Deposition of W and W-RE alloys by gas-phase and plasma chemical methods
A thermodynamic analysis of the temperature dependence of the isobaric-isothermal potential processes of rhenium, tungsten and their compositions from a mixture of a metal fluorides with molecular and atomic hydrogen is provided. The dependence of the deposition rate of tungsten and tungsten-rhenium...
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| Дата: | 2016 |
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Національний науковий центр «Харківський фізико-технічний інститут» НАН України
2016
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| Назва видання: | Вопросы атомной науки и техники |
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| Цитувати: | Deposition of W and W-RE alloys by gas-phase and plasma chemical methods / P.I. Glushko, A.I. Yevsiukov, А.Yu. Ghuravlyov, N.А. Hovanskiy, D.A. Khizhnyak, B.M. Shirokov, А.V. Shijan // Вопросы атомной науки и техники. — 2016. — № 1. — С. 108-111. — Бібліогр.: 2 назв. — англ. |
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nasplib_isofts_kiev_ua-123456789-1117482025-02-09T13:53:23Z Deposition of W and W-RE alloys by gas-phase and plasma chemical methods Осадження W і W-Re-сплавів газофазним і плазмохімічним методами Осаждение W и W-Re-сплавов газофазным и плазмохимическим методами Glushko, P.I. Yevsiukov, A.I. Ghuravlyov, А.Yu. Hovanskiy, N.А. Khizhnyak, D.A. Shirokov, B.M. Shijan, А.V. Физика и технология конструкционных материалов A thermodynamic analysis of the temperature dependence of the isobaric-isothermal potential processes of rhenium, tungsten and their compositions from a mixture of a metal fluorides with molecular and atomic hydrogen is provided. The dependence of the deposition rate of tungsten and tungsten-rhenium alloys executed by plasma chemical and gas-phase methods on the substrate temperature, to power fed into discharge and the ratio of initial reagents is studied. Проведено термодинамічний аналіз температурної залежності ізобарно-ізотермічного потенціалу процесів отримання ренію, вольфраму і сплавів на їх основі з суміші фторидів металів з молекулярним і атомарним воднем. Досліджено залежність швидкості осадження вольфраму і вольфрам-ренієвих сплавів газофазним і плазмохімічним методами від температури підкладки, що вкладена в розряд потужності, і співвідношення вихідних реагентів. Проведено дослідження швидкості осадження W і W-Re-сплавів, що отримані газофазним і плазмохімічним методами, залежно від співвідношення H₂:MeF₆. Проведен термодинамический анализ температурной зависимости изобарно-изотермического потенциала процессов получения рения, вольфрама и сплавов на их основе из смеси фторидов металлов с молекулярным и атомарным водородом. Исследованы зависимости скорости осаждения вольфрама и вольфрам-рениевых сплавов газофазным и плазмохимическим методами от температуры подложки, вкладываемой в разряд мощности, и соотношения исходных реагентов. Проведено исследование скорости осаждения W и W-Re-сплавов, полученных газофазным и плазмохимическим методами, в зависимости от соотношения H₂:MeF₆. 2016 Article Deposition of W and W-RE alloys by gas-phase and plasma chemical methods / P.I. Glushko, A.I. Yevsiukov, А.Yu. Ghuravlyov, N.А. Hovanskiy, D.A. Khizhnyak, B.M. Shirokov, А.V. Shijan // Вопросы атомной науки и техники. — 2016. — № 1. — С. 108-111. — Бібліогр.: 2 назв. — англ. 1562-6016 https://nasplib.isofts.kiev.ua/handle/123456789/111748 539:2:538:975 en Вопросы атомной науки и техники application/pdf Національний науковий центр «Харківський фізико-технічний інститут» НАН України |
