Upload
vanngoc
View
247
Download
6
Embed Size (px)
Citation preview
Revista Romn de Materiale / Romanian Journal of Materials 2014, 44 (3), 283 291 283
STABILITATEA MASELOR FOSFATICE FLUORURATE PE ALIAJE DE CoCrMo
ABOUT STABILITY OF ELECTRODEPOSITED FLUORIDATED PHOSPHATE MASSES ON CoCrMo ALLOYS
DANIELA COVACIU ROMONI, GEORGETA VOICU, DANIELA IONI, IOANA DEMETRESCU Universitatea POLITEHNICA Bucureti, str. G. Polizu, nr. 1, 011061, sect. 1, Bucureti, Romania
CoCrMo alloys are extensively used in
tissue engineering in both dental and orthopaedic applications and are highly recommended due to the good ratio quality /price comparing with other metallic biomaterials. The present approach is related to electrodeposition of fluoridated phosphate masses with good ratio calcium to phosphorus close to the one existing in bone.
SEM and EDX analysis confirm that the electrochemical method for deposition of fluoridated apatite on CoCrMo is efficient and the results were quantified using electrochemical and mechanical measurements.
Aliajele de CoCrMo sunt des utilizate n ingineria
tisular, att n aplicaiile stomatologice ct i n cele ortopedice i sunt recomandate datorit raportului bun calitate/ pre comparndu-le cu alte biomateriale metalice. Abordarea actual este legat de electrodepunerea maselor fosfatice fluorurate cu raport bun calciu fosfor, apropiat de raportul molar existent n os.
Analizele SEM i EDX confirm c metoda electrochimic pentru depunerea maselor apatitice pe aliajul de CoCrMo este eficient iar rezutatele au fost cuantificate prin msurtori electrochimice i mecanice.
Keywords: CoCrMo alloys, electrochemical deposition, SEM, EDX, artificial saliva, physiological serum 1. Introduction
Having very good mechanical properties as
castability, corrosion and wear resistance CoCrMo alloys [1] noowdays, are extensively used in tissue engineering in both dental and orthopaedic applications [2,3]. Even as heads in artificial joints. CoCrMo alloys have been introduced in bioapplications at the begging of the last century, but due especially to its problems with ion release for a period of time was used with limitations. A remarkable comeback was known in its using after introducing largely the surface engineering procedures [4,5] and the type of Ni-free alloy according to ASTM F-75 standard [6]. In medicine regeneration, CoCrMo alloys are highly recommended due to the good ratio quality /price and comparing with other metallic biomaterials as stainless steels [7] which have disadvantage in corrosion resistance or with titanium alloys which have demerit in wear resistance [2], despite the large variety of surface modifications proposed for enhancing their performance especially at the surface level [8].
The wear resistance of the CoCrMo alloys is due to the carbide structure found in both cast and wrought alloys. The hardness and elongation is attributable to the martensite transformation induced by strain [9]. The resistance to corrosion is
due to its passive film formed at the surface in various bioliquids [10]. The existence of a small amount of nickel as an impurity, despite the fact International Agency for Research on Cancer (IARC) of the World Health Organization (WHO) estimates that nickel is carcinogenic [11], is able to maintain workability. More recently, taking into account the bacteria extension, and knowing the silver effect in enhancing antibacterial function new coatings having antibacterial inhibition effect were elaborated on the CoCrMo alloy surface [12] including hydroxyapatite (HA) as bioactive component and silver as antibacterian agent as well. Hydroxyapatite as bioactive coating was elaborated via various procedures [13,14] leading to various properties. It has been reported that plasma-sprayed HA coatings dissolve and degrade quickly, resulting in the weakening of the coating-substrate bonding or the implant fixation to the host tissues [15]. For this reason any changes to the HA that result in a higher chemical stability would be an advantage.
Impregnations to the HA crystal structure the chemical elements such as Fluoride by substituting OH groups was performed successfully on various alloys [16,17].
The present approach is related to electrodeposition of fluoridated phosphate masses with good ratio calcium to phosphorus close to the
Autor corespondent/Corresponding author, E-mail: [email protected]
284 D.C one existingto dissolutiotrying to electrochemcorrosion prelease evacomparisoncoated allosolution is d
2. Experim
For
were used polished on1200) and aFor 15 minuacetone anfrom the Srinsed in dtemperaturewas (NH4)2CaCl22H2Oelectrolyte ufluoridated titanium [18order to encoating by thydroxyl ioCoCrMo all
2.1. Coatin
The different te22oC (sam(Figure 1.)electrode (aand CoCrMWorking pathe experimpotentiostatequipped w
Aftecalcinated Thermal trethe crystalCoCrMo safor strengthFigure 2 selectrochemcoatings on
CoP
Covaciu Romon
g in bone, inon. Firstly the
establishmical behavparameters ialuation withn of electrooy in saliva discussed as
ental
r electrodeposamples o
n SiC abrasafter that etcutes the sam
nd ethanol inSiC paper. distilled watee. The cont2HPO4 0.025
O 0.042 M,used in litera
hydroxyap8]. A volumenhance the dthe release oons. The oy its accord
ng process coating proc
emperatures:mple B) usi) with a panode), Ag/AMo as worarameters arments were pt/ galvanosta
with Volta Maer electrode
at 4000C eatment wasllinity and amples. Calchening the shows variatmical deposn CoCrMo sa
WorkoCrMo Sample
Proba CoCrMo
A B
ni, G. Voicu, D. order to proe aim of pres a relaiour of sucn bioliquids
h mechanicaochemical sand in phy
s well.
