The effect of unintentional oxygen incorporation into Cr-CrN-DLC coatings deposited by MePIIID method using filtered cathodic vacuum arc carbon and metal plasma
The multilayer Cr-CrN-DLC coatings deposited by MePIIID method on substrates made of high speed steel HS 6-5-2 were studied. The streams of filtered carbon and metal arc plasma were used in both ion implantation and deposition phases. Investigation of the chemical composition of Cr-CrN-DLC coatings...
Saved in:
| Date: | 2010 |
|---|---|
| Main Authors: | , , |
| Format: | Article |
| Language: | English |
| Published: |
Національний науковий центр «Харківський фізико-технічний інститут» НАН України
2010
|
| Subjects: | |
| Online Access: | https://nasplib.isofts.kiev.ua/handle/123456789/17497 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Journal Title: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Cite this: | The effect of unintentional oxygen incorporation into Cr-CrN-DLC coatings deposited by MePIIID method using filtered cathodic vacuum arc carbon and metal plasma / J. Walkowicz, J. Bujak, V. Zavaleyev // Вопросы атомной науки и техники. — 2010. — № 6. — С. 179-181. — Бібліогр.: 3 назв. — англ. |
Institution
Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1859734116477435904 |
|---|---|
| author | Walkowicz, J. Bujak, J. Zavaleyev, V. |
| author_facet | Walkowicz, J. Bujak, J. Zavaleyev, V. |
| citation_txt | The effect of unintentional oxygen incorporation into Cr-CrN-DLC coatings deposited by MePIIID method using filtered cathodic vacuum arc carbon and metal plasma / J. Walkowicz, J. Bujak, V. Zavaleyev // Вопросы атомной науки и техники. — 2010. — № 6. — С. 179-181. — Бібліогр.: 3 назв. — англ. |
| collection | DSpace DC |
| description | The multilayer Cr-CrN-DLC coatings deposited by MePIIID method on substrates made of high speed steel HS 6-5-2 were studied. The streams of filtered carbon and metal arc plasma were used in both ion implantation and deposition phases. Investigation of the chemical composition of Cr-CrN-DLC coatings revealed considerable amount of oxygen in deposited DLC film. Additional alloying of DLC films with chromium reduced the concentration of oxygen. The presence of oxygen affects the properties of DLC coatings, which was confirmed by the investigation of the hardness and adhesion.
Изучаются многослойные покрытия Cr-CrN-DLC, осажденные методом MePIIID, на подложках из быстрорежущей стали HS 6-5-2. Отфильтрованные потоки углеродной и металлической плазмы использовались в ионной имплантации и осаждении покрытий. Исследование химического состава Cr-CrN-DLC-покрытий показало значительное количество кислорода в осажденных DLC-пленках. Дополнительное легирование пленок DLC хромом сократило концентрацию кислорода. Присутствие кислорода влияет на свойства покрытий DLC, которые были подвержены исследованиям на твердость и адгезию.
Вивчаються багатошарові покриття Cr-CrN-DLC, осадженні методом MePIIID, на підкладках з швидкорізальної сталі HS 6-5-2. Відфільтровані потоки вуглецевої та металевої плазми використовувались в іонній імплантації та осадженні покриттів. Дослідження хімічного складу Cr-CrN-DLC-покриттів виявило значну кількість кисню в осаджених DLC-плівках. Додаткове легування плівок DLC хромом зменшило концентрацію кисню. Присутність кисню впливає на властивості покриттів DLC, які були досліджені на твердість та адгезію.