| institution |
Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| collection |
DSpace DC |
| language |
English |
| topic |
Физика и технология конструкционных материалов Физика и технология конструкционных материалов |
| spellingShingle |
Физика и технология конструкционных материалов Физика и технология конструкционных материалов Glushko, P.I. Yevsiukov, A.I. Ghuravlyov, А.Yu. Hovanskiy, N.А. Khizhnyak, D.A. Shirokov, B.M. Shijan, А.V. Deposition of W and W-RE alloys by gas-phase and plasma chemical methods Вопросы атомной науки и техники |
| description |
A thermodynamic analysis of the temperature dependence of the isobaric-isothermal potential processes of rhenium, tungsten and their compositions from a mixture of a metal fluorides with molecular and atomic hydrogen is provided. The dependence of the deposition rate of tungsten and tungsten-rhenium alloys executed by plasma chemical and gas-phase methods on the substrate temperature, to power fed into discharge and the ratio of initial reagents is studied. |
| format |
Article |
| author |
Glushko, P.I. Yevsiukov, A.I. Ghuravlyov, А.Yu. Hovanskiy, N.А. Khizhnyak, D.A. Shirokov, B.M. Shijan, А.V. |
| author_facet |
Glushko, P.I. Yevsiukov, A.I. Ghuravlyov, А.Yu. Hovanskiy, N.А. Khizhnyak, D.A. Shirokov, B.M. Shijan, А.V. |
| author_sort |
Glushko, P.I. |
| title |
Deposition of W and W-RE alloys by gas-phase and plasma chemical methods |
| title_short |
Deposition of W and W-RE alloys by gas-phase and plasma chemical methods |
| title_full |
Deposition of W and W-RE alloys by gas-phase and plasma chemical methods |
| title_fullStr |
Deposition of W and W-RE alloys by gas-phase and plasma chemical methods |
| title_full_unstemmed |
Deposition of W and W-RE alloys by gas-phase and plasma chemical methods |
| title_sort |
deposition of w and w-re alloys by gas-phase and plasma chemical methods |
| publisher |
Національний науковий центр «Харківський фізико-технічний інститут» НАН України |
| publishDate |
2016 |
| topic_facet |
Физика и технология конструкционных материалов |
| url |
https://nasplib.isofts.kiev.ua/handle/123456789/111748 |
| citation_txt |
Deposition of W and W-RE alloys by gas-phase and plasma chemical methods / P.I. Glushko, A.I. Yevsiukov, А.Yu. Ghuravlyov, N.А. Hovanskiy, D.A. Khizhnyak, B.M. Shirokov, А.V. Shijan // Вопросы атомной науки и техники. — 2016. — № 1. — С. 108-111. — Бібліогр.: 2 назв. — англ. |
| series |
Вопросы атомной науки и техники |
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2025-11-26T12:57:24Z |
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1849857773923205120 |
| fulltext |
ISSN 1562-6016. PASТ. 2016. №1(101), p. 108-111.
UDC 539:2:538:975
DEPOSITION OF W AND W-RE ALLOYS BY GAS-PHASE
AND PLASMA CHEMICAL METHODS
P.I. Glushko, A.I. Yevsiukov, А.Yu. Ghuravlyov, N.А. Hovanskiy, D.A. Khizhnyak,
B.M. Shirokov, А.V. Shijan
National Science Center “Kharkov Institute of Physics and Technology”,
Kharkov, Ukraine
A thermodynamic analysis of the temperature dependence of the isobaric-isothermal potential processes of rhe-
nium, tungsten and their compositions from a mixture of a metal fluorides with molecular and atomic hydrogen is
provided. The dependence of the deposition rate of tungsten and tungsten-rhenium alloys executed by plasma
chemical and gas-phase methods on the substrate temperature, to power fed into discharge and the ratio of initial
reagents is studied.
