REVESTIMENTOS MULTIFUNCIONAIS A
BASE DE CARBONO APLICADOS EM
COMPRESSORES HERMÉTICOS SEM
ÓLEO.
José Daniel Biasoli de Mello
Laboratório de Tribologia e Materiais – Faculdade de Engenharia Mecânica
Universidade Federal de Uberlândia, Brazil
Laboratório de Materiais – Faculdade de Engenharia Mecânica
Universidade Federal de Santa Catarina, Brazil
COLLABORATORS:
 Aloísio Nelmo Klein - LabMat - UFSC
 Andreas Polycarpou - UIUC - TAMU.
 Cristiano Binder - LabMat - UFSC
 Diego Salvaro - UFSC
 Gisele Hannes - LabMat - UFSC
 Henara Lilian Costa - L. T. M. - U.F.U
 Luciano Castro Lara - UFU-UFES
 Marcelo Braga dos Santos U.F.U.
 Marcio Silverio - EMBRACO S A
Milena Barbosa Vellanga - UFSC
 Nicholaos G. Demas - ANL
 Pedro Shioga - UFSC
 Roberto Binder - EMBRACO S A
Acknowledgements :
The author acknowledge the following agencies for funding this
research: Fulbright; CNPq, BNDES, FINEP, FAPEMIG and CAPESProex (Brazil) as well as Whirlpool/Embraco.
Hermetic compressor??
Refrigeration: Home energy consumption
17.3%
United States Environmental Protection Agency, Partnerships for Home Energy Efficiency Report
47%
Programa Nacional de Conservação de Energia Elétrica, Pesquisa de Posse de Equipamentos e Hábitos de Uso – Ano Base 2005, Classe
Residencial, Relatório Brasil
Refrigeration: Commercial energy consumption
USA
Commercial energy
consumption = 0.719
Quad = 208.24 GWh
Navigant Consulting Inc, Energy savings potential and R&D opportunities for commercial refrigeration – Final Report, September 2009, 211 pages.
Any improvement in the
efficiency of the hermetic
compressor may have a
substantial impact on the global
energy balance and, as a
consequence, on the
environment.
The refrigeration industry has moved on from CFC based
refrigerants such as R-12 to environmentally friendly HFC based
refrigerants like R134a and more recently to the harmless isobutene
R600a.
Refrigerant
CFC R12
HCFC R22
HFCR 134a
Propane R230
Butane R600
Isobutane R600a
Life Time ODP HGWP
(years)
120
15
16
Months
Weeks
< 1 Week
1
<1
0
0
0
0
Toxicity
Air Flammability
7100
TLV= 1000ppm
1500
3200
AEL= 1000 ppm
<5
Low
< 5 Slightly anaesthetic - TLV= 800ppm
<0.01
Slightly anaesthetic - TLV= ND
LEL
UEL
Volume %
Not flammable
Not flammable
2.1
9.5
1.8
8.5
1.8
8.5
ODP = Ozone Depletion Potential - HGWP = Halocarbon Global Warming Potential - TLV= Threshold limit value
AEL = Acceptable exposure limit - LEL = Lower explosive limit - UEL = Upper explosive limit
Moreover, due to miscibility issues with HFC refrigerants, the
compressor lubricants have also changed from mineral type
lubricant to synthetic polyolester (POE) and polyalkylene glycol
(PAG) lubricants.
ARLTERNATIVE REFRIGERANT
&
ARLTERNATIVE LUBRICANTS
⇓
Increase in severity of tribological contacts
+
Smaller clearances and increased speeds
+
Miscibility oil – refrigerant / insulation
+
Limited lubrication: boundary and mixed lubrication regimes
⇓
TOWARDS OIL-LESS COMPRESSORS
SOLID LUBRICATION AND SOLID
LUBRICANTS
Whirlpool-Embraco:Brazilian Compressor Company
Factories in 5 countries
38,000,00 compressors/year
1+ compressor/second
 23% global market share
 1/4 refrigerators worldwide uses Embraco compressors
80 countries
12000 direct employees
500 people R&D
Strong cooperation with Universities
High complexity
 Life > 10 years (warranty)
 Tidy tolerances
Oil viscosity: 5-10 Iso
On -off
Circular Motion
Single speed
Many tribological contacts
Oil for lubrication
Incremental
1998
1974
Fullmotion
Circular Motion
Variable speed
Many tribological contacts
Oil for lubrication
On -off
Circular Motion
Single speed
Many tribological contacts
Oil for lubrication
?