|
| first_indexed | 2025-12-01T14:23:51Z |
| format | Article |
| fulltext |
THE EFFECT OF UNINTENTIONAL OXYGEN INCORPORATION
INTO Cr-CrN-DLC COATINGS DEPOSITED BY MePIIID METHOD USING
FILTERED CATHODIC VACUUM ARC CARBON AND METAL PLASMA
J. Walkowicz1, J. Bujak2, V. Zavaleyev1
1 Institute of Mechatronics, Nanotechnology and Vacuum Technique,
Koszalin University of Technology, Koszalin, Poland;
2Institute for Sustainable Technologies - NRI, Radom, Poland
E-mail: jan.walkowicz@tu.koszalin.pl
The multilayer Cr-CrN-DLC coatings deposited by MePIIID method on substrates made of high speed steel
HS 6-5-2 were studied. The streams of filtered carbon and metal arc plasma were used in both ion implantation and
deposition phases. Investigation of the chemical composition of Cr-CrN-DLC coatings revealed considerable amount of
oxygen in deposited DLC film. Additional alloying of DLC films with chromium reduced the concentration of oxygen.
The presence of oxygen affects the properties of DLC coatings, which was confirmed by the investigation of the
hardness and adhesion.
PACS: 81.15.Jj
1. INTRODUCTION
Metal Plasma Immersion Ion Implantation and
Deposition (MePIIID) is a hybrid process, widely used for
simultaneous implantation and deposition of metallic and
ceramic films in reactive and non-reactive environments
[1]. Most of papers on the MePIIID method report the use
of curved magnetic filters for removing microdroplets
from metallic plasma flow used for implantation and
deposition of metallic components of coatings, and
methane or acetylene as a carbon carrying media for DLC
films deposition.
In this paper, the modification of hybrid MePIIID
process is presented, which consists in the use of
combined techniques of filtering cathodic arc plasma
flows – carbon plasma flow by T-shape magnetic filter
and chromium plasma flow by electrostatic filter.
2. EXPERIMENTAL TECHNIQUES
The synthesis of Cr-CrN-DLC coatings was carried
out using the modernized vacuum arc device developed
especially for MePIIID technology. The coatings were
deposited on the substrates made from high speed steel
HS 6-5-2 mounted in the zone where carbon and
chromium plasma flows mixed (Fig. 1).
Fig. 1. The substrate immersed in the flows of chromium
plasma (from the left) and carbon plasma (from the right)
passing through the separators during
the MePIIID process
Before the placement in the vacuum chamber the
substrates were ground and polished to the roughness of
Ra = 0,06 μm and then washed and degreased in
trichloroethylene. The initial vacuum in the chamber was
at the level of 1×10-5 mbar. As source materials for
deposition of Cr-CrN-DLC coatings a pure chromium (Cr
99.999%) and a pure carbon (C 99,999%) cathodes were
used. Arc currents of 75A for chromium and 90A for
carbon were applied. The magnetic flux density along the
T-shaped filter axis amounted to 16 mT, the electrostatic
filter was biased with the positive potential of 27 V.
All experiments consisted of four stages of technological
process:
1. substrate etching and heating by the bombardment
with argon ions in arc enhanced glow discharge (AEGD),
2. ion implantation and deposition of chromium
sublayer from filtered vacuum arc plasma,
3. deposition of CrN coating from filtered chromium arc
plasma in nitrogen atmosphere,
4. deposition of DLC coating from filtered carbon arc
plasma in argon atmosphere.
The parameters of deposition of multilayer Cr-CrN-DLC
coatings are shown in the Table below. The substrate
temperature during the experiments was measured by the
infared pyrometer Raytek Termalert 4. The hardness of
the coatings was measured using nano-hardness tester
CSEM with a Berkovich pyramid. Quantitative analysis
of the coatings composition was carried out using radio
frequency glow discharge optical emission spectrometer
(RF GDOES) JY10000RF produced by the company
Jobin Yvon Horiba. Analysis of the sample surfaces
composition was also performed by the X-ray
Photoelectron Spectroscopy (XPS) using the spectrometer
produced by the company Vacuum Systems Workshop
Ltd. (VSW) England. The surface morphology of the
coatings and their roughness parameters were studied
using an atomic force microscope (AFM) Q-Scope 250
produced by the company Quesant Instrument
Corporation.
