Tribocorrosion-Testing protocol

UMR LGF

Center for Health Engineering Jean GERINGER*

ENSM-SE/[email protected]

Training school for Master, Ph.D students and engineers Protection against Bio-Tribocorrosion in industry

Tribocorrosion-Testing protocol •

ENSM-SE: Ecole Nationale Supérieure des Mines de Saint-Etienne-France

Context Training School-Centrale Paris- 02/13/2013

http://en.wikipedia.org/wiki/Tribocorrosion

Tribocorrosion occurs in many engineering fields. It reduces the life-time of pipes, valves and pumps, of waste incinerators, of mining equipment or of medical implants, and it can affect the safety of nuclear reactors or of transport systems. On the other hand, tribocorrosion phenomena can also be applied to good use, for example in the chemical-mechanical planarization of wafers in the electronics industry [4] or in metal grinding and cutting in presence of aqueous emulsions. Keeping this in mind, we may define tribocorrosion in a more general way independently of the notion of usefulness or damage or of the particular type of mechanical interaction: Tribocorrosion concerns the irreversible transformation of materials or of their function as a result of simultaneous mechanical and chemical/electrochemical interactions between surfaces in relative motion

 Tribocorrosion: huge field of investigations  Need tribocorrosion investigations for understanding degradations and consequences…

2


 Hip replacement: Diseases, accidents, ageing, etc.  Hip Prostheses: ~ 160,000/year in France; 257,000/year in US http://migliorelaw.com/dangerous-medical/dupuy-hip

 One in every 30 Americans  $3-4 billions/year in US  Reintervention: patient concerns and economical issues

 1 implant for life: ultimate goal

1 of the major issue about retrieval implants 3


http://www.shezadmalik.com/

According to a British health agency, the Medicines and Healthcare Products Regulatory Agency (MHRA), millions of people worldwide who have received metal-onmetal hip replacement may need to get blood tests for the rest of their lives. Many metal hip replacement systems contain chromium and cobalt in the ball-andsocket device, which became popular because they would be more durable to younger, more active hip patients. DePuy Orthopaedics, a division of Johnson and Johnson, has issued a recall of its ASR XL Acetabular System and ASR Hip Resurfacing System hip replacement devices after medical studies demonstrated that they were more than twice as likely to fail than other hip replacements

 MoM problems  Need tribocorrosion investigations for lifetime of implants…

4

Strategy

Bio-tribocorrosion Materials for implants

Materials science, Biomaterials Tribology, Bio-tribocorrosion

How do we investigate the problem? What kind of protocol? Sharing results with different labs 5

Roadmap Training School-Centrale Paris- 02/13/2013

Introduction / Problems 1- Electrochemical investigations  Aims  Protocol  Results/comparative results and conclusions

2- Tribocorrosive investigations/synergism approach  Aims  Protocol for measuring synergy  Results and conclusions

3- Fretting corrosion case  Device  Protocol  Results/synergy/debris(AFM)

6

Electrochemical investigations /protocol Training School-Centrale Paris- 02/13/2013

COST 533 ‘Materials for Improved Wear Resistance of Total Artificial Joints’. Pr. Anna Igual Munoz / Dr. Stéfano Mischler Electrochemical methods for characterisation of CoCrMo biomedical alloys in simulated body fluids Organized within COST 533 and endorsed by EFC-WP18 REPORT 1: PRELIMINARY RESULTS (DC data) REPORT 2: RESULTS FROM ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY (EIS) WORKING PARTY 18 TRIBOCORROSION. - EUROPEAN FEDERATION OF CORROSION 7


Aims ‘Biocorrosion of Co-Cr-Mo alloy dedicated to orthopedic implants Complexity of the biological environment More than 20 components. Tests with Phosphate Buffered Solution with and without albumin 15 labs (8 different countries) / test of reproductibility Open circuit potential, polarization curves Electrochemical Impedance Spectroscopy

8


Data Example: OCP

9


All results are available in the report. Almost the same results for all experiments (OCP, ipp, Ecorr, Eb) Study of the repeatability. EIS results: Rsolution, Rpolarization, Constant Phase Element (CPE) Paying attention on two labs results for comparaison 1 from ENSM-SE / 1 from INSA de Lyon Matériaux & Techniques 95, 417–426 (2007) 10.1051/mattech:2008038

10


CoCrMo alloy, composition Elements

Co

Cr

Mo

Si

Mn

C

Al

Mass %

64.81

28.17

5.82

0.36

0.78

0.04

0.02

Electrochemical device, INSA device

Different electrochemical device, ENSM-SE, no image 11


Polishing process Till alumina powder of 1µm (diameter) After polishing and ‘washing’ step, the last one was ‘distilled’ water. 2 types of solution Elements

