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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
REVESTIMENTOS MULTIFUNCIONAIS A BASE DE CARBONO APLICADOS EM COMPRESSORES HERMÉTICOS SEM
ÓLEO.
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 CAPES-Proex (Brazil) as well as Whirlpool/Embraco.
Refrigeration: Home energy consumption
17.3%
47%
United States Environmental Protection Agency, Partnerships for Home Energy Efficiency Report
Programa Nacional de Conservação de Energia Elétrica, Pesquisa de Posse de Equipamentos e Hábitos de Uso – Ano Base 2005, Classe Residencial, Relatório Brasil
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.
Refrigeration: Commercial energy consumption
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.
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
Air Flammability LEL UEL
Refrigerant Life Time (years)
ODP HGWP Toxicity
Volume %
CFC R12 120 1 7100 TLV= 1000ppm Not flammable
HCFC R22 15 < 1 1500 - -
HFCR 134a 16 0 3200 AEL= 1000 ppm Not flammable
Propane R230 Months 0 < 5 Low 2.1 9.5
Butane R600 Weeks 0 < 5 Slightly anaesthetic - TLV= 800ppm 1.8 8.5
Isobutane R600a < 1 Week 0 <0.01 Slightly anaesthetic - TLV= ND 1.8 8.5
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.
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 +
Limited lubrication: boundary and mixed lubrication regimes
Smaller clearances and increased speeds +
TOWARDS OIL-LESS COMPRESSORS SOLID LUBRICATION AND SOLID
LUBRICANTS
⇓
⇓
Miscibility oil – refrigerant / insulation +
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
On -off Circular Motion Single speed Many tribological contacts Oil for lubrication
High complexity Life > 10 years (warranty) Tidy tolerances Oil viscosity: 5-10 Iso
Incremental
1974 On -off Circular Motion Single speed Many tribological contacts Oil for lubrication
1998 Fullmotion
Circular Motion Variable speed Many tribological contacts Oil for lubrication
? Paradigm shift
⇓ Oil Less
Lubrication and lubricants
20%
Others10%
Materials40%
Mechanical Systems
30%
Jost, H.P.; Tribology-Origin and Future; Wear, 136, (1990) 1-17.
However ….
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
top efficiency compressor complies with some of today's strictest efficiency regulations
less temperature variation healthier food.
free up to 20 liters of cabinet space. new designs and architectures for refrigerators
WISEMOTION
the world’s first oil-free compressor for home appliances
COATING
SUBSTRATE
•Aluminun •Anodyzed Al •Al12%Si •Al 6351-T6 •Al 6351-T6 Anodized •1020 Steel •Gray cast iron • Sintered iron
Family Material A DLC MeC:DLC B DLC A:CH C Layered solid Me:MoS2 D Composite (metal) NiP + PTFE E Polymer (composite) PTFE + Polyamide F Polymer (composite) Polyamide imide + graphite + PTFE G Ceramic Anodyzed Al H Polymer PTFE I DLC A:CH J Composite (polymer) MoS2 Organic Matrix
H Composite (polymer) MoS2 Inorganic Matrix
Screening commercially available coatings:
0.13
0.10
0.140.12
0.080.06
0.08 0.080.10
0.13 0.13 0.130.15
0.600.59
0.50
0.55
0.51
0.04
0.080.09
0.06
0.09
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
B-
AÇ
O
B-A
l_T
6
B-F
oF
o
E-A
ÇO
E-A
lSi
E-A
l_T
6
E-A
l-A
no
E-F
oF
o
E-S
INT
ER
A-A
ÇO
A-F
oF
o
A-S
INT
ER F
D-A
ÇO
D-A
l_T
6
D-A
lSi
D-F
oF
o
D-S
INT
ER
C-A
ÇO
C-A
l_T
6
C-A
lSi
C-F
oF
o
C-S
INT
ER
Co
efi
cie
nte
de
atr
ito
Fri
ctio
n C
oeff
icie
nt
291
2
3373
311
667248
1030
110
2865
38473600
68
5000
0.90.8
0.1
0.2
0.5
761
7750
15774
0
1
10
100
100010000
B- A
ÇO
B-A
l_T6
B-FoFo
E-AÇOE-A
lSi
E-Al_T6
E-Al-A
no
E-FoFo
E-SINTER
A-A
ÇO
A-FoFo
A-SIN
TER
F
D-A
ÇO
D-A
l_T6D-A
lSi
D-FoFo
D-SIN
TER
C-A
ÇO
C-A
l_T6C-A
lSi
C-FoFo
C-SIN
TER
Durabilidade ( N
.m )
D10A
(Al +
Al2
O3
+ M
oS2
vern
iz)
10 m
m -
16 m
m -
10 m
in p
atam
ar -
7N (5
N)0
10
20
30
40
50
60
0
50
100
150
200
250
300
350
Tem
po (m
in)
Potencial do contato (m
V) /
Carga (N)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Coeficiente de atrito
Pote
ncia
l de C
onta
to
Carga
Coefic
ient
e de a
trito
0.13
0.10