PROBLEMS OF ATOMIC SCIENCE AND TECHNOLOGY. 2010. № 6. 179
Series: Plasma Physics (16), p. 179-181.
Parameters of deposition of multilayer Cr-CrN-DLC coatings
Stage of the
process
Gas, pressure
p [mbar]
Substrate BIAS
UBIAS [kV]
Pulse duration
τ [μs]
Pulse frequency
f [kHz]
Substrate temp.
T [°C]
Process time
t [min]
Substrate etching
(AEGD)
Ar
5,0×10-3 2 20 2 90 15
Cr implantation
and deposition
Without gas
1,0×10-5 2 20 2 100 10
CrN coating
deposition
N2
4,0×10-3 2 20 2 115 20
DLC coating
deposition
Ar
1,2×10-4 2/4/6 20 1/2/2,5 165…200 30
3. RESULTS AND DISCUSSION
The total thickness of Cr-CrN-DLC coatings obtained
was about 2,2 μm. Investigation of surface morphology of
Cr-CrN coatings showed that the electrostatic separator
does not remove completely droplet phase from the
plasma flow (Fig. 2).
Fig. 2. The surface morphology of Cr-CrN coating
deposited with the use of the electrostatic separator
The presence of droplets on the substrate surface shows
that part of the droplets pass through a filter to the
substrate, spreading over its surface, stick on it and are
immured by the deposited flux.
The surface morphology of the investigated DLC
coatings deposited using the T-shaped magnetic filter
confirms high effectiveness of cleaning carbon plasma
from the microparticles in this system (Fig. 3).
Fig. 3. Surface morphology of DLC coatings deposited
with the use of the magnetic separator
The presence of a small number of defects on the surface
shows that most of the carbon particulates remains inside
the filter and only the smallest microparticles can pass
due to the rebounding inside plasma guide [2]. Using the
RF GDOES method the distribution of the concentrations
of Cr-CrN-DLC coating components throughout the
coating thickness was determined (Fig. 4).
Fig. 4. Concentration profiles of Cr-CrN-DLC
coating components
In the investigated samples with Cr-CrN-DLC coatings a
high concentration of oxygen of 38…45 at. % was
observed on the surface of DLC film. The infiltration of
oxygen during the experiment was excluded because
vacuum of 1×10-5 mbar was reached before each stage of
the process and high purity gases (99,9999%) were used.
Local maximum of nitrogen concentration coinciding
with the maximum of oxygen concentration suggested
that most likely, oxygen penetrated into the vacuum
chamber and the coating when the chamber was open to
the atmosphere, despite the fact that the substrates were
previously cooled to the temperature of 50°C and the
chamber was heated with warm water.
In order to prevent oxygen infiltration into the coating
two additional stages of the process were included:
− pre-sputtering of the carbon cathode by arc discharge,
− doping of deposited DLC coating with chromium.
Pre-sputtering of the cathode did not yielded significant
results, but doping of DLC coating with Cr allowed the
oxygen concentration to be significantly reduced (Fig. 5).
Fig. 5. C1s peaks of XPS spectrum of DLC coating
doped with chromium
180
The analysis of C1s peaks of XPS spectrum of DLC film
doped with Cr indicates predominant occurrence of sp3
and sp2 carbon bonds. Energy shift from 285 eV to
284 eV indicates the sp3 → sp2 phase transformation in
the DLC film due to the temperature rise caused by its
bombardment with Cr ions.
Increasing the substrate temperature to 200°C and an
increase in ion energy up to 6 keV decreases the
microhardness and the Young modulus, and thus internal
stresses [3], of the film (Fig. 6).
a
b
Fig. 6. Dependence of hardness (a) and Young modulus
(b) of Cr-CrN-DLC coatings on the substrate BIAS
It is also noticed that the maximum critical load has
increased from 15 to 26 N, with substrate BIAS increase
from 2 kV to 6 kV, and was consistent with low internal
stress at high accelerating potential on the substrate of
6 kV (Fig. 7).