Paradigm shift
⇓
Oil Less
However ….
Mechanical
Systems
30%
Lubrication and
lubricants
20%
Others
10%
Materials
40%
Jost, H.P.; Tribology-Origin and Future; Wear, 136, (1990) 1-17.
WiseMotion
the world’s first oil-free compressor for home appliances
WISEMOTION
80+ patents
Linear Motion
Variable displacement
Single tribological contact
NO oil for lubrication
WISEMOTION
the world’s first oil-free compressor for home appliances
 free up to 20 liters of cabinet space.
 new designs and architectures for refrigerators
 top efficiency compressor
 complies with some of today's strictest efficiency
regulations
 less temperature variation
 healthier food.
WISEMOTION
the world’s first oil-free compressor for home appliances
Screening commercially available coatings:
SUBSTRATE
COATING
•Aluminun
•Anodyzed Al
•Al12%Si
•Al 6351-T6
•Al 6351-T6 Anodized
•1020 Steel
•Gray cast iron
• Sintered iron
Family
A
DLC
B
DLC
C
Layered solid
D
Composite (metal)
E Polymer (composite)
F Polymer (composite)
G
Ceramic
H
Polymer
I
DLC
J Composite (polymer)
H Composite (polymer)
Material
MeC:DLC
A:CH
Me:MoS2
NiP + PTFE
PTFE + Polyamide
Polyamide imide + graphite + PTFE
Anodyzed Al
PTFE
A:CH
MoS2 Organic Matrix
MoS2 Inorganic Matrix
B- AÇO
7
15
74
C-SINTER
C-FoFo
C-AlSi
C-Al_T6
C-AÇO
D-SINTER
D-FoFo
D-AlSi
D-Al_T6
D-AÇO
F
A-SINTER
A-FoFo
A-AÇO
E-SINTER
E-FoFo
E-Al-Ano
E-Al_T6
E-AlSi
E-AÇO
B-FoFo
00
50
Coeficiente de atrito
0.5
B-Al_T6
0
1
76
50
0.1
E-Al_T6
E-AlSi
E-AÇO
B-FoFo
B-Al_T6
B- AÇO
E-FoFo
E-Al-Ano
A-AÇO
E-SINTER
Durabilidade ( N.m )
68
0.8
0.09
0.08
00
36
0.2
0.2
10
30
10
0.09
100
A-FoFo
0.8
0.08 0.08
0.5
74
77
157
0.04
0.06
1
2
0.09
0.04
C-SINTER
0.08
C-FoFo
1000
C-AlSi
C-Al_T6
C-AÇO
D-SINTER
D-FoFo
D-AlSi
D-Al_T6
D-AÇO
F
A-SINTER
0
11
0.06
50
0.10
7
66
0.9
77
0.08
10
20
50
30
40
50
Po
t
Ca enci
al
r
de
Co ga
Co
efi
nta
ci e
to
nte
de
atr
i to
60
10
10
0
15
0
Te
mp
o(
mi
n)
20
0
25
0
30
0
35
0
D
mm 10A
- 1 (Al +
6m
m Al 2O
-1
0m 3+M
in
o
pa S2 v
tam er
ar ni z)
-7
N(
5N
)
Coeficiente
de atrito
Friction
Coefficient
0
0
0.15
73
33
0.10
0.08
0.13
0.06
00
10
0.15
0.51
0.06
0.13
47
38
0.50
761
0.1
0.55 0.08
0.9
667
65
28
De Mello et al, Unpublished
0.13
0
10
110
Durabilidade
2
248
0.12
1
31
0.10
0.59
0
00
10
en
c
Po
t
0.14
8
24
ia l
do
Ca co
r
ga ntat
(N o (m
)
V)
/
10000
1
29
0.60
1
0.13 0.13 0.13
Coeficiente de atrito
0
0.4
68
0
0.1
0.2
0.3
0.4
fic
0.08
5000
0.09
)
0.12
0.13
Co
e
1030
Load Cell
.m
0.14
3847 3600
0.50
10
0.55
(N
0.10
0.3
O
Ç
-A
T6
B
l_
-A
Fo
B
o
-F
O
B
Ç
i
-A
E
lS
-A
E
T6
l_
-A
no
E
l-A
o
-A
oF
E
-F
R
E
TE
O
IN
Ç
-S
E
-A
o
A
oF
-F
R
A
TE
F
IN
-S
A
0.1
0.5
O
Ç
-A
D
T6
l_
i
-A
S
l
D
-A
o
D
oF
-F
R
D
TE
IN
O
Ç
-S
D
-A
C
T6
l_
i
-A
lS
C
-A
o
C
oF
-F
R
C
TE
IN
0.13
0.60
de
da
ili
ab
ur
0.2
311
0.6
D
0.3
-S
C
0.0
291
0.5
0.6
to
0.5
2865
tr i
0.6
 ranking of the available coatings;
0.1
 development
of methodology to characterize coatings;
 proprietary
knowhow .