osition of phoof CoCrMo. sive papers hed in HF 4%
mples were un order to reFinally the er and drietent of elec5 M, NH4F , almost siature for elecatite on s
e of H2O2 3%deposition prof H2 gas anchemical c
ding to ASTM
cess was pe 28oC (samng a electr
platinum plaAgCl as referking electrre presentedperformed usat controlled ster 4 Softwa
eposition all temperature
s made in orthe purity
cination was bonds of ation of poteition of fluo
amples.
ing parameters Cur
Densi
Ioni, I. Deme
ovide resistasent researction betwh coating frand from i
al propertiesstability of ysiological N
osphate masSamples w(600, 800
% for 2 minuultrasonicatedemove partic
samples wed at the roctrolyte solu 0.012 M milar with
ctrodepositiostainless s
% was addedrocess of dend productioncomposition M F75 [6].
erformed at mple A) androchemical
ate as counrence electroode (cathod
d in Table 1.sing a PGZ
by a compuare. samples w
e for 1 horder to increof the coaalso, benefi
patite coatinntial in timeoridated apa
for coating procrrent Density itate de curent[mA/cm2]
-1
etrescu / About CoCrM nce
ch is een rom ons
s. A the
NaCl
sses were and tes. d in cles
were oom tion and the
n of teel d in nse n of
of
two d at cell nter ode de). . All 301 uter
were our. ase
ated icial ngs. e of atite
F(Cpoce(Cpo
F
s2sh
yy
cre
cess/ ParametriEle
time / Tim
t stability of elecMo alloys
ig. 1 - ElectrolyCoCrMo), 2-REotentiostat/ galvelulei electrochCoCrMo), 2-ERoteniostat/ galv
ig. 2 - Coating p
Curvehown below8oC have stecond equaave standard
= - 0.80368 += - 0.88625 +
The man be descrieactions.
i de lucru pentruectrodeposition
mp de electrodep[min]
60
ctrodeposited flu
ytic cell scheme E (Ag/AgCl), vanostat, 6-magimice folosite
R (Ag/AgCl), 3-vanostat, 6-agita
process/ Proces
e equations w; equation (tandard devition (2) for d deviation, R
+ 0.1388 e0.07+ 0.43206 e-0
mechanism ofbed as a ser
u procesul de de
punere
uoridated phosp
used in coating3-CE (Pt), 4
gnetic stirrer, 7n procesul de CE (Pt), 4-soluator magnetic, 7
sul de depunere
for coating 1) for coatediation, R2 = coated CoCR2 = 0.92
7442x
0.02516x
f electrolytic ries of electro
epunere Deposition tem
Temperatura de[oC] 28 22
phate masses on
g process: 1-W4-electrolyte, 57-stirrer/ Schem
depunere: 1-Euie electrolit, 57-agitator.
e.
process ard CoCrMo a0.65 and th
CrMo at 22oC
(1) (2)deposition ochemical
Table
mperature e depunere
n
WE 5-
ma EL 5-
re at e C
) )
1
D.Covaciu Romoni, G. Voicu, D. Ioni, I. Demetrescu / Stabilitatea maselor fosfatice fluorurate pe aliaje de CoCrMo 285
The possible sources of OH- at the cathode are [19] O 2H O 4e 4HO (3) NO H O 2e 2HO NO (4) 2H O 2e H 2HO (5)
Hydroxide ions, generated during the electrodeposition process, resulted in an increase of the pH in the vicinity of the cathode; which led to the occurrence of the following reactions: H PO e HPO H (6) H PO 2e PO H (7) H PO HPO H (8) HPO PO H (9)
The precipitation of phosphate ions occurred due to the acid-base reactions, which are vital for the crystallization process of formation of FHA coating film according to the following reaction: H PO HO HPO H O (10)
H PO H O 2e H PO 2HO (11)
The suitable local chemical environment in the vicinity of the cathode enabled the HPO42- ions to react with the Ca2+ ions [17]. Ca HPO H O CaHPO 2H O (12)
The coating, after alkaline treatment, was converted to HA according to the following reaction: 10CaHPO 2HO Ca PO OH 4PO 10H (13)
Calcium deficient hydroxyapatite was formed as follows [20] 10 x Ca 6 x PO
xHPO 2 x HO Ca HPO PO OH (14) where 0 < x 2.