Tungsten is widely used in various fields of science
and technology as a construction material. However, a
major disadvantage of tungsten, which hinders its
broader use, is a cold cracking, a lack of plasticity at
low temperatures. Various methods, including the gas
phase method, are used for condensates obtaining from
tungsten and its alloys. Hydrogen reduction of metal
fluorides allows to obtain the condensates at relatively
low temperatures (~ 0.2 Tm) and at a comparatively high
deposition rate. The rhenium alloyage of tungsten con-
tributes to a plasticity improvement, decreasing the duc-
tile-brittle transition temperature of tungsten. To study
the laws of the plasma-chemical and gas-phase deposi-
tion of W, Re and W-Re alloys from a mixture of fluo-
ride metals with hydrogen have been performed a
thermodynamic analysis of reduction reactions of tung-
sten hexafluoride and rhenium with molecular and
atomic hydrogen, its goal was to determine the tempera-
ture conditions of chemical reactions. The equations of
interaction in chemical reactions of the reagents with
molecular and atomic hydrogen have the form:
WF6 +3H2↔W+6HF, (1)
WF6 +6H↔W+6HF, (2)
ReF6 +3H2↔Re+6HF, (3)
ReF6 +6H↔Re+6HF. (4)
The Fig. 1 shows the thermodynamic dependence of
Gibbs energy on temperature hexafluoride rhenium and
tungsten when recovering it by molecular hydrogen.
From Fig. 1 it is clear that the behavior of the isoba-
ric-isothermal potentials of the hydrogen reduction reac-
tions of tungsten hexafluoride and rhenium by molecu-
lar hydrogen with increasing temperature indicates on
increasing of the thermodynamic probability of the re-
duction reactions [1].
Fig. 2 shows the results of the temperature depen-
dence of the isobaric-isothermal potential for recovery
of tungsten hexafluoride and rhenium by atomic hydro-
gen. Comparison of these plots indicates that the Gibbs
energy has more negative value in case of fluorides
tungsten and rhenium reduction by atomic hydrogen. In
addition, the thermodynamic probability of reduction of
rhenium hexafluoride both by molecular and atomic
hydrogen is higher as the Gibbs energy has more nega-
tive value in comparison with the tungsten hexafluoride
reduction.
Fig. 1. Temperature dependence of the isobaric-
isothermal potential of the following reactions:
1 ReF6+3H2→Re+6HF; 2 WF6+3H2→W+6HF
400 600 800 1000 1200 1400 1600
-400
-350
-300
-250
2
1
G
ib
b
s
e
n
e
rg
y
,
k
c
a
l
/
m
o
l
Temperature, К
Fig. 2. Temperature dependence of the isobaric-
isothermal potential reactions of atomic hydrogen
fluoride reduction: 1 – ReF6+6H→Re+6HF;
2 – WF6+6H→W+6HF
Experiments on the gas-phase deposition of tungsten
and tungsten-rhenium condensates (Fig. 3) were carried
out at a pressure of 2·10
3
Pa in the reaction chamber, H2
flow rate 45 l/h and with ratio H2: WF6 = 10:1. Rheni-
um low-alloyed condensates of tungsten fluoride were
deposited from the gas mixture H2 + (97% WF6 +
3% ReF6) = 10:1. Tungsten-rhenium alloys with Re
content more than 12% were obtained from the gas
phase H2 + (88% WF6 + 12% ReF6) = 10:1. Silicon sub-
strates were used for gas-phase and plasma chemical
deposition.
400 450 500 550 600 650 700
50
100
150
200
250
300
350
V
d
e
p
,
(µ
m
)
T,
0
C
H
2
+ (97% WF
6
+3% ReF
6
)
H
2
+ WF
6
H
2
+ (88% WF
6
+ 12% ReF
6
)
Fig. 3. Dependence of the deposition rate of tungsten
and tungsten-rhenium alloys on temperature, in various
gas mixtures
Analysis of the obtained curves shows that the depo-
sition rate of pure tungsten and tungsten with a little
additive of rhenium is almost identical, and the deposi-
tion rate of the W-Re alloy with rhenium content more
than 9% is higher in entire temperature range. If the
deposition rate of the alloy is expressed as sum of two
independent deposition rates of pure rhenium and tung-
sten, it is obvious that the temperature change affects
only the deposition rate of tungsten and has virtually no
effect on the deposition rate of rhenium. This fact indi-
cates that the presence of rhenium hexafluoride in the
gas phase intensifies the recovery process of tungsten
hexafluoride. Moreover, intensification at low tempera-
tures is higher than at high temperatures.