0.0
0.2
de
a
3373
0.4
ie n
te
0.7
0.7
0.59
Abrasive
0.51
Sample
0.7
Screening commercially available coatings:
In spite of considerable research developments, through
more than 2000 published papers from the past 25 years,
there exists no single solid lubricant that can provide
both low friction and wear over broad use conditions,
temperatures and environments.
⇓
Multi purpose
Multi layer
DLC
Donnet, C. and Erdemir, A. , Historical developments and new trends in tribological and solid lubricant coatings, Surface and Coatings Technology 180 –
181 (2004) 76–84
Counter body
Low friction
Load Bearing
Wear resistant
Substrate
Sphere, cylinder, real component
DLC
CrN
ε, γ’, diffusion
1020, 1045
Thickness
Environment
Air
CO2
R600a
R134a
Effect of the environment:
25000
20000
Counts
50 µm
15000
10000
G
Sp2
D
3
Sp
5000
0
700
900
1100
1300
1500
1700
1900
2100
-1
Raman shift ( cm )
30
Hardness ( GPa )
25
1020
20
19
15
13.5
12
10
5
0
0
20
40
60
80
100
120
140
160
Depth ( nm )
Proprietary magnetron sputtered diode multi functional CrN - Si rich DLC on finely
ground (Sq= 0.23±0.025 µm) AISI 1020 steel. De Mello, JDB, et al., Wear. v.267, p.907 - 915, 2009
Effect of the environment:
High Pressure Tribometer (HTP) - simulating typical operating
conditions found in air conditioning and refrigeration compressors.




Actual environment ( hermetic compressors),
Unlubricated ,
CO2 and R600a at 100 KPa environmental pressure,
Reference: unpressurized tests conducted in air.
, 4.5 Hz
DLC-CrN coated 1020 disk
445N
De Mello, JDB, Binder, R., Demas, N.G., Polycarpou, A.A., Effect of the actual environment present in hermetic compressors on the tribological behaviour of a Si-rich
multifunctional DLC coating. Wear. v.267, p.907 - 915, 2009
Effect of the environment:
0.35
0.30
AIR
R600a
CO2
0.20
0.15
0.19
0.13
0.10
0.35
0.05
0.30
0.00
R600a
0.25
CO2
AIR
Environment
0.20
4.00
0.10
3.50
-18
0.15
0.05
-1
3.18
3.00
0.00
-1 -1
Wear Rate ( m . mm .s .N ).10
2.50
0
5
10
15
20
Test Time ( min )
25
30
35
2.78
2.08
2.00
3
Friction Coefficient
0.40
0.30
0.25
Friction Coefficient
0.45
Steady-state values
1.50
1.00
0.50
0.00
R600
CO2
Air
R600a
CO2
20000
18000
16000
Air
Virgin
R600_Wear Scar
CO2_Wear Scar
Air_Wear Scar
Counts
14000
12000
10000
8000
6000
D
G
1337±1 1580±3
4000
2000
ID/IG=0.85±0.02
0
 Chemically,
remarkable
differences
between
the tribo
700 no 900
1100
1300
1500
1700
1900
shift (cm )
layers formed in differentRaman
atmospheres.