Addition of NaF into the electrolyte led to the occurrence of the following reactions. At the early stage, Ca2+ ions rapidly consumed the F ions in the electrolyte to form CaF2 which can be expressed as follows [20] Ca PO OH 10F 7 n H
5CaF H O 3 n H PO nH PO (15)
CaF2 particles reacted with the HPO42- ions in the solution to form FHA [20] 5CaF 3 n H PO nHPO
1 x H O Ca PO OH F 10 x F 7 x n H
where (0 < x < 1, 0< n < 3) (16) Combining reactions (15) and (16) resulted in the formation of FHA via the following reaction: 10Ca 6PO xF 2 x HO Ca PO F OH (17)
3. Results and discussions 3.1. X-Ray Diffraction Analysis X-Ray Diffraction analysis was performed for the coated samples of CoCrMo at 22C with Empirean PANalytical Diffractometer with radiation Cu (=1.5406). The acquisition was done from 10 to 80 degrees 2 with 0.02 degres step and acquisition time with 2 seconds step. Incidence angle was 1 degree. In Figure 3 is presented XRD analysis for coated CoCrMo samples.
From the XRD analysis it can be observed the deceleration of the mineralogical crystalline phases of fluorohydroxyapatite and CaHPO4.
Fig. 3 - XRD analysis of coated CoCrMo/ Analiza XRD a probelor acoperite de CoCrMo.
3.2. Scanning electron microscopy analysis
Coated samples of CoCrMo alloy were investigated with a scanning electron microscope HITACHI, S-2600N Model coupled with energy-dispersive X-ray spectroscopy (EDX) for morphology determinations. In Figure 4 are presented images with SEM characterization.
The coated CoCrMo samples shows morphologies which are characteristic to hydroxyapatite according to literature data and the synthesized deposit on CoCrMo alloy consists of spherical particles formed of plaques with very small dimensions (Figure 4). The coating is not uniform on all over the surface probably due to deposition conditions.
The fluoride presence was not observed in elemental analysis, due to the fact that the scanning electron microscope used was limited and does not detect halogens, but the fluoride existence in the coating was confirmed from FT-IR spectra at 719 cm-1. In the literature, Freund, describes a relation between the introduction of fluoride in hydroxyapatite and the increase of a band around 720-740 cm-1 [21].
The difference between coated CoCrMo at 28oC and the coated CoCrMo at 22oC shows a better adherence on the metallic substrate and a more uniform deposition for the electrochemical deposition carried at 22 degrees.
286 D.C
Fig. 4 - SEM ia), b)
Fig. 5 -EDX
FiguCoCrMo saraports Ca/
Covaciu Romon
images of apatiCoCrMo acope
spectra of apati
Fig. 6 - T
ure 5 showamples and pP.
ni, G. Voicu, D.
te coatings: a), erit la 28oC, c), d
ite coatings: a)
Tafel plots for co
ws EDX spepermit la calc
Ioni, I. Deme
b) Coated CoCd) CoCrMo acop
Coated CoCrMo280C; b)
oated and uncoa
ectra of coaculation of mo
etrescu / About CoCrM
CrMo at 28oC; c)perit la 22oC.
o at 280C; b) Co) CoCrMo acope
ated CoCrMo a
ated olar
pp
t stability of elecMo alloys
), d) Coated Co
oated CoCrMo aerit la 220C
lloy/ Curbele Ta
The resence of cresence of io
ctrodeposited flu
CrMo at 22oC/ I
at 220C/ Spectru
afel pentru aliaju
EDX spectrcalcium and ons substrate
uoridated phosp
Imagini SEM de
ul EDX: a) CoC
ul CoCrMo.