Microstructure of pure and low-alloyed condensates
of tungsten is columnar, it is typical for gas-phase mate-
rials, the grain sizes are almost identical to all growing
layer. The condensates, obtained from the gas phase
composition of H2 + (88% WF6 and 12% ReF6) at
Tdep = 550 °C and higher, have columnar violations and
appearing of jagged borders. Electron diffraction studies
of tungsten-rhenium alloys showed that the structure of
the deposited tungsten-rhenium alloys have two types of
grains. Some is the -solution (Fig. 4,a), the others
have a lamellar structure (see Fig. 4,b) and consist with
a sum of the -solution and structure of the A-15 type
phase a.
The plates themselves have a thin structure. The
dark field image in a reflex of the of the A-15 structure
gives grounds to assert that the plates themselves is the
-solution with the introduction of a microlayer A-15,
and the border between the plates is not the A-15 type.
The plates are perpendicular arranged to the growth
direction.
Mechanical properties of the condensates, deposited
from the gas phase of various composition, was meas-
ured by the presented values of the bending strength
( ben ) and the temperature of brittle-plastic transition
(Тb). The measurement results of the values ben and
Тb for samples obtained at the temperatures of 450, 550,
and 650 °C are presented in the Table.
Fig. 4. Fractography of a fracture tungsten-rhenium
alloy: a -solution, b -phase solution plus the
structural A-15, x20000
The experimental studies of the plasma chemical
deposition of tungsten and W-Re alloys of the metals
with the mixture of hydrogen fluoride were carried out
in the flow type horizontal reactor [2]. The plasma dis-
charge in the reactor was excited by the high-frequency
generator VChG-25/0.44 with the operating frequency
of 0.44 MHz. The ranges of tested parameters: the pres-
sure in the reactor from 5·10
2
to 1,3·10
3
Pa, the sub-
strate temperature from 400 to 700 °C, the ratio H2
МеFn from 3:1 to 15:1, the discharge capacity from
1 to 6 kW. Fig. 5 shows the dependencies of the deposi-
tion rates W, and W-Re alloy on temperature, obtained
by the plasma chemical vapor deposition method. In the
condensates of the tungsten-rhenium alloy, obtained by
the plasma-chemical method, the phase of the A-15
structural type is absent.
Flexural strength and temperature of the brittle-plastic transition condensates obtained under various deposition
conditions
Condensate
composition
Measured value Тdep = 450 С Тdep = 550 С Тdep = 650 С
W 340 365 415
W+3% Re
ben , MPa 280 785 770
W+11% Re 775 850 885
W 580 630 550
W+3% Re Тb, С 225 245 210
W+11% Re 180 220 205
400 450 500 550 600 650 700
150
200
250
300
350
400
450
V
b
e
d
(
µ
m
/h
)
Temperature,
0
С
1
2
3a
400 450 500 550 600 650 700
250
300
350
400
450
V
d
e
p
(
µ
m
/h
)
Temperature,
0
С
1
2
3
,
b
Fig. 5. Dependence of the deposition rate of W (a) and W-Re alloy (b) by the plasma-chemical method
on the substrate temperature, with power fed into discharge of 1 1.5 kW; 2 3.5 kW; 3 6 kW
Fig. 6 shows the dependence of the deposition rates
of W and W-Re alloys, obtained by plasma-chemical
and gas-phase methods on the ratio of the initial rea-
gents.
2 4 6 8 10 12 14 16
20
40
60
80
100
120
140
160
180
V
d
e
p
(µ
m
/s
)
H
2
:MeF
6
1
2
3
4
Fig. 6. Kinetics of the deposition W and W-Re alloys,
on ratio of H2:MeF6: 1 – W-gas phase;
2 – W-Re-gas phase; 3 – W-plasma-chemical;
4 – W-Re-plasma-chemical
The study of the flow rate dependence from the rea-
gent ratio showed that during increasing of the H2: MeF6
ratio a maximum is observed, its presence can be ex-
plained by depletion of the vapor-gas mixture caused by
a metal fluorides.