Fig. 7. Changes in the critical load of adhesion with
substrate BIAS for Cr doped Cr-CrN-DLC coatings
4. CONCLUSIONS
The paper presents research on the properties of
Cr-CrN-DLC coatings. GDOES spectra showed the
presence of oxygen impurity in the film, but doping of
DLC coatings with Cr reduced the oxygen amount. It was
also shown that the adhesion of the Cr-CrN-DLC coatings
obtained by the MePIIID method, can be improved with
increasing substrate BIAS, and respectively, internal
stresses of the coatings will decrease, but the hardness of
the films will also decrease.
REFERENCES
1. A. Anders. Energetic deposition using filtered cathodic
arc plasmas // Vacuum. 2002, v. 67, p. 673-686.
2. I.I. Aksenov, V.E. Strel’nitskij, V.V. Vasilyev,
D.Yu. Zaleskij. Efficiency of magnetic plasma filters//
Surface and Coatings Technology. 2003, v 163-164,
p. 118-127.
3. X. Zhang, Z. Wu, X. Wu, L. Qin, X. Yu, Y. Xu,
H. Zhang. Structure and properties of tetrahedral
amorphous carbon films implanted with Ti ion//
Surface and Coatings Technology. 2007, v. 201,
p. 5219-5222.
Article received 13.09.10
ЭФФЕКТ НЕПРЕДНАМЕРЕННОГО ВНЕДРЕНИЯ КИСЛОРОДА В Cr-CrN-DLC-ПОКРЫТИЯ,
ОСАЖДЕННЫЕ МЕТОДОМ MePIIID, С ИСПОЛЬЗОВАНИЕМ ФИЛЬТРОВАННОЙ
ВАКУУМНО-ДУГОВОЙ УГЛЕРОДНОЙ И МЕТАЛЛИЧЕСКОЙ ПЛАЗМЫ
Я. Валькович, Я. Буяк, В. Завалеев
Изучаются многослойные покрытия Cr-CrN-DLC, осажденные методом MePIIID, на подложках из
быстрорежущей стали HS 6-5-2. Отфильтрованные потоки углеродной и металлической плазмы использовались
в ионной имплантации и осаждении покрытий. Исследование химического состава Cr-CrN-DLC-покрытий
показало значительное количество кислорода в осажденных DLC-пленках. Дополнительное легирование
пленок DLC хромом сократило концентрацию кислорода. Присутствие кислорода влияет на свойства покрытий
DLC, которые были подвержены исследованиям на твердость и адгезию.
ЕФЕКТ НЕНАВМИСНОГО ПРОНИКНЕННЯ КИСНЮ У Cr-CrN-DLC-ПОКРИТТЯ,
ОСАДЖЕННІ МЕТОДОМ MePIIID, З ВИКОРИСТАННЯМ ФІЛЬТРОВАНОЇ
ВАКУУМНО-ДУГОВОЇ ВУГЛЕЦЕВОЇ ТА МЕТАЛЕВОЇ ПЛАЗМИ
Я. Валькович, Я. Буяк, В. Завалєєв
Вивчаються багатошарові покриття Cr-CrN-DLC, осадженні методом MePIIID, на підкладках з
швидкорізальної сталі HS 6-5-2. Відфільтровані потоки вуглецевої та металевої плазми використовувались в
іонній імплантації та осадженні покриттів. Дослідження хімічного складу Cr-CrN-DLC-покриттів виявило
значну кількість кисню в осаджених DLC-плівках. Додаткове легування плівок DLC хромом зменшило
концентрацію кисню. Присутність кисню впливає на властивості покриттів DLC, які були досліджені на
твердість та адгезію.