NaCl

KCl

KH2PO4

Na2PO4

Albumin

Solution 1

8.192

0.223

0.136

1.420

0

Solution 2

8.192

0.223

0.136

1.420

1.000

Concentrations ± 0.002 g.L-1 Temperature was maintained at 37°C

12


Electrochemical protocol 1- OCP measurement during 10 minutes 2- Cathodic polarization during 5 minutes at -1.25V/SHE 3- Cyclic voltammetry from -1.25V to 1.5 V/SHE, rate of 2mV.s-1 Experimental device Potentiostat trademark 2 Working electrode, WE (cm ) Reference electrode, RE Counter electrode, CE Distance RE-WE (mm) Volume of solution (mL) pH Temperature (°C) Fixing temperature

ENSM-SE PARSTAT 2263 1.76  1 ECS (0.250 V/ESH) Platinium wire 82 20  1 7.6  0,1 37  2 Heating band

INSA PARSTAT 2273 1.76  1 ECS (0.246 V/ENH) Graphite 10  2 50  2 7.6  0,1 37  1 Double wall

- The heating device was stopped during EIS measurements for avoiding electromagnetic perturbations. 13


2nd round 1- Cathodic polarization during 5 minutes at -1.25V/SHE 2- OCP 10 minutes / OCP 60 minutes 3- Polarization +0.15 V/SHE / OCP 60 minutes 4- EIS at 0.15 V/SHE / OCP, 10 MHz – 0.01Hz (10 pts/decade, ±10 mV) 1st round

2nd round

Log (Current density

0

-1.3

-0.8

-0.3 -1

0.2

0.7 1.2 Potential / V vs. SHE

-2 -3

E

-4 -5 -6

Real part

+0,15 V vs. SHE

-7 -8 14

Rs

Rs+Rp


Results, statistical analysis: Experiment 1 Polarization

Average values Standard deviation Different average values Labs, 5% Different average values Solution, 5%


PBS ENSM-SE OCP (V vs. SHE) -0.320 0,.022

Yes

icorr (A/cm2)

icorr (A/cm2)

Yes

-3.0E-08 2.4E-08 NO NO

Ecorr (V vs. SHE)

-0.263 0.033 Yes NO

Ecorr (V vs. SHE)

-0.519 0.090

-2.2E-08 1.6E-08

Ecorr (V vs. SHE)

-0.320 0.153

-0.469 0.049

NO

2

2

ipp (A/cm )

7.7E-06 2E-07 OUI

OUI yes

yes

OUI

ipp (A/cm ) 1.3E-05 3E-06

6.4E-06 6E-07

OUI yes

Eb (V vs. ESH)

Eb (V vs. ESH) 0799 0.799 0.024

0.033

2

ipp (A/cm ) 8.7E-06 2E-07

0755 0.755 0.033 NO NO

-2.0E-08 3.8E-08

NO

Eb (V vs. ESH)

15

-4.3E-09 2.7E-09

icorr (A/cm2)

NO

2


icorr (A/cm2)

-0.353 0.005

NO

ipp (A/cm ) Average values Standard deviation Different average values Labs, 5% Different average values Solution, 5%

INSA OCP (V vs. SHE)

0.295 -0.295 0.020 0.02

-0.221 0.020

Yes Yes

Ecorr (V vs. SHE) Average values Standard deviation Different average values Labs, 5% Different average values Solution, 5%

PBS+BSA ENSM-SE OCP (V vs. SHE)

INSA OCP (V vs. SHE)

0.024

Eb (V vs. ESH) 0.762 0.012

NO

NO

Between 2 labs: no reproductibility of OCP and ipp

0.787 0.038


Results, experiment 2, +0.15V/SHE: PBS 500 400 300

T e st T e st T e st T e st T e st T e st

1 2 3 1 2 3

E N S M -S E E N S M -S E E N S M -S E IN S A IN S A IN S A

200 100 0

Z re a l / ko h m .cm

0 ,1 H z 0

200

400

600

2

800

6

10

5

10

4

10

T1 ENSM-SE T2 ENSM-SE T3 ENSM-SE T1 INSA T2 INSA T3 INSA

3

10

2

10

1

10

-3

-1

10

10

2

0,1 Hz

Z real / kohm.cm 0

50

100

150

200

250

2

Impedance (magnitude) / ohm.cm

2

-ZIm / kohm.cm

ENSM-SE ENSM-SE ENSM-SE INSA INSA INSA

10

6

10

5

10

4

10

3

1

3

10

2

10

1

10

5

10 10 Frequency / Hz

-3

40 20

1 2 3 1 2 3

10


-1

100 80 60 40


10

PBS+BSA: discrepancy

7

10

Test Test Test Test Test Test

T1 T2 T3 T1 T2 T3

60

20 0 10

1

3

5


10

7

Phase / °

16

180 160 140 120 100 80 60 40 20 0

1 2 3 1 2 3

80

0

PBS+BSA Test Test Test Test Test Test

100

Phase / °

-ZIm / kohm.cm

2

600


2

Test 1 ENSM-SE Test 2 ENSM-SE Test 3 ENSM-SE Test 1 INSA Test 2 INSA Test 3 INSA


Results, experiment 2, +0.15V/SHE: Experiment 2 EIS (+ 0.15 V vs. SHE)

PBS

PBS+BSA

ENSM-SE

INSA

ENSM-SE

INSA

Rsolution (Ohm.cm2)

