dubnyakov, "Laser hardening of copper alloys," Trakt. Sel'khozmash., No. 4, 30-32
(1984).
V. N. Dubnyakov and I. B. Malysheva, "The influence of the metastable condition of the
surface layers of solids on friction and wear," Trenie Iznos,- i, No. 5, 925-929 (1983).
V. N. Dubnyakov and S. F. Pulim, "The role of the metastable condition of the surface
layers of nonferrous alloys in the wear resistance of contacting pairs," Trenie Iznos, ~,
No. 6, 988-994 (1984).
I. S. Miroshnichenko, A. K. Petrov, et al., Zavod. Lab., No. 12, 1479-1481 (1972).

703