181
|
| id | nasplib_isofts_kiev_ua-123456789-17497 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1562-6016 |
| language | English |
| last_indexed | 2025-12-01T14:23:51Z |
| publishDate | 2010 |
| publisher | Національний науковий центр «Харківський фізико-технічний інститут» НАН України |
| record_format | dspace |
| spelling | Walkowicz, J. Bujak, J. Zavaleyev, V. 2011-02-26T23:00:30Z 2011-02-26T23:00:30Z 2010 The effect of unintentional oxygen incorporation into Cr-CrN-DLC coatings deposited by MePIIID method using filtered cathodic vacuum arc carbon and metal plasma / J. Walkowicz, J. Bujak, V. Zavaleyev // Вопросы атомной науки и техники. — 2010. — № 6. — С. 179-181. — Бібліогр.: 3 назв. — англ. 1562-6016 https://nasplib.isofts.kiev.ua/handle/123456789/17497 The multilayer Cr-CrN-DLC coatings deposited by MePIIID method on substrates made of high speed steel HS 6-5-2 were studied. The streams of filtered carbon and metal arc plasma were used in both ion implantation and deposition phases. Investigation of the chemical composition of Cr-CrN-DLC coatings revealed considerable amount of oxygen in deposited DLC film. Additional alloying of DLC films with chromium reduced the concentration of oxygen. The presence of oxygen affects the properties of DLC coatings, which was confirmed by the investigation of the hardness and adhesion. Изучаются многослойные покрытия Cr-CrN-DLC, осажденные методом MePIIID, на подложках из быстрорежущей стали HS 6-5-2. Отфильтрованные потоки углеродной и металлической плазмы использовались в ионной имплантации и осаждении покрытий. Исследование химического состава Cr-CrN-DLC-покрытий показало значительное количество кислорода в осажденных DLC-пленках. Дополнительное легирование пленок DLC хромом сократило концентрацию кислорода. Присутствие кислорода влияет на свойства покрытий DLC, которые были подвержены исследованиям на твердость и адгезию. Вивчаються багатошарові покриття Cr-CrN-DLC, осадженні методом MePIIID, на підкладках з швидкорізальної сталі HS 6-5-2. Відфільтровані потоки вуглецевої та металевої плазми використовувались в іонній імплантації та осадженні покриттів. Дослідження хімічного складу Cr-CrN-DLC-покриттів виявило значну кількість кисню в осаджених DLC-плівках. Додаткове легування плівок DLC хромом зменшило концентрацію кисню. Присутність кисню впливає на властивості покриттів DLC, які були досліджені на твердість та адгезію. en Національний науковий центр «Харківський фізико-технічний інститут» НАН України Низкотемпературная плазма и плазменные технологии The effect of unintentional oxygen incorporation into Cr-CrN-DLC coatings deposited by MePIIID method using filtered cathodic vacuum arc carbon and metal plasma Эффект непреднамеренного внедрения кислорода в Cr-CrN-DLC-покрытия, осажденные методом MePIIID, с использованием фильтрованной вакуумно-дуговой углеродной и металлической плазмы Ефект ненавмисного проникнення кисню у Cr-CrN-DLC-покриття, осадженні методом MePIIID, з використанням фільтрованої вакуумно-дугової вуглецевої та металевої плазми Article published earlier |
| spellingShingle | The effect of unintentional oxygen incorporation into Cr-CrN-DLC coatings deposited by MePIIID method using filtered cathodic vacuum arc carbon and metal plasma Walkowicz, J. Bujak, J. Zavaleyev, V. Низкотемпературная плазма и плазменные технологии |