ra analysis phosphoruse, cobalt, chr
phate masses on
epuneri apatitice
rMo acoperit la
revealed th, but also thromium and
n
e:
e e
D.Covaciu Rom
molybdenumcoated CoCat 28oC and
EDXcoating at 2CoCrMo sacalcium, beCa/P in characterizaperformed o
3.3. Stabili
masssaliva
3.3.1. ElectAppl
(FHA), Ca10degree of fHA coating,seen from determinatio
CoCsamples w(NaCl 0.9%electrochemelectrochemcyclic voltaartificial sal
TafThe
in the intervcircuit pot2mV/seconusing the ssystem usesaliva and pelectrolytes
TheVoltaMaste
The3) were recimmersed ithe coated a
Fig. 7
Prot
ectiv
e
moni, G. Voicu,
m. Molar ratCrMo alloy ad 1.88 for coaX analyses s
28oC is a littleample at 22eing much
bones. Nation of thon coated Co
ity of CoCrMses in salina trochemicalication of 0(PO4)6(OH)2fluoridation , could providelectrochemons. CrMo samp
were charac% wt %) amical methomical impedammetry. Thiva Afnor is pfel plots e Tafel plots val 200/+ 2tential and ds. The detesame three ed for coatipsysiologicals. e polarizatir 4 Software
e smallest cucorded in cain artificial salloy has a g
- Protective effi
020406080
, D. Ioni, I. De
ios of phospare 1.40 for cated CoCrMoshows that Ce bit deficien2oC is easilcloser to thNext deterhe coated oCrMo at 22
Mo coated wne solution
l characterizfluoridated
2xFx where 0 (FHA) in c
de better stamical data an
ples and cocterized in and in artifods, such adance spece chemical presented in
determinatio200mV in ref
with a erminations w
electrodes ing process l serum (NaC
on curves are presenturrent densitase of coatedsaliva, but ingood corrosio
ciency/ Eficien
emetrescu / Sta
phate massescoated CoCro at 22oC. CoCrMo samt in calcium, ly overcome
he molar raprminations CoCrMo w
oC.
with phosphn and artifi
zation hydroxyapa
< x < 2 is thcomparison wability as cannd ions relel
oated CoCrsaline solu
ficial saliva as Tafel plctroscopy compositionTable 2.
on were carference to oscan rate were performsystem as using artifi
Cl 0.9% wt%
obtained ed in Figure ty values (Tad CoCrMo an both solution resistance
a acoperirii.
abilitatea maselo
s of rMo
mple but
e in port
for were
hate icial
atite e with n be ase
rMo tion by
ots, and n of
ried pen
of med
the icial ) as
by 6.
able alloy ons e.
pccim
athabvep
ptheababhpmth[2
eth
recpa
plis
be
rese
esCthpscd
or fosfatice fluor
Accorlots it is obvase of coateoverage wi
mprove the aThe c
lloy is coatehan in artifggressive. Py phosphatealues are lectropositiveassive chara
As faorosity is a
he interactionspecially thllows a deeiomaterial, ttachment cae a way to appens for ossible to
materials, to hus limiting t24].
The sstimated by
he following e
Where
esistances oating/substotential diffenodic Tafel c
The orosity fromsted in Table
The ce calculatequation [25]:
Whereesistances oubstrate. Thquation 19 is
FHA cfficiency in aliva. It ca
CoCrMo imprhe corrosivehysiological ubstrate. FHorrosive meecline the co
rurate pe aliaje
rding to obvious that coed alloy andith fluoridat
anticorrosion corrosion raed and in sficial saliva,
Polarization re masses adisplaced fe domain, acter. ar as the bcrucial parans at the impe reaction eper penetraand thus
an be reachetune the stifnatural bonereduce the match that
the so-called
urface porosy potentiodyequation:
e Rp and Rof the barate pair, re
erence betwecoefficient ofcalculated
m the potente 2. coating proteed using th:
e Rop and f the uncoate
he protectives shown in Fcoating shophysiologican be seen roved, after Fe action of
serum froHA coating reedium into thorrosion rate
de CoCrMo
btained datarrosion rate we can conted phosphproperties.
ates are lowaline solutio, the latterresistances aand corrosiofrom electro
indicating
bioactivity ismeter, since
plant host tissrate. A po
ation of celhigher lev
ed [22]. Poroffness of a mes [23]. In t
stiffness ot of natural d stress shi
sity fraction namic polar
Rp0 are theare substraespectively, een them, af the substratvalues of tiodynamic a
ective efficiehe using t
Rp are theed/ substrate
e efficiency cFigure 7.
wed a highal serum thathat the cor
FHA coatingf the artificm penetrateduce the dihe substrate.
287
a from Tafeis smallest infirm that thhate masse
wer when thon are higher being lesare enhanceon potentialonegative t
a possibl
s concernede it influencesue interface
orous coatinls inside thvels of ceosity can alsmaterial, as his way, it i
of biomedicabone tissue
ielding effec
for FHA warization usin
(18)
e polarizatiote and thEcorr is thand a is thte. the coatin
analyses ar
ency (Pi) cathe followin
(19)e polarizatioe coated barcalculated fo
her protectivan in artificiarrosion rate o. FHA inhibitial saliva oing into thffusion of th
e and hence
7
el n e
es
e er ss d s o e
d, es e, g e
ell o it s al e, ct
as g
n e e e
g re
n g
n re or
e al of ts or e e e,
288 D.C
Fig
.