Rsolution (Ohm.cm2)

Rsolution (Ohm.cm2) Rsolution(Ohm.cm2)

Average value

31

26

29

26

Standard deviation

10

2

3

3

Different average values Labs, 5%

NO

Different average values Solution, 5%

NO

NO

Rp (Ohm.cm2)

Rp (Ohm.cm2)

Average value Standard deviation Different average values Labs, 5%

NO


NO

NO

Rp (Ohm.cm2)

Rp (Ohm.cm2)

1,2E+06

1,0E+06

8,7E+05

8,2E+05

4,E+05

2,E+05

1,6E+05

3,7E+05

NO NO

PBS+BSA: less protection Role of albumin: promoting dissolution of CoCrMo, metal oxidation 17

Electrochemical investigations /protocol

300 200 100

200

180 160 140 0,1 Hz 120 100 80 60 40 20 0 0 50

18

400

600

5

10

4

60

3

40

10

T1 ENSM-SE T2 ENSM-SE T3 ENSM-SE T1 INSA T2 INSA T3 INSA

2

10

1

10

-3

-1

10

2

Zreal / kohm.cm 100

150

200

250

20 0

1

10

2

800


80

10

3

6

10

5

10 10 Frequency / Hz T2 ENSM-SE T3 ENSM-SE T1 INSA T2 INSA T3 INSA

2

0

2

Zreal / kohm.cm

100


7

10

10


5

10

100 80

4

60

3

40

2

20

1

0

10 10 10 10

-3

10

-1

10

1

3


5

10

Phase / °

-ZIm / kohm.cm

2

0

0,1 Hz

6

10

Phase /

400


500



600

-ZIm / kohm.cm2

Results, experiment 3, OCP:

Training School-Centrale Paris- 02/13/2013



Results, experiment 3, OCP: Experiment 3 EIS (OCP)

19

PBS ENSM-SE

INSA

PBS+BSA ENSM-SE

INSA

Average value Standard deviation

OCP (V vs. SHE) OCP (V vs. SHE) OCP (V vs. SHE) OCP (V vs. SHE) -0,020 -0,195 -0,249 -0,246 0,025 0,024 0,013 0,030


YES


YES


Rsolution(Ohm.cm2) Rsolution(Ohm.cm2) Rsolution (Ohm.cm2) Rsolution(Ohm.cm2) 33 24 26 29 2 1 6 2


YES


NO


Rp (Ohm.cm2) Rp (Ohm.cm2) Rp (Ohm.cm2) Rp (Ohm.cm2) 1,3E+05 2,4E+05 2,1E+05 3,2E+05 3,E+04 4,E+04 3,E+04 4,E+04


YES


YES

NO NO

NO NO

YES NO

PBS+BSA:  protection Role of albumin: promoting protection at OCP for CoCrMo



Conclusions, electrochemistry without friction: -

Effect of polishing: key role Aeration of the solution should be different, differential aeration Protective effect of albumin at OCP From the inter-laboratories study: trend can be different: protective effect and deleterious effect  improvement of this kind of experiments

Pure electrochemistry: discrepancy of results

What happens with friction? 20





21

Tribocorrosive investigations / synergism approach Training School-Centrale Paris- 02/13/2013

COST 533 ‘Materials for Improved Wear Resistance of Total Artificial Joints’. Pr. Pierre Ponthiaux / Pr. Jean Pierre Celis Tribocorrosion testing for the characterization of CoCrMo biomedical alloys in simulated body fluids Organized within COST 533 and endorsed by EFC-WP18

WORKING PARTY 18 TRIBOCORROSION. - EUROPEAN FEDERATION OF CORROSION – EUREKA-ENIWEP 22

Tribocorrosive investigations / synergism approach

Protocol of preparation: - Same samples, CoCrMo - Paying attention on polishing procedure - Solutions: the same as first step


Origin: inter-laboratories study Focus on results from ENSM-SE lab Friction corrosion apparatus:

23

Conditions: rotation speed 120 rpm (2Hz), radius of wear track area 5mm 1 mechanical contact: rotation


Protocol of testing: - 1st experiment - Open Circuit Potential (Eoc), fluctuations below 1mV.min-1 - EIS measurement, ac amplitude of 10 mV at Eoc Starting frequency is from 105Hz to 10-2Hz at a rate of 10 measurements of frequency/decade (Data quality?). - 2nd experiment - Eoc 2 minutes - Eoc during sliding 1,800 contacts - Eoc 10 minutes after friction - 3rd experiment - Polarization at Eoc, 1 min - After 1 min, friction under polarization, 105Hz to 10-2Hz at a rate of 10 measurement of frequency/decade. - 4th experiment - Measurement of the wear track  Atrack and Wtrack 24


Results from ENSM-SE:

Experiment 1: Rp, ipassive=B (24mV)/Rp

25


Results: Experiments 2-3: Ao ‐Atr

Ao ‐Atr

Atr = Arepass +Aact

Atr = Aact

2 resistances, 2 zones:

1 1 1   R ps Ract R pass 26

Resistance of the passive layer

R pass 

rp Ao  Aact

ract  Ract Aact


Results: Experiments 2-3: Current density

i act

B  ract

Material loss due to corrosion

W

c act

 iact Aact

M Nt lat nFd

M= 58.26 g.mol-1; n= 2.36 ; d= 7.44 g.cm-3. F= 96,485 C.mol-1

Mechanical wear c Wactm  Wtr  Wact 27


Results (ENSM-SE):

Open Circuit Potential

Wear volume

mV/SCE

µm3

-400 -450

4

5

6

13

7

8

9

10

11

12

10 000 000

6 000 000

-500

4 000 000

-550

2 000 000

-600

4

test4 test5 test6 test13

28

8 000 000

Eavf Epdtf Rpavf (mV/SCE) (mV/SCE) (ohm) -374 -564 245 -382 -581 184 -408 -568 186 -417 -548 130

albumine : tests to chose test7 -384 test8 -443 test9 -447 test10 -440 test11 -465 test12 -482

-466 -469 -474 -470 -462 -470

175 227 205 285 148 130

600 400 800 300 400 600 600 200 500 800

Rppdtf (ohm) 3 054 4 193 3 817 4 006 2 2 2 2 3 2

432 367 762 883 064 548

5

6

13

7

µ V (µm3) 0.19 3 633 755 0.22 3 091 233 0.18 3 291 824 3 208 666 0.1 0.11 0.06 0.11 0.12

8 7 6 5 6 8

282 963 622 938 499 372

275 058 666 992 201 784

8

9

% corr 44 37 38 37 27 27 28 31 24 23

10

11

12


Results (ENSM-SE): 1- From the electrochemical point of view: albumin protects metal surface, OCP is higher with albumin 2- From the mechanical point of view and the wear rate: Albumin less protective for CoCrMo, Wear rate is higher than the one without albumin 3- Calculation of wear rate due to corrosion 4- Opening to new ways for experimental protocols 5- Understanding the synergism during friction-corrosion process? Definition of the experimental process

29

Tribocorrosive investigations / synergism approach Total wear volume


Corrosive wear volume without mechanics

Synergy between corrosion and wear

W  Wm  Wc  W Mechanical wear volume without corrosion

Synergism: mechanical wear due to corrosion

Synergy ‘so-so’

W  Wmc  Wcm  Wi  fundamental approach, to determine each term 30

Synergism: corrosive wear due to mechanics





31


Iliac bone

Screw

Head Metal/Ceramic

F retting corrosion Inflam mation of bone tissues

Fretting corrosion

Cracks

degradations

Cancellous bone

Acetabular cup Metal/Ceramic Polymer: UHMWPE Acetabular insert Metal (without?)

Cortical bone Bone cement PMMA principally Physiological liquid Femoral stem 316L (with or without bone cement) Ti-6Al-4V (without cement, with coatings)

 Focus on fretting corrosion between 316L/PMMA  PMMA close to bone or bone cement 32

Fretting corrosion Training School-Centrale Paris- 02/13/2013

 Fretting corrosion**: friction under small displacements between two surfaces in liquid medium, part of tribocorrosion field **Eden

et al. (1911); Uhlig et al. (1950); Waterhouse et al. (1970); Mischler et al. (1992)

-a (S. Fouvry et al.)

o Contact: cylinder (PMMA)/plane (316L SS)

z

a x

y

Cylindrical sample x

2a L

2a Plane sample

e = D/a < 1

33

L: contact length

o

Central area never exposed to fresh solution

o

Central area  stationary solution without O2  differential aeration

o

Corrosion assisted by crevice effect

y

2D


 Mechanical setup

Bumper

Pellier et al., Wear 2011

 Small displacements between samples in corrosive medium 34


load (N) Tangential

80

 Tangential load, friction coefficient  Dissipated Energy, Ed (J), area of the curves Ft-D  Cumulated Dissipated Energy (J) Σ Ed, fretting log

60 40 20 0 -20 -40 -60 Im

0

20 po se 40 dd 60 isp lac em 80 en t (µ m)

) 0.08 m m ( 0.04 nt e 0.00 em -0.04 ac l sp -0.08 Di

 Fixing device with Zircalloy alloy  3 electrodes setup  Same disposal for each experiment, reproductibility benefits 35

Fretting motion ± 40µm


Electrochemistry Electrochemical conditions Step 1 Step 2 Step 3 Step 4 Step 5

Applied Potentialpotential applied:

OCP

-400 or -800 mV(SCE)

Cathodic polarization: -1 V(SCE), 5 min without fretting: 1 h + EIS

without fretting: 10 min + EIS

with fretting: 4 h + 10 EIS regular distribution without fretting: 14 h + 2 EIS after fretting stop and 1 EIS after 14 h

without fretting: 10 min + 2 EIS after fretting stop without fretting: 14 h OCP measurement and 1 EIS after 14 h

Established from Round Robin COST 533, WP 18

    36

Step 1: homogeneization of the oxides layer Step 2: potential conditioning Step 3: fretting experiments Steps 4 & 5: after fretting


Solutions  Aim: studying effect of 1:1 solutions (NaCl) + 1 protein (Albumin)  Effect of Cl- on corrosion of stainless steel  Effect of albumin

 NaCl: 10-3, 10-2, 10-1, 1 mol.L-1  Albumin: 0, 1, 20 g.L-1

37


Open Circuit Potential, live

Crevice corrosion? 38

Bubbles release

Role of albumin-synergy approach Training School-Centrale Paris- 02/13/2013

 Synergy: total wear ≠ corrosive wear + mechanical wear  W W: synergy between corrosion and mechanical wear

Total wear volume

୫ Mechanical wear without corrosion At cathodic potential -800 mV(SCE)

ୡ

ୡ୫

୫ୡ

Stack et al.