-1
Results and discussion:
R600a
1 mm
1 mm
1 mm
CO2
Air
Results and discussion:
R600a
50 µm
Air
50 µm
Results and discussion:
Air
CO2
R600a
Effect of the environment:
R600a
CO2
Air
0.25
Sq
Spk
0.21
0.20
0.20
0.20
Sq, Spk ( µm )
0.18
0.15
0.14
0.13
0.10
0.09
0.08
0.05
0.00
original
R600a
CO2
Air
De Mello, JDB, Binder, R., Demas, N.G., Polycarpou, A.A., Effect of the actual environment present in hermetic compressors on the tribological behaviour of a Si-rich
multifunctional DLC coating. Wear. v.267, p.907 - 915, 2009
Results and discussion:
Effect of the environment:
R600a
CO2
Air
0.5 mm
0.5 mm
0.5 mm
Wear Rate ( m3.mm-1.s-1.N-1 ). 10-18
18.00
16.00
14.00
12.91
12.00
10.00
8.50
8.00
6.00
4.85
4.00
2.00
0.00
R600a
CO2
Air
De Mello, JDB, Binder, R., Demas, N.G., Polycarpou, A.A., Effect of the actual environment present in hermetic compressors on the tribological behaviour of a Si-rich
multifunctional DLC coating. Wear. v.267, p.907 - 915, 2009
Effect of the environment:
4000
α-Fe2O3 Fe3O4
3500
CO2
air
R600a
3000
Counts
2500
2000
1500
1000
500
0
100
300
500
700
900
1100
1300
1500
1700
1900
2100
Raman Shift ( cm-1 )
De Mello, JDB, Binder, R., Demas, N.G., Polycarpou, A.A., Effect of the actual environment present in hermetic compressors on the tribological behaviour of a Si-rich
multifunctional DLC coating. Wear. v.267, p.907 - 915, 2009
Effect of the environment:
0,40
4,0
0,35
3,5
WC-Co
1
0,8
0,25
3,0
2,5
0,20
2,0
0,15
1,5
0,10
0,6
0,4
Resistência de Contato - R1 [ KOhm ]
R134a
Carga Normal - Fz [ Kgf ]
Coeficiente de Atrito - COF [ u ]
0,30
1,0
0,2
COF
0,05
0,5
Fz
R1
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
0,0
20000
0
400
Tempo [ segundos ]
Carga Normal
0.09
Cobertura
Flexível
(Latex)
Deslocador
Entrada de gás
Durability (N.m)
Amostra
Porta Amostra
0.10
0.09
300
Esfera
Saída de gás
0.1
350
Sensor
Porta
Esfera
0.12
250
0.08
Surface durability
Friction Coefficient
200
371
150
0.06
0.04
216
100
Friction Coefficient
0,00
0.02
50
40
0
0.00
AIR
R 600a
R134a
Environment
Silverio, M., de Mello, J.D.B., Binder, R., Effect of refrigerant gases on the tribological behavior of a CrN-SiDLC multifunctional coating applied to soft substrate. First
International Brazilian Conference on Tribology – TriboBr-2010, 2010, Rio de Janeiro – RJ, p.616 - 624
Effect of the environment:
Silverio, M., de Mello, J.D.B., Binder, R., Effect of refrigerant gases on the tribological behavior of a CrN-SiDLC multifunctional coating applied to soft substrate. First
International Brazilian Conference on Tribology – TriboBr-2010, 2010, Rio de Janeiro – RJ, p.616 - 624
Effect of the environment:
150 N
R134a
DLC
AISI 304
3 Hz
R134a
Barbosa, M.V.; Hammes, G.; Binder, C.; Klein, A. N.; De Mello J. D. B.; Physicochemical characterization of tribolayers by Micro-Raman and GDOES analyses ,
Tribology International, v 81, p223-230, 2015.