Fig. 9 - Bode acope
Covaciu Romon
ChemSubst
Quantit
Soluti
Electricorr[A
EcorRp [
Vcorr [P(
. 8 - Nyquist dia
diagrams for Cerit i neacoperi
ni, G. Voicu, D.
mical compositiotance Naty (g/L) 0.
Electrochemicaions
rodes A/cm2] rr [V] /cm2] [mm/Y] %)
agrams for CoCCoCrMo acop
CoCrMo and coit n soluie de s
Ioni, I. Deme
on of artificial saaCl KCl7 1.2
al paramettres fArtificial
CoCrMo 0.258
-0.481 10.63104
2.9610-3 -
rMo and coatedperit i neacope
oated CoCrMo saliv artificial i
etrescu / About CoCrM
aliva Afnor/ ComNa2HPO
0.26
from Tafel plots/saliva (Afnor)
CoCrMo0.090.05
21.721.139
13.4
d CoCrMo in arterit n soluie de
in artificial sal
i soluie salin.
t stability of elecMo alloys
mpoziia chimicO4 NaHCO3
1.5
/ Parametri elec
o/FHA C99 55 104 310-3 541
tificial saliva and saliv artificial
iva and in salin
ctrodeposited flu
saliva artificialKSCN 0.33
ctrochimici din cPhysiologica
(NaCl 0.9CoCrMo
0.546 -0.381
33.58103 5.4610-3
-
d in saline soluti soluie salin
ne solution/ Dia
uoridated phosp
l Afnor CH4ON2
1.3
curbele Tafel al serum 9%) CoCrMo/FHA
0.125 0.111
11.42104 1.7210-3
14.64
ion/ Diagramele
agramele Bode
phate masses on
Table
Table
e Nyquist pentru
pentru CoCrM
n
2
3
u
Mo
D.Covaciu Rom
Fig. 10 - Cylicacope
EleThe
Spectroscousing workiKHz, final fThe three Ag/AgCl, Pt
Figucoated andand in salin
Figuand uncoatsaline solut
EleelectrochemdeterminatioRsol (R1) transfer reCoCrMo/ ephase elemat the interfconstant phinterface.
Thesurface is consisting ohigh impedprotection, impedance,in bioapplic
moni, G. Voicu,
c Voltammetry perite i neacope
ctrochemicae Electrpy (EIS) deteing parameterequency 50
electrodes t, CoCrMo anure 8 presd uncoated e solution. ure 9 presented CoCrMotion. ctrochemica
mical imons are preis solution resistance (pelectrolyte inment (electricface CoCrMhase elemen
e EIS results composedof an inner dance and and an ou
, which can sation, includ
EleSolutions/ Solu
Electrodes Electric circui
Rsol (R1) [/cmRp (R2 ) [/cm
CPE1 n1
CPE2 n2
, D. Ioni, I. De
plots for coated rite
l Impedancerochemical erminations ers for initial
0 MHz and 1system w
nd CoCrMo csent Nyquist
CoCrMo in
nt Bode diago in artificia
l parammpedance esented in Tresistance, Rpolarisation terface), CPc double layo/ electrolyte
nt of the coa
s indicated thd of a bibarrier layeresponsible
uter porous sustain a suiing cell adhe
ectrochemical pii Arti
CoCit
m2] 29.7m2] 11.54
0.100.9
- -
emetrescu / Sta
and uncoated C
e SpectroscopImpeda
were performl frequency 0mV amplitu
was the sacoated. t diagrams
artificial sa
rams for coal saliva and
meters frspectrosc
Table 4, whRp (R2) is lo
resistance PE1 is constyer capacitae) and CPE2
ating/ electro
hat the CoCr-layered ox
er associatede for corros
layer of loitable behavesion.
paramettres fromificial saliva/ Sa
CrMo C
70
4104
10-3 91
abilitatea maselo
CoCrMo sample
py nce
med 100 ude. me:
for aliva
ated d in
rom copy here oad
at tant nce 2 is
olyte
rMo xide d to sion wer iour
F
m EIS diagramsaliva articifial CoCrMo/FHA
119.31 27.52104 10.0310-5
0.99 50.3410-5
0.48
or fosfatice fluor
es/ Curbele de
ig. 11 - a) Ca2+ rNaCl 0.dissolutiionilor de
s/ Parametri elecS
CoC
9.5
32.9012.40
0.9--
rurate pe aliaje
volatametrie cic
release in NaCl9%; b) An emon at interface/e calciu la interf
ctrochimici din dSaline Solution/ CrMo
58
07103 010-5 91 - -
de CoCrMo
clic pentru pro
0.9%/ Dizolvarmpirical model / Un model emfa.
diagramele EIS Soluie salin
CoCrMo/FHA
15.31 10.29104 9.7310-5
0.81 93.2510-5
0.49
289
obele de CoCrM
rea ionilor Ca2+ iof calcium ion
mpiric al dizolvr
Table
A
9
Mo
in ns rii
4
290 D.C
In bin artificial resistance values are Tafel plotsmaterials ccorrosion rserum. Canphysiologicaof magnitudsaliva, indcharacter on2 we can electrolyte interface odiffusive ch
CycFor
working pa800mV, E2mV/seconvoltammetryCoCrMo saphysiologica
All confirm thaimproved aggression to the fact aggressive solution, wh 3.3.2. Ca2+
0.9%Cal
sample obpresented imodel of dtime was uthe evolutiostate.