0.140.12
0.08
0.060.08 0.08
0.10
0.13 0.13 0.13
0.600.59
0.50
0.55
0.51
0.04
0.080.09
0.06
0.09
0.15
291
2
3373
311
667
248
1030
110
28653847 3600
68
5000
0.9 0.8
0.1
0.2
0.5
761
77
50
157
74
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
B-
AÇ
O
B-A
l_T
6
B-F
oF
o
E-A
ÇO
E-A
lSi
E-A
l_T
6
E-A
l-A
no
E-F
oF
o
E-S
INT
ER
A-A
ÇO
A-F
oF
o
A-S
INT
ER F
D-A
ÇO
D-A
l_T
6
D-A
lSi
D-F
oF
o
D-S
INT
ER
C-A
ÇO
C-A
l_T
6
C-A
lSi
C-F
oF
o
C-S
INT
ER
Co
efi
cie
nte
de
atr
ito
0
1
10
100
1000
10000
Du
rab
ilid
ad
e (
N.m
)
Coeficiente de atrito
Durabilidade
SampleLoad Cell
Abrasive
De Mello et al, Unpublished
ranking of the available coatings; development of methodology to characterize coatings; proprietary knowhow .
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.
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
⇓ Multi purpose
Multi layer DLC
Screening commercially available coatings:
Substrate 1020, 1045
Load Bearing Wear resistant
CrN ε, γ’, diffusion
Low friction DLC
Thickness
Counter body Sphere, cylinder, real component
Environment Air CO2
R600a R134a
Proprietary magnetron sputtered diode multi functional CrN - Si rich DLC on finely ground (Sq= 0.23±0.025 µm) AISI 1020 steel.
50 µm
0
5000
10000
15000
20000
25000
700 900 1100 1300 1500 1700 1900 2100
Raman shift ( cm-1 )
Cou
nts
DSp3
GSp2
19
13.512
0
5
10
15
20
25
30
0 20 40 60 80 100 120 140 160
Depth ( nm )H
ardn
ess
( G
Pa
)1020
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.
DLC-CrN coated 1020 disk
445N
, 4.5 Hz
Actual environment ( hermetic compressors), Unlubricated , CO2 and R600a at 100 KPa environmental pressure, Reference: unpressurized tests conducted in 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:
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0 5 10 15 20 25 30 35
Test Time ( min )
Fri
ctio
n C
oef
fici
ent
AIR
R600a
CO2
0.13
0.19
0.30
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
R600a CO2 AIR
Environment
Fri
ctio
n C
oef
fici
ent
Steady-state values
2.08
2.78
3.18
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
R600 CO2 Air
Wea
r R
ate
( m
3 . mm
-1.s
-1.N
-1 ).
10-1
8
Effect of the environment:
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
700 900 1100 1300 1500 1700 1900
Raman shift (cm-1)
Cou
nts
VirginR600_Wear ScarCO2_Wear ScarAir_Wear Scar
ID/IG=0.85±0.02
D G 1337±1 1580±3
Air R600a CO2
Chemically, no remarkable differences between the tribo layers formed in different atmospheres.
50 µm
R600a
Air
50 µm
Results and discussion:
Air CO2 R600a
Results and discussion:
0.21
0.20
0.18
0.13
0.20
0.14
0.09
0.08
0.00
0.05
0.10
0.15
0.20
0.25
original R600a CO2 Air
Sq, S
pk (
µm
)
Sq
Spk
CO2 R600a 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:
Results and discussion:
4.85
8.50
12.91
0.00
2.00
4.00
6.00
8.00
10.00
12.00
14.00
16.00
18.00
R600a CO2 Air
Wea
r R
ate
( m
3 .mm
-1.s
-1.N
-1 )
. 10-1
8
0.5 mm
R600a
0.5 mm
CO2
0.5 mm
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:
0
500
1000
1500
2000
2500
3000
3500
4000
100 300 500 700 900 1100 1300 1500 1700 1900 2100
Raman Shift ( cm-1 )
Cou
nts
CO2airR600a
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:
α-Fe2O3 Fe3O4
Deslocador
Sensor
Amostra
Porta Amostra
Carga Normal
Entrada de gás Saída de gás
Cobertura Flexível (Latex)
Porta Esfera
Esfera
Effect of the environment:
0,00
0,05
0,10
0,15
0,20
0,25
0,30
0,35
0,40
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000
Tempo [ segundos ]
Coe
ficie
nte
de A
trito
- C
OF
[ u
]
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
Car
ga N
orm
al -
Fz
[ Kgf
]
COF
Fz
R1
1
0,8
0,6
0,4
0,2
0
Res
istê
ncia
de
Con
tato
- R
1 [ K
Ohm
]R134a
WC-Co
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
40
216
371
0.09 0.09
0.1
0
50
100
150
200
250
300
350
400
0.00
0.02
0.04
0.06
0.08
0.10
0.12
Dur
abil
ity
(N
.m)
Environment
Fri
ctio
n C
oeff
icie
ntSurface durability
Friction Coefficient
AIR R 600a R134a
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:
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.