Effect of the environment:
150 N
R134a
DLC
AISI 304
3 Hz
Barbosa, M.V.; Hammes, G.; Binder, C.; Klein, A. N.; De Mello J. D. B.; Physicochemical characterization of tribolayers by Micro-Raman and GDOES analyses ,
Tribology International, v 81, p223-230, 2015.
Effect of layers thickness:
Proprietary magnetron sputtered diode multi functional CrN - Si rich DLC on finely
ground (Sq= 0.23±0.025 µm) AISI 1020 steel.
Sample
Family 1
Family 2
1_A
1_B
1_C
2_A
2_B
DLC
Thickness (µm)
1.36±0.05
1.78±0.07
1.53±0.05
1.14±0.06
1.23±0.05
Thin
CrN
Thickness (µm)
2.72±0.07
3.19±0.05
3.49±0.09
1.44±0.08
1.38±0.05
E (GPa)
111
105
81
220
203
Substrate
10000
14
A1
300
9000 70
2 families
Substrate
CrN
Thick
A4
A5
A4
A4
A5
10 50
7000
200
60008
40
A4
150
5000
A5
6 30
4000
100
30004
A2
A2
A1
20
A1
50
A3
A3
20002 10
0
10002
DLC
A3
8000 60
Hardness (GPa)
1µm
A3
250
Critical load (N)
DLC
A2
Critical load LC2
12
Young'sCounts
modulus (GPa)
CrN
Critical load LC1
E (GPa)
86
84
75
307
235
0
0
0 0
0
0
2,5
1
5
3
10
3,5
15
4
(µm)
2 Layer thickness
3
4
Load (mN)
Sample
1000
2000
4,5
20
5
3000
5
25
5,5
6
4000
Raman shift (cm -1)
1µm
L.O.C. Lara, J.D.B. De Mello, Influence of layer thickness on hardness and scratch
resistance of Si-DLC/CrN coatings, Tribology - Materials, Surfaces & Interfaces v.6, p
168, 2012 .
Effect of layers thickness:
• Modified PLINT & PARTNERS TE 67 - High frequency acquisition system;
LVDT; LabVIEW® - Matlab ®
3D Triboscopy
Fn
Load Cell
Ft
+
-
LVDT
• 2D proposed by Belin-1993;
• Locate microscopic tribological events and
study their evolution during the test;
• Information with local details as well as a
global evolution of the tribological
phenomena.
• High spatial and temporal resolution;
• 3D triboscopic map where z is the variable
being measured (friction coefficient), x is the
position of the counter body within each
cycle (measured by an additional LVDT
sensor) of test and y is the total sliding
distance
M. B. dos Santos, H.L. Costa, J.D.B. de Mello, Potentiality of 3D triboscopy to monitor friction and wear, Wear (2014), p.1134 - 1144.
Effect of layers thickness:
Thin
Thick
L. O. C. Lara, H. L. Costa, J. D. B. De Mello, Influence of Layer Thickness on Sliding Wear of Multifunctional Tribological Coatings, Industrial Lubrication and
Tribology, (2015), v.460, p.460 - 467,
Effect of layers thickness: Constant normal load
L. O. C. Lara, H. L. Costa, J. D. B. De Mello, Influence of Layer Thickness on Sliding Wear of Multifunctional Tribological Coatings, Industrial Lubrication and
Tribology, (2015), v.460, p.460 - 467,
Effect of layers thickness: Constant normal load
(a)
(b)
L. O. C. Lara, H. L. Costa, J. D. B. De Mello, Influence of Layer Thickness on Sliding Wear of Multifunctional Tribological Coatings, Industrial Lubrication and
Tribology, (2015), v.460, p.460 - 467,
Effect of layers thickness:
10.00
Shear stress (GPa)
Interface shear stress
Interface critical stress
FilmDoctor
1.00
Thin = 50 – 100 N
Indentation
0.10
0
100
200
300
400
500
Load (N)
FilmDoctor
Thick = 10 N
Indentation
L. O. C. Lara,, J. D. B. De Mello, Quantitative measurement of the interface adhesion of a multifunctional coating, Nanobioletters, (2015), in press
Evolution and stability of tribolayers:
 Home made emulator
 Testing the real components
 Special atmosphere
 350 Hz
 Test time: 180, 500, 1000 and 2500 h
Salvaro, D et al , Genesis and stability of tribolayers in solid lubrication: case of pair DLC-STAINLESS steel, Proceedings of TriboBR2014- Second International
Brazilian Conference on Tribology, November 2014, Brazil also Journal of Materials Research Technology, (2015), In press.