Fig. 12 - ConCoCpen(b).
Covaciu Romon
both cases, saliva, the of the subscorrelated
s. In artificovered and resistance cn be noticedal serum thede smaller dicating a of the serum.say that at thexist a capa
of CoCrMo/Faracter throu
clic Voltammr cyclic voltaarametters wE2 = 150ds. In Figuy curves famples in soal serum.
electrochat the phospcorrosion rof the solutthat that scharacter
hich causes a
ion release%) cium ions r
btained at 2in Figure 11issolution atntil 100 hou
on in time re
ntact angle valCrMo sample (ntru proba CoC
ni, G. Voicu, D. in physiologcoating layetrate (Rp vawith valuescial saliva, uncovered,
compared tod that in cae Rp value ithan the Co
much mo. From the vhe interface acitive charaFHA/electrolyugh obtained
metry ammetry detwere: E0 = -0 mV anure 10 arefor uncoateolutions, artif
emical cphate massresistance. tions studiedsaline solutio
due to frea stronger co
e in saline
release on c220C in sal together w
t interface. Turs and it is epresents a
ues for uncoat(b)/ Valorile un
CrMo neacoper
Ioni, I. Deme
gical serum er improves alues). Also obtained fr
both studshows a beo physiolog
ase of CoCrs with an oroCrMo/ artifiore aggressalues of n1 of the CoCr
acter and at yte we haved porous laye
erminations -800mV, E1nd scan re shown cyd and coaficial saliva
haracterizaties coating Regarding
d the results on has a mee Cl- ionsorrosion.
solution (N
coated CoCrine solutionith an empir
The observato mention ttrend to ste
ted (a) and conghiului de conrit (a) i acop
etrescu / About CoCrM and the Rp
rom died etter gical Mo/ rder icial sive and Mo/ the
e a er.
the = -rate yclic ated and
ons has the led
more in
NaCl
rMo n is rical tion that ady
oated ntact
perit
3
pp(dFd
ais
pasrea
3
dwgV
avoh
ddP
bSadscH7w
acac
4
epDmfl
umpas
t stability of elecMo alloys
3.4. Contact The d
erformed wrocedure sudrop) of dis
Figure 12 theetermination
For ngle values
s 96.30 whichIn c
hosphate mangle is 15uperhydrophelation with bngles the bio
3.5. MicroharThe V
eterminationwith Buehler
for 10 secoVickers units
The lloy was 46alue 310 Hbtained valardness due
Adheetermined aevice for det
Pull- off adheProte
y determininStrength) wh
ttached withiameter) waurface coveromponents
Henkel). The 2 hours at r
with the speeBy co
dherence teoated CoCrnd 2.69 MPoating layer
4. Conclusio
SEM lectrochemichosphate m
Diffraction amineralogical uorohydroxy
An esing ele
measurementhosphate mlloy is morealiva and ph
ctrodeposited flu
Angle measdeterminatiowith CAM upposes to stilled watere values reprns. all uncoateare bigger t
h indicate a hase of Coasses coatin.3 fact thathilic charactebiocompatibocompatibility
rdness and Vickers test ns of metallicequipment b
onds and was(HV). obtained va9 HV. ComHV accordinue is highe
e to the coatision of saccording totermining thesion AT-A ( Dctive coating
ng the higheshich is requh adhesive cas closely red with epo
(epoxy-patcadhesive wa
room temped of 0.875 Momparison tests [26], tMo samples
Pa), probablywas not unif
ons and EDX a
cal methodasses on Co
analysis procrysta
yapatite and Cefficiency evctrochemicats and we
masses electe stable in ysiological N
uoridated phosp
surements on of contac
100 Equiplace an e
r on sampleresent the av
d CoCrMo than 950 andhydrofob chaoCrMo withng the averagt puts in eer. The hydroility and for y is higher.