| title | The effect of unintentional oxygen incorporation into Cr-CrN-DLC coatings deposited by MePIIID method using filtered cathodic vacuum arc carbon and metal plasma |
| title_alt | Эффект непреднамеренного внедрения кислорода в Cr-CrN-DLC-покрытия, осажденные методом MePIIID, с использованием фильтрованной вакуумно-дуговой углеродной и металлической плазмы Ефект ненавмисного проникнення кисню у Cr-CrN-DLC-покриття, осадженні методом MePIIID, з використанням фільтрованої вакуумно-дугової вуглецевої та металевої плазми |
| title_full | The effect of unintentional oxygen incorporation into Cr-CrN-DLC coatings deposited by MePIIID method using filtered cathodic vacuum arc carbon and metal plasma |
| title_fullStr | The effect of unintentional oxygen incorporation into Cr-CrN-DLC coatings deposited by MePIIID method using filtered cathodic vacuum arc carbon and metal plasma |
| title_full_unstemmed | The effect of unintentional oxygen incorporation into Cr-CrN-DLC coatings deposited by MePIIID method using filtered cathodic vacuum arc carbon and metal plasma |
| title_short | The effect of unintentional oxygen incorporation into Cr-CrN-DLC coatings deposited by MePIIID method using filtered cathodic vacuum arc carbon and metal plasma |
| title_sort | effect of unintentional oxygen incorporation into cr-crn-dlc coatings deposited by mepiiid method using filtered cathodic vacuum arc carbon and metal plasma |
| topic | Низкотемпературная плазма и плазменные технологии |
| topic_facet | Низкотемпературная плазма и плазменные технологии |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/17497 |
| work_keys_str_mv | AT walkowiczj theeffectofunintentionaloxygenincorporationintocrcrndlccoatingsdepositedbymepiiidmethodusingfilteredcathodicvacuumarccarbonandmetalplasma AT bujakj theeffectofunintentionaloxygenincorporationintocrcrndlccoatingsdepositedbymepiiidmethodusingfilteredcathodicvacuumarccarbonandmetalplasma AT zavaleyevv theeffectofunintentionaloxygenincorporationintocrcrndlccoatingsdepositedbymepiiidmethodusingfilteredcathodicvacuumarccarbonandmetalplasma AT walkowiczj éffektneprednamerennogovnedreniâkislorodavcrcrndlcpokrytiâosaždennyemetodommepiiidsispolʹzovaniemfilʹtrovannoivakuumnodugovoiuglerodnoiimetalličeskoiplazmy AT bujakj éffektneprednamerennogovnedreniâkislorodavcrcrndlcpokrytiâosaždennyemetodommepiiidsispolʹzovaniemfilʹtrovannoivakuumnodugovoiuglerodnoiimetalličeskoiplazmy AT zavaleyevv éffektneprednamerennogovnedreniâkislorodavcrcrndlcpokrytiâosaždennyemetodommepiiidsispolʹzovaniemfilʹtrovannoivakuumnodugovoiuglerodnoiimetalličeskoiplazmy AT walkowiczj efektnenavmisnogoproniknennâkisnûucrcrndlcpokrittâosadžennímetodommepiiidzvikoristannâmfílʹtrovanoívakuumnodugovoívuglecevoítametalevoíplazmi AT bujakj efektnenavmisnogoproniknennâkisnûucrcrndlcpokrittâosadžennímetodommepiiidzvikoristannâmfílʹtrovanoívakuumnodugovoívuglecevoítametalevoíplazmi AT zavaleyevv efektnenavmisnogoproniknennâkisnûucrcrndlcpokrittâosadžennímetodommepiiidzvikoristannâmfílʹtrovanoívakuumnodugovoívuglecevoítametalevoíplazmi AT walkowiczj effectofunintentionaloxygenincorporationintocrcrndlccoatingsdepositedbymepiiidmethodusingfilteredcathodicvacuumarccarbonandmetalplasma AT bujakj effectofunintentionaloxygenincorporationintocrcrndlccoatingsdepositedbymepiiidmethodusingfilteredcathodicvacuumarccarbonandmetalplasma AT zavaleyevv effectofunintentionaloxygenincorporationintocrcrndlccoatingsdepositedbymepiiidmethodusingfilteredcathodicvacuumarccarbonandmetalplasma |