Evolution and stability of tribolayers:
Piston DLC
DLC
AISI 304
R134a
Test time (h)
Cylinder AISI 304
Test time (h)
Salvaro, D et al , Genesis and stability of tribolayers in solid lubrication: case of pair DLC-STAINLESS steel, Proceedings of TriboBR2014- Second International
Brazilian Conference on Tribology, November 2014, Brazil also Journal of Materials Research Technology, (2015), In press.
Tribolayer thickness (µm)
Evolution and stability of tribolayers:
Cylinder
Piston
Test time (h)
Salvaro, D et al , Genesis and stability of tribolayers in solid lubrication: case of pair DLC-STAINLESS steel, Proceedings of TriboBR2014- Second International
Brazilian Conference on Tribology, November 2014, Brazil also Journal of Materials Research Technology, (2015), In press.
Evolution and stability of tribolayers: GDOES
15 min
45 min
DLC
AISI 304
30 min
120 min
Barbosa, M.V.; Hammes, G.; Binder, C.; Klein, A. N.; De Mello J. D. B.; Physicochemical characterization of tribolayers by Micro-Raman and GDOES analyses ,
Tribology International, (2015), v 81, p 223-230.
Evolution and stability of tribolayers: GDOES
Barbosa, M.V.; Hammes, G.; Binder, C.; Klein, A. N.; De Mello J. D. B.; Physicochemical characterization of tribolayers by Micro-Raman and GDOES analyses ,
Tribology International, v 81, p 223-230, 2015.
γ'
ε
Nitride Layers:
dif.
CHИ®
*Patent pending
T (°C)
P (Torr)
T (h)
Gas (%)
Phases
550
2
1.5
90N2-9H2-1CH4
ε
570
2
4.0
20N2-80H2
γ’
480
2
1.5
5N2-95H2
Diffusion
Shioga, P., Binder, C., Klein, A.N., De Mello, J.D.B., Effect of Different Plasma Nitride Layers on the Tribological Performance of DLC Coatings, Proceedings of
the Technical Conference Society of Vacuum Coaters, 2014. Chicago., 2014. Sponsored student.
dif.
Nitride Layers: Adhesion
γ'
ε
0.60
VDI 3198 + Image analysis
Spalled area (mm2)
0.50
0.40
0.30
0.20
0.10
0.00
Epsilon
Gamma
Diffusion
Shioga, P., Binder, C., Klein, A.N., De Mello, J.D.B., Effect of Different Plasma Nitride Layers on the Tribological Performance of DLC Coatings, Proceedings of
the Technical Conference Society of Vacuum Coaters, 2014. Chicago., 2014. Sponsored student.
Nitride Layers:
Si3N4
10 Hz
Durability (N.m)
µ
Diffusion
13,000
0.05
6000
0.12-0.1
ε
600
0.2
γ’
Nitride Layers:
14
4.00
Durability
Adhesion
3.00
Durability (N.m). 103
10
2.50
8
2.00
6
1.50
4
1.00
2
0.50
0
0.00
Epsilon
Gamma
Delamination area-1 (1/mm2)
3.50
12
Diffusion
Shioga, P., Binder, C., Klein, A.N., De Mello, J.D.B., Effect of Different Plasma Nitride Layers on the Tribological Performance of DLC Coatings, Proceedings of
the Technical Conference Society of Vacuum Coaters, 2014. Chicago., 2014. Sponsored student.
8000 pistons in a unique thermal cycle
EP.2294598 : "Plasma process and reactor for treating metallic pieces"
Concluding Remarks:
 Plant in operation in Monterrey, Mexico;
 600,000 compressores in 2015;
 1,500,000 compressors in two years time (2017).
Thank you !
[email protected]
[email protected]