Adherence used for M
c materials wby applying as expressed
alue for coaparing with ng to ASTer and indng layer. studied coo ASTM D4e adhesion tDeFelsko , Ug adhesion wst pullout streuired for decoating. This related to t
oxy resin adhch-907 Hysas allowed torature. Tests
MPa. he literaturethe obtaineds are modesy due to the form.
analysis cond for deoCrMo is effoves the elline phCaHPO4 as wvaluation wal and
found thatrodeposited both electro
NaCl solution
phate masses on
ct angle wapment. Th
equal volumes surface.Iverage from
the contacd the averagaracter. h fluoridatege for contacevidence thophilicity is ismall contac
tests Microhardneswas performea load of 20 by using th
ated CoCrMthe standar
TM F75, thicates bette
oatings wa4511 with type PosiTesUSA). was evaluateength (pull-o
etach a dolldolly (10mm
the sample'hesive in tw
sol Loctite o strength fos were mad
e data of thd values fost (2.79 MP
fact that th
nfirm that theposition oficient. X-Raexistence ohases owell. as quantifie
mechanicaat fluoridate
on CoCrMolyte artificia
n respectively
n
as e e n 5
ct e
d ct e n ct
ss d 0 e
o rd e
er
as a st
d ff ly m 's
wo /
or e
e or a e
e of ay of of
d al d o al y.
D.Covaciu Romoni, G. Voicu, D. Ioni, I. Demetrescu / Stabilitatea maselor fosfatice fluorurate pe aliaje de CoCrMo 291
The mechanical properties meaning microhardness and adherence are better for nanosized coatings as well.
Acknowledgements
The work has been funded by the Sectoral Operational Programme Human Resources Development 2007-2013 of the Ministry of European Funds through the Financial Agreement POSDRU/ 159/1.5/S/134198.
REFERENCES
1. N. Maruyama, H. Kawasaki , A. Yamamoto , S. Hiromoto, H.
Imai, and T. Hanawa, Friction-Wear properties of Nickel-Free Co-Cr-Mo alloy in a simulated body fluid, Materials Transactions, 2005, 46 (7), 1588.
2. G. Manivasagam, D. Dhinasekaran, and A. Rajamanickam, Biomedical Implants: Corrosion and its Prevention - A Review, Recent Patents on Corrosion Science, 2010, 2, 40.
3. D. Ioni, I. Man, and I. Demetrescu, The behaviour of electrochemical deposition of phosphate coating on CoCr bio alloys, Key Engineering Materials, 2007, 330-332, 545.
4. Arnold H. Deutchman, Robert J. Partyka, and Robert J. Borel, Orthopaedic implants having self-lubricated articulating surfaces designed to reduce wear, corrosion, and ion leaching, US Patent No 20080221683, September, 11, 2008.
5. D. Portan, D. Ioni, and I. Demetrescu, Monitoring TiO2 nanotubes elaboration condition, a way for obtaining various characteristics of nanostructures, Key Engineering Materials, 2009, 415, 9.
6. ASTM F75-12 Standard Specification for Cobalt- 28 Chromium-6 Molybdenum Alloy Castings and Casting Alloy for Surgical Implants (UNS R30075), doi:10.1520/F0075-12.
7. G. Totea, I.V. Branzoi, and D. Ioni, Lactic acid influence on the electrochemical behaviour of stainless steel and CoCrMo alloy in human serum, Revista de Chimie, 2013, 64 (6) ,625.
8. M. Mindroiu , E. Cicek, F. Miculescu, and I. Demetrescu, The influence of thermal oxidation treatment on the electrochemical stability of TiAlV and TiAlFe alloys and their potential application as biomaterials, Revista de Chimie, 2007,58 (9), 858.
9. P. Huang, and H.F. Lopez, Strain induced epsilon-martensite in a Co-Cr-Mo alloy: grain size effects, Materials Letters, 1999, 39 (4), 244.
10. I. Miloev, and H.-H. Strehblow, The composition of the surface passive film formed on CoCrMo alloy in simulated physiological solution, Electrochimica Acta, 2003, 48 (19), 2767.
11. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans, Surgical Implants and other Foreign Bodies (International Agency for Research on Cancer, World Health Ornization, 74, Lyon, France, 1999.
12. D. Ioni, C. Ungureanu,and I. Demetrescu, Electrochemical and Antibacterial Performance of CoCrMo Alloy Coated with Hydroxyapatite or Silver Nanoparticles, Journal of Materials Engineering and Performance, 2013, 22 (11), 3584.
13. E.Dinu, M.Brsan,C.Ghiulic, G.Voicu, and E. Andronescu, Synthesis and characterization of hydroxyapatite obtained by sol gel method, Romanian Journal of Materials, 2013, 43 (1), 55.
14. V. Stanic, Dj. Janackovic, S. Dimitrijevic, S. B. Tanaskovic, M. Mitric, M. S. Pavlovic, A. Krstic, D. Jovanovic, and S. Raicevic, Synthesis of antimicrobial monophase silver-doped hydroxyapatite nanopowders for bone tissue engineering, Applied Surface Science, 2011, 257 (9), 4510.