Corrosion-induced wear Wear-induced corrosion

Corrosive wear without fretting (can be neglected in this case, ~ 0.01 % of W)

Wmc  

 Measuring the current density at applied potential  Synergistic mechanisms 39

t

I * t * M n* F *d

-400 mV(SCE) Training School-Centrale Paris- 02/13/2013

 Current density drop during fretting corrosion 5

Time (s)

Corrosion current I (µA)

0

5000

10000

15000

I

-5

-15 A = 0 g.L-1 A = 1 g.L-1 A = 20 g.L-1 -25

 Albumin decreases I under fretting corrosion conditions 40

Role of albumin-synergy approach Training School-Centrale Paris- 02/13/2013

 W, total wear volume Measurement by optical profilometry  Wc, corrosive wear without friction Wc ~ 0.01 – 0.1 % of total wear volume  NO significant

 Wm, mechanical wear without corrosion Measurement under cathodic polarization, -800 mV(SCE) NO significant corrosion, by optical profilometry, Wm = 0.3 ± 0.1x106 µm3 

Wmc, corrosive wear enhanced by mechanics under fretting Calculated thanks to Faraday law

W 

Wcm, mechanical wear enhanced by corrosion Rest of the global equation

41

Wear volumes OCP Training School-Centrale Paris- 02/13/2013

 Influence of albumin during OCP experiments 6 A = 0 g. L-1

16 OCP conditions

14

A = 1 g. L-1 A = 20 g. L-1

Wear volume of PMMA (106 µm3)

Wear volume of 316L (106 µm3)

5

316L

4

3

2

A = 0 g. L-1

OCP conditions

PMMA

A = 1 g. L-1 A = 20 g. L-1

12 10 8 6 4

1

2 0

0 10-3

10-2 Ionic strength (mol.L-1)

10-1

1

-3

10 0.001

10-1

-2

10 0.01 Ionic strength

0.1

(mol.L-1)

 WPMMA > W316L SS  Albumin  WPMMA  W316L SS (no statistically different for 316L)  Expected protective effect of Albumin on corrosion of 316L under fretting 42

11

Synergistic approach Applied potential -400 mV Training School-Centrale Paris- 02/13/2013

 Influence of albumin on W A = 0 g.

16

‐400 mV/SCE

A = 0 g.

A = 1 g.

14

A = 20 g.

12

‐400 mV/SCE

A = 1 g.

Wear volume of PMMA (106 µm3)

Wear volume of 316L (106 µm3)

5

PMMA

316L

6

4

3

2

1

A = 20 g.

10 8 6 4 2 0

0 10-3 0.001

-2 10 0.01

Ionic strength / mol.L-1

-1 10 0.1

11

10-3 0.001

-2 10 0.01

Ionic strength /

-1 10 0.1

mol.L-1

 WPMMA > W316L SS  Albumin  WPMMA  W316L SS, same trends than the ones at OCP  Protective effect of Albumin on corrosion of 316L under fretting 43

11

Synergistic approach Applied potential -400 mV Training School-Centrale Paris- 02/13/2013

 Synergistic terms

Geringer, Wear 2012,

 Wc NO significant  0 g.L-1 Albumin: Cl-  Wmc , mechanics enhances corrosion degradations  20 g.L-1 Albumin: Cl-  Wcm , corrosion enhances mechanics degradations 44

Role of coating on debris Training School-Centrale Paris- 02/13/2013

 AFM, 316L SS without albumin E= - 400 mV(SCE) a) NaCl 10-3 mol.L-1 b) NaCl 1 mol.L-1

OCP c) NaCl 10-3 mol.L-1 d) NaCl 1 mol.L-1

D3100 AFM equipped with a Nanoscope 5 Bruker NanoscopeTM

 Applied potential,  Cl-, enhancing wear track area  OCP,  Cl-, enhancing wear track area (less than – 400 mV(SCE)) 45


 AFM, OCP, 316L SS

a) NaCl 10-3 mol.L-1, 0 g.L-1 b) NaCl 10-3 mol.L-1, 20 g.L-1

c) NaCl 1 mol.L-1, 0 g.L-1 d) NaCl 1 mol.L-1, 20 g.L-1

 10-3 mol.L-1 of Cl- with albumin, adsorption of layer, protective effect  1 mol.L-1 of Cl- with albumin, less adsorption due to active corrosion 46