CONCLUSION
A thermodynamic analysis of the temperature de-
pendence of the isobaric-isothermal potential processes
of rhenium, tungsten and their compositions from a
mixture of metal fluorides with hydrogen is provided. It
is shown that in the atomic hydrogen medium, the re-
duction reaction of fluoride rhenium proceeds at lower
temperatures than in the molecular hydrogen medium.
Kinetic of W and W-Re alloys deposition by gas
phase plasma-chemical methods from a temperature of
the substrate and power fed into discharge was studied.
It was determined that the deposition rate of tungsten
and tungsten-rhenium alloys increases with the tempera-
ture of a substrate and power fed into the discharge.
The study of the deposition rate of W and W-Re al-
loys, obtained by gas phase and plasma-chemical meth-
ods depending on the H2:MeF6 ratio was conducted.
When the magnitude of the ratio is increasing, the depo-
sition rate is increasing and reaches its maximum at the
ratio of 10:1, and then starts to decrease. Herewith the
deposition rate of the condensates, obtained by the
plasma-chemical deposition method is approximately
two times higher in comparison with the gas-phase
method.
REFERENCES
1. L.S. Polak. Kinetika i termodinamika khimi-
cheskikh reaktsiy v nizkotemperaturnoy plazme. M.:
«Nauka», 1965, 254 p. (in Russian).
2. P.G. Kryshtal', B.M. Shirokov. Otsenka dis-
sotsiatsii molekulyarnogo vodoroda v impul'sno-
periodicheskom vysokochastotnom razryade nizkogo
davleniya // Vísnik natsíonal'nogo tekhníchnogo uníver-
sitetu «KHPI». 2007, №8, p. 54-64 (in Russian).
Article received 22.07.2015
ОСАЖДЕНИЕ W И W-Re-СПЛАВОВ ГАЗОФАЗНЫМ И ПЛАЗМОХИМИЧЕСКИМ
МЕТОДАМИ
П.И. Глушко, А.И. Евсюков, А.Ю. Журавлёв, Н.А. Хованский, Д.А. Хижняк, Б.М. Широков, А.В. Шиян
Проведен термодинамический анализ температурной зависимости изобарно-изотермического потенциа-
ла процессов получения рения, вольфрама и сплавов на их основе из смеси фторидов металлов с молекуляр-
ным и атомарным водородом. Исследованы зависимости скорости осаждения вольфрама и вольфрам-
рениевых сплавов газофазным и плазмохимическим методами от температуры подложки, вкладываемой в
разряд мощности, и соотношения исходных реагентов. Проведено исследование скорости осаждения W и
W-Re-сплавов, полученных газофазным и плазмохимическим методами, в зависимости от соотношения
H2:MeF6.
a b
V
b
e
d
,
m
/h
V
b
e
d
,
m
/h
V
d
e
p
,
m
/s
ОСАДЖЕННЯ W І W-Re-СПЛАВІВ ГАЗОФАЗНИМ І ПЛАЗМОХІМІЧНИМ МЕТОДАМИ
П.І. Глушко, О.І. Євсюков, О.Ю. Журавльов, М.О. Хованський, Д.О. Хижняк, Б.М. Широков, О.В. Шиян
Проведено термодинамічний аналіз температурної залежності ізобарно-ізотермічного потенціалу проце-
сів отримання ренію, вольфраму і сплавів на їх основі з суміші фторидів металів з молекулярним і атомар-
ним воднем. Досліджено залежність швидкості осадження вольфраму і вольфрам-ренієвих сплавів газофаз-
ним і плазмохімічним методами від температури підкладки, що вкладена в розряд потужності, і співвідно-
шення вихідних реагентів. Проведено дослідження швидкості осадження W і W-Re-сплавів, що отримані
газофазним і плазмохімічним методами, залежно від співвідношення H2:MeF6.
|