15. S. Overgaard, K. Soballe, K. Josephsen, E.S. Hansen, and C. Bunger, Role of different loading conditions on resorption of hydroxyapatite coating evaluated by histomorphometric and stereological methods, Journal of Orthopaedic Research, 1996, 14 (6), 888.
16. F.Bir, H. Khireddine, A. Touati, D. Sidane, S. Yala, and H. Oudadesse, Electrochemical depositions of fluorohydroxyapatite doped by Cu2+, Zn2+, Ag+ on stainless steel substrates, Applied Surface Science, 2012, 258 (18), 7021.
17. J. Wang, Y. Chao, Q. Wan, Z. Zhu, and H. Yu, Fluoridated hydroxyapatite coatings on titanium obtained by electrochemical deposition, Acta Biomaterialia, 2009, 5 (5) ,1798.
18. G. Totea, D. Ioni, R. M. Katunar, S. Cere, and I. Demetrescu Elaboration and characterization of the electrodeposited phosphates masses doped with various ions on stainless steel, Digest Journal of Nanomaterials and Biostructures, 2014, 9 (2), 575.
19. C. Wen, S. Guan, L. Peng, C. Ren, X. Wang, and Z. Hu, Characterization and degradation behavior of AZ31 alloy surface modified by bone-like hydroxyapatite for implant applications, Applied Surface Science, 2009, 255 (13-14), 6433.
20. N. Dumelie, H. Benhayoune, C. Rousse-Bertrand, S. Bouthors, A. Perchet, L. Wortham. J. Douglade, D. Laurent-Maquin, and G. Balossier, Characterization of electrodeposited calcium phosphate coatings by complementary scanning electron microscopy and scanning-transmission electron microscopy associated to X-ray microanalysis, Thin Solid Films, 2005, 492 (1-2), 131.
21. G. Pennel, G. Leroy, C. Rey, B. Sombret, J.P. Huvenne, and E. Bres, Infrared and Raman microspectrometry study of fluor-fluor-hydroxy and hydroxyl-apatite powders, Journal of Materials Science: Materials in Medicine, 1997, 8, 271.
22. M. Rouahi, E. Champion, P. Hardouin, and K. Anselme. Quantitative kinetic analysis of gene expression during human osteoblastic adhesion on orthopaedic materials, Biomaterials, 2006, 27 (14), 2829.
23. M.B. Schaffler, and D.B. Burr, Stiffness of compact bone: Effects of porosity and density. Journal of Biomechanics, 1988, 21 (1), 13
24. K. S. Katti, Biomaterials in total joint replacement, Colloids and Surfaces B: Biointerfaces, 2004, 39 (3), 133.
25. H.-G. Kim, S.-H. Ahn, J.-G. Kim, S. J. Park, and K.-R. Lee, Corrosion performance of diamond-like carbon (DLC)-coated Ti alloy in the simulated body fluid environment, Diamond and Related. Materials, 2005, 14 (1), 35.
26. D-M. Liu, Q. Yang, and T. Troczynski, Sol-gel hydroxyapatite coatings on stainless steel, Biomaterials, 2002, 23 (3), 691.
***************************************************************************************************************************
/ColorImageDict > /JPEG2000ColorACSImageDict > /JPEG2000ColorImageDict > /AntiAliasGrayImages false /DownsampleGrayImages true /GrayImageDownsampleType /Bicubic /GrayImageResolution 300 /GrayImageDepth -1 /GrayImageDownsampleThreshold 1.50000 /EncodeGrayImages true /GrayImageFilter /DCTEncode /AutoFilterGrayImages true /GrayImageAutoFilterStrategy /JPEG /GrayACSImageDict > /GrayImageDict > /JPEG2000GrayACSImageDict > /JPEG2000GrayImageDict > /AntiAliasMonoImages false /DownsampleMonoImages true /MonoImageDownsampleType /Bicubic /MonoImageResolution 1200 /MonoImageDepth -1 /MonoImageDownsampleThreshold 1.50000 /EncodeMonoImages true /MonoImageFilter /CCITTFaxEncode /MonoImageDict > /AllowPSXObjects false /PDFX1aCheck false /PDFX3Check false /PDFXCompliantPDFOnly false /PDFXNoTrimBoxError true /PDFXTrimBoxToMediaBoxOffset [ 0.00000 0.00000 0.00000 0.00000 ] /PDFXSetBleedBoxToMediaBox true /PDFXBleedBoxToTrimBoxOffset [ 0.00000 0.00000 0.00000 0.00000 ] /PDFXOutputIntentProfile () /PDFXOutputCondition () /PDFXRegistryName (http://www.color.org) /PDFXTrapped /Unknown
/Description >>> setdistillerparams> setpagedevice