 AFM, - 400 mV(SCE), 316L SS

a) NaCl 10-3 mol.L-1, 0 g.L-1 b) NaCl 10-3 mol.L-1, 20 g.L-1

c) NaCl 1 mol.L-1, 0 g.L-1 d) NaCl 1 mol.L-1, 20 g.L-1

 10-3 mol.L-1 of Cl- with albumin, adsorption of layer, protective effect  1 mol.L-1 of Cl- with albumin, floculation of particles, debris less than 1µm 47


 AFM, - 400 mV(SCE), 316L SS a)

b)

a) NaCl 1 mol.L-1, 0 g.L-1 b) NaCl 1 mol.L-1, 20 g.L-1

V = 16.4 106 µm3

 1 mol.L-1 of Cl- with albumin, more localized damages of 316L  Without albumin, more homogeneous damages and W(0 g.L-1)>W(20 g.L-1) 48

a)


 Particles diameter on 316L SS - 400 mV(SCE)

a) NaCl 1 mol.L-1, 0 g.L-1 b) NaCl 1 mol.L-1, 20 g.L-1

V = 16.4 106 µm3

 With albumin; promotion of floculation  Without albumin: particles diameter less than 100 nm  Studying biocompatibility with this size of particles? 49

Role of coating on debris

a)


 Particles diameter on 316L SS OCP(SCE)

0.7 NaCl 10-3 mol.L-1, A = 0Vg.L = -116.4 106 µm3 NaCl 10-3 mol.L-1, A = 20 g.L-1 0.6 NaCl 1 mol.L-1, A = 0 g.L-1 NaCl 1 mol.L-1, A = 20 g.L-1 0.5

4

3

Number of particles/µm2

Number of particles/µm2

- 400 mV(SCE)

2

1

0 0

20

40

60 80 100 120 140 160 180 200 Particles diameter (nm)

NaCl 10-3 mol.L-1, A = 0 g.L-1 NaCl 10-3 mol.L-1, A = 20 g.L-1 NaCl 1 mol.L-1, A = 0 g.L-1 NaCl 1 mol.L-1, A = 20 g.L-1

0.4 0.3 0.2 0.1 0 0

20

40

60 80 100 120 140 160 180 200 Particles diameter (nm)

 At applied potential, less particles  More particles around 40 nm  Highest concentration of albumin, number of particles  50

Conclusions Training School-Centrale Paris- 02/13/2013

 Fretting-corrosion influence on hip implants  Health impact  Specific device for studying fretting corrosion of materials

 Wear volumes and synergistic approach  Definition thanks to Round Robin, COST 533  Albumin protects 316L SS against fretting-corrosion  Albumin: effect of corrosion on mechanics, Wcm 

 Atomic Force Microscopy investigations  Covering stainless steel surface by albumin at low concentrations of Cl Floculation promoted at highest concentrations  Diameter of particles, around 50nm  Albumin seems related to higher number of particles (PMMA); OCP and -400 mV(SCE) 51

Take home message Training School-Centrale Paris- 02/13/2013

 Bio Tribocorrosion  Friction corrosion // Fretting corrosion (friction under small displacements)  Studying local phenomena by macroscopic tools   seeing ‘bugs on the ground from the top of Eiffel Tower’…

 Challenges  Definitions of protocols (Round Robin, common works are helpful)  Understanding the influence of one parameter amongst more than 100  Proteins effect on tribocorrosion + other ions and so on

 1st way: understanding all influences during the first time



 2nd way: step by step and trying to understand inter-influences 52



Future directions Training School-Centrale Paris- 02/13/2013

 Finding and understanding the evolution of synergism according to potential  About the formalism of synergy, new ways of modeling? To link with microscopic degradations  AFM during electrochemical tests  Modeling thanks to the Point Defect Model  Predicting the evolution of steady state thickness on 316L  Fitting parameters of the model thanks EIS experiments during fretting  Understanding the role of albumin on covering process and so on 53


 EIS: insights for understanding evolution  According to a fretting test 54

 According to ionic strength evolution


 Modeling with genetic algorithm, innovative way  Lss evolution in accordance with experimental facts 55