DLC
AISI 304 R134a
150 N
3 Hz
R134a
Effect of the environment:
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.
DLC
AISI 304 R134a
150 N
3 Hz
Effect of layers thickness:
Sample DLC CrN
Thickness (µm) E (GPa) Thickness (µm) E (GPa)
Family 1 1_A 1.36±0.05 111 2.72±0.07 86 1_B 1.78±0.07 105 3.19±0.05 84 1_C 1.53±0.05 81 3.49±0.09 75
Family 2 2_A 1.14±0.06 220 1.44±0.08 307 2_B 1.23±0.05 203 1.38±0.05 235
Proprietary magnetron sputtered diode multi functional CrN - Si rich DLC on finely ground (Sq= 0.23±0.025 µm) AISI 1020 steel.
Substrate
CrN
DLC
1µm
DLC
CrN
Substrate
1µm
Thin 2 families Thick
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 .
0
10
20
30
40
50
60
70
0 5 10 15 20 25H
ard
nes
s (G
Pa)
Load (mN)
A3 A4
0
50
100
150
200
250
300
2 2,5 3 3,5 4 4,5 5 5,5
Yo
un
g's
mo
du
lus
(GP
a)
Layer thickness (µm)
A1A2 A3
A4A5
A1 A2 A3
A4A5
0
2
4
6
8
10
12
14
0 1 2 3 4 5 6
Cri
tica
l lo
ad (
N)
Sample
Critical load LC1 Critical load LC2
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
0 1000 2000 3000 4000
Co
un
ts
Raman shift (cm-1)
A1 A2 A3 A4 A5
• Modified PLINT & PARTNERS TE 67 - High frequency acquisition system; LVDT; LabVIEW® - Matlab ®
• 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
3D Triboscopy
Effect of layers thickness:
Load Cell
LVDT
+-
Fn
Ft
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,
(a)
(b)
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:
0.10
1.00
10.00
0 100 200 300 400 500
Sh
ear
stre
ss (
GP
a)
Load (N)
Interface shear stress Interface critical stress
Thick = 10 N
Thin = 50 – 100 N
FilmDoctor
FilmDoctor
Indentation
Indentation
L. O. C. Lara,, J. D. B. De Mello, Quantitative measurement of the interface adhesion of a multifunctional coating, Nanobioletters, (2015), in press
Home made emulator Testing the real components Special atmosphere 350 Hz Test time: 180, 500, 1000 and 2500 h
Evolution and stability of tribolayers:
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
Test time (h) Cylinder AISI 304
Test time (h)
DLC AISI 304
R134a
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.
Test time (h)
Tri
bola
yer
thic
knes
s (µ
m)
Cylinder
Piston
Evolution and stability of tribolayers:
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.
DLC
AISI 304
15 min
45 min
30 min
120 min
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, (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.
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
Nitride Layers: ε γ' dif.
CHИ® *Patent pending
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.
γ'
ε
Nitride Layers: Adhesion
0.00
0.10
0.20
0.30
0.40
0.50
0.60
Epsilon Gamma Diffusion
Spal
led
area
(mm
2 )
VDI 3198 + Image analysis
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:
10 Hz
Si3N4
Durability (N.m) µ Diffusion 13,000 0.05
ε 6000 0.12-0.1 γ’ 600 0.2
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
0
2
4
6
8
10
12
14
Epsilon Gamma Diffusion
Del
amin
atio
n ar
ea-1
(1/m
m2 )
Dur
abil
ity
(N.m
). 1
03
Durability Adhesion
Nitride Layers:
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.
EP.2294598 : "Plasma process and reactor for treating metallic pieces"
8000 pistons in a unique thermal cycle
Concluding Remarks:
Plant in operation in Monterrey, Mexico; 600,000 compressores in 2015;
1,500,000 compressors in two years time (2017).