Publications Training School-Centrale Paris- 02/13/2013  ‘Fretting-corrosion of materials used as orthopaedic implants’, Wear 259 (2005) 943-951 J. Geringer, B. Forest, P. Combrade  ‘Wear analysis of materials used as orthopaedic implants’, Wear 261 (2006) 971–979 J. Geringer, B. Forest, P. Combrade  ‘Wear of poly (methyl methacrylate) against a metallic surface in dry conditions’, Polymer Engineering and Science, 47 (2007), 633-648 J. Geringer, B. Forest, P. Combrade  ‘Caractérisation par spectroscopie d’impédance électrochimique d’un alliage de Co-Cr-Mo dans différents milieux simulant le liquide physiologique’, Matériaux & Techniques, 95 (2007), 417-426 J. Geringer, B. Normand, R. Diemiaszonek, C. Alemany-Dumont, N. Mary  ‘Friction-corrosion of AISI 316L/bone cement and AISI 316L/PMMA contacts: ionic strength effect on tribological behaviour’ Wear, 207 (2009), 763-769 J. Geringer, F. Atmani, B. Forest  ‘Assessing the tribocorrosion behaviour of Cu and Al by electrochemical impedance spectroscopy’ Tribology International, 43 (2010), 1991-1999 J. Geringer, B. Normand, C. Alemany-Dumont, R. Diemiaszonek,  ‘Influence de la teneur en protéines de solutions physiologiques sur le comportement électrochimique du Ti-6Al-4V : reproductibilité et représentation temps-fréquence.’ Matériaux & Techniques, 98 (2010) 59-68 J. Geringer, L. Navarro, B. Forest  : ‘Fretting corrosion with proteins: the role of organic coating about the synergistic mechanisms’ Thin solid films, accepted, 10.1016/j.tsf.2012.09.095 J. Geringer, J. Pellier, M.L Taylor, D.D. Macdonald  ‘Atomic Force Microscopy investigations on pits and debris related to fretting-corrosion between 316L SS and PMMA. Wear, 292-293 (2012) 207-217 J. Geringer, J. Pellier, F. Cleymand, B. Forest  ‘Modeling fretting corrosion wear of 316L SS against Poly(methyl methacrylate) with the point defect model: fundamental theory, assessment and outlook’ Electrochimica Acta, 79 (2012) 17-30 J. Geringer, D.D. Macdonald  ‘Electrochemical Impedance Spectroscopy insights for fretting corrosion experiments.’ Tribology International, accepted, doi: j.triboint.2012.10.027 J. Geringer, J. Pellier, M.T. Taylor, D.D. Macdonald  ‘Role of proteins on the electrochemical behavior of implanted metallic alloys, reproducibility and time-frequency approach from EIS (Electrochemical Impedance Spectroscopy)’ Intech, Ed Pr. Reza Fazel, ISBN 979-953-307-028-4, 2011 J. Geringer, L. Navarro  ‘Fretting-corrosion in biomedical implants’ Book Chapter, ‘Tribocorrosion of passive metals and coatings’, Eds Pr. D. Landolt & Dr. S. Mischler, Woodhead Publishing Limited, in press J. Geringer, B. Boyer, Kyungmok Kim  ‘Synergism effects during friction and fretting corrosion experiments - Focusing on biomaterials used as orthopedic implants.’ Edited by Pr. P. Davim, Department of Mechanical Engineering, University of Aveiro, Biomaterials and medical tribology: Research & development, Woodhead Publishing Limited. Accepted in progress J. Geringer, M.T. Mathew, M.A. Wimmer, D.D. Macdonald  ‘Applications of computational modeling for joint replacements chap 19: Computational modeling of hip implants’ Edited by Pr. Z. Jin Woodhead limited publishing, accepted J. Geringer, L. Imbert, Kyungmok Kim  ‘Ionic strength effect during fretting-corrosion on a ‘model’ contact: PMMA-stainless steel. Application to orthopaedic implants’ PPUR book, in press J. Pellier, J. Geringer, B. Forest  ‘Fretting-corrosion between 316L SS and PMMA: influence of ionic strength, protein and electrochemical conditions on material wear. Application to orthopedic implants.’ Wear, 271 (2011) 1563-1571 J. Pellier, J. Geringer, B. Forest  ‘Analysis of energy dissipation in fretting corrosion experiments with materials used as hip prosthesis’ Wear, 296 (2012) 497-503 doi: 10.1016/j.wear.2012.07.014 K. Kim, J. Geringer  ‘Fretting corrosion damage of total hip prosthesis: friction coefficient and damage rate constant approach’ Tribology International, accepted, 10.1016/j.triboint.2012.10.008 K. Kim, J. Geringer 19 articles and book chapters 20 proceedings 15 posters

56

Next meetings Training School-Centrale Paris- 02/13/2013

 Tribocorrosion meeting, Cefracor, Saint-Etienne, France, March 22th 2013  ICMCTF 2013, San Diego CA-USA, April 29th to May 3rd 2013 http://www2.avs.org/conferences/icmctf/pages/symposium_d.html D2. Coatings for Bio-corrosion, Tribo-corrosion, and Bio-tribology Session Chairs Margaret Stack, University of Strathclyde, UK, [email protected] Mathew Mathew, Rush University Medical Center, USA, [email protected] Jean Geringer, Ecole Nationale Superieure des Mines, [email protected] This session seeks papers on coatings designed for bio- and tribo-corrosion resistance and degradation of bio-implant and other relevant surfaces, both in vitro and in vivo, applicable to a range of environments including replacement joints for enhanced articulation and dental materials. Papers on mechanistic descriptions, life cycle modeling, surface modification for bio-compatibility, sliding wear, abrasion, erosion, and fretting wear of the performance of thin films in tribo-corrosion environments are also welcome. The session will provide a forum to discuss the state-of-theart understanding of the degradation of thin films in a multidisciplinary format to include the action of corrosion, tribo-corrosion, and bio-tribo-corrosion environments on material loss mechanisms. Invited Speakers Jeremy Gilbert, Syracuse University, USA, “Biomaterials: Electrochemical Behavior of Medical Alloys in Orthopedics and Dentistry and Their Interaction with the Biological System” Pagona Papakonstantinou, University of Ulster, UK, “Carbon Nanotubes and Graphene for Biological Sensing”

 Tribocorrosion 2014, Glasgow UK

Welcome aboard! 57

Acknowledgements Training School-Centrale Paris- 02/13/2013

 Loire council and St-Etienne Métropole-Région Rhône-Alpes, France Financial supports

 Pr. Farizon; Dr. R. Phillipot, Dr. B. Boyer Saint-Etienne Hospital Joint lab with orthopedic surgeons

 Dr. Cleymand from ENSM-Nancy-France for AFM investigations.  All members of 107 & 206A office Penn State University  Members of the Tribocorrosion community (Worldwide)

58


Thank you for your attention Dr. Jean Geringer [email protected] 59

Additional slides Training School-Centrale Paris- 02/13/2013

Appendix

60

EIS approach Training School-Centrale Paris- 02/13/2013

 Applied potential, -400 mV(SCE) Rp

Q/10

n

40

-8

20

-12

-16

NaCl, 10-1 mol.L-1

-20

0 0

5,000

10,000 Time (s)

61

0.95

0.75

n, CPE parameter

I

Polarization resistance Rp (k), Q/10 (10-1µS.sn)

Corrosion current (µA)

-4

0.55

15,000

   

 current density = metal dissolution  Rp consistent with metal dissolution  n: surface less and less homogeneous  Q: capacitance effect due to Fe ions?


 Applied potential, -400 mV(SCE)

80

40

1E-3

1E-2

1E-1

0 1E+0

Ionic strength, Ic (mol.L-1)

1E-3

1E-2

1E-1

0 1E+0


0.6

1E-2

1E-1


0.5 1E+0

nmf

0.8

0.7

62

400

0.9

0 g.L-1 1 g.L-1 20 g.L-1

1E-3

800

Rp_mf (k)

120

Qmf (µS.sn)

0 g.L-1 1 g.L-1 20 g.L-1

1,200

0 g.L-1 1 g.L-1 20 g.L-1

 20 g.L-1of albumin: significant impact  Albumin: 0-1 g.L-1, no difference  no effect of 20 g.L-1 albumin on Q  Albumin allows big value of n; homogeneous adsorption


900

0 g.L-1 1 g.L-1 20 g.L-1

30

1E-2

500

0 1E+0

1E-1

-30

300

Rp

1E-3

700

Q

 Applied potential, -400 mV(SCE)

100

g.L-1

0 1 g.L-1 20 g.L-1

-60


-90

63

1E-2

1E-1


n

0.10

0.05

1E-3

1E-2

1E-1

1E+0-100

Ionic strength, Ic (mol.L-1) 0.15

0 g.L-1 1 g. L-1 20 g.L-1

1E-3

0.00 1E+0 -0.05

 Rp: relevant effect of albumin, Alb 20 g.L-1 Alb, Ic , Rp, chlorides promote dissolution and difference due to fretting less highlighted with Alb  Q: albumin does not change pseudo capacitance. Effect of surface outside fretting zone. Adsorption of Alb decreases the effect of fretting-corrosion


0

I=f(E) NaCl 1 mol. L-1, A = 0 g.L-1 NaCl 1 mol.L-1, A = 20 g.L-1 NaCl 10-3 mol.L-1, A = 0 g.L-1 NaCl 10-3 mol.L-1, A = 20 g.L-1

system without fretting

-2

log(I)

-4

-6

-8

-10 -1

-0,8

-0,6

-0,4

-0,2

Potential E (V(SCE))

    64

Usual results Potentio-dynamic, voltammetry experiments Highest Cl-, lower potential, enhancing corrosion Protective effect of albumin

0

0,2

0,4

Role of albumin-synergy approach Wear volumes Training School-Centrale Paris- 02/13/2013

 Wear track area  Fixation of sample

Bruker Nanoscope ex. Veeco NT 9100

 Acquisition  Filtering  RMS plane  Cylindrical shape, filtering  Defining reference plane  3 measurements per length  Value of wear volume

2mm 0.64mm 65

Role of albumin-synergy approach Wear volumes Training School-Centrale Paris- 02/13/2013

 Wear track area  ‘W’ wear shape for 316L  ‘U’ wear shape for PMMA Wear track of 316L

Wear track of PMMA

2mm 0.64mm

0.64mm SFB 2011

66

Experiments Training School-Centrale Paris- 02/13/2013

 Electrochemical setup  OCP: device with 2 electrodes, reference electrode: (SCE, E = +246 mV(SHE, Saturated Calomel Electrode) working electrode (Stainless steel 316L)  Applied potential, reference electrode: (SCE, E = +246 mV(SHE, Saturated Calomel Electrode) working electrode (Stainless steel 316L) counter electrode Pt.  Electrical insulation thanks to Zircalloy

Bumper

67

Fretting motion ± 40µm