development and sem/eds characterisation of porous ...€¦ · development and sem/eds...

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WSN 80 (2017) 29-42 EISSN 2392-2192

Development and SEM/EDS characterisation of

porous coatings enriched in magnesium and copper obtained on titanium by PEO with ramp voltage

Krzysztof Rokosza, *Tadeusz Hryniewiczb, Kornel Pietrzakc, Łukasz Dudekd

Division of Bioengineering and Surface Electrochemistry, Department of Engineering and Informatics Systems, Faculty of Mechanical Engineering, Koszalin University of Technology,

Racławicka 15-17, PL 75-620 Koszalin, Poland

E-mail address: [email protected], [email protected],

[email protected], [email protected],

*Corresoponding author: [email protected]

ABSTRACT

In the present paper, the SEM and EDS results of porous and enriched in calcium and/or zinc

coatings, which were obtained during 3-minute treatments by Plasma Electrolytic Oxidation/ Micro

Arc Oxidation processes on CP Titanium Grade 2 at ramp potentials (liner polarization) from 0 up to

650 VDC in electrolytes containing 500 g Mg(NO3)2∙6H2O and/or 500 g Cu(NO3)2∙3H2O in 1 L H3PO4,

are reported. It was found that the obtained coatings, dependent on the PEO process conditions, have

pores with different shapes and diameters. The Mg/P and Cu/P ratios by atomic concentration are the

same and equal to 0.09±0.01 (by wt %) | 0.11±0.01 (by at%) and/or 0.40±0.08 (by wt %) | 0.19±0.04

(by at%), respectively. That may testify the hydroxyapatite-like structures of Mg-Ti-PO43–

and/or Cu-

Ti-PO43–

have been identified to occur.

Keywords: Plasma Electrolytic Oxidation (PEO), Micro Arc Oxidation (MAO), CP Titanium Grade 2,

calcium nitrate Mg(NO3)2∙6H2O, zinc nitrate Ca(NO3)2∙3H2O, ramp voltage, linear polarization

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World Scientific News 80 (2017) 29-42

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1. INTRODUCTION

Titanium and its alloys are key biomaterials used for medical devices like orthopaedic

and dental implants. This is because titanium holds a unique combination of surface and bulk

properties, which includes high surface TiO2 stability, Young’s modulus closer to that of

human bone and high specific strength [1-3]. The surface topography and composition of

surface layer play important roles on guiding the bone integration between the implant surface

and cells. The manufacturing process can improve the corrosion resistance, wear behavior and

affect various other functional properties. The surface modification of titanium and its alloys

has increased the number of potential applications of these materials in different fields and

industries, such as aerospace, marine, chemical industry, automotive and biomaterials [3-5].

Metals have poor biocompatibility because metals or alloys tend to release metal ions

that cause pathological changes in cells, alter genes, and form cancer cells. An appropriate

surface treatment is critically required for the biomedical implants such as dental implants,

artificial hips and knee components to modify and improve their bioactivity and mechanical

properties. To improve the chemical features and biocompatible abilities, numerous surface

modification techniques have been progressively developed and applied to different metals,

alloys or ceramics for biomedical purposes. Moreover, enhancing the corrosion resistance of

titanium and its alloys are crucial to increasing the biocompatibility. The life quality of

patients could be improved by using biomaterials that may interact with biological systems

having minimal flaws and long service. Therefore, thanks to improved properties, they may be

used for manufacturing human body implants [3-6].

This paper is a continuation of the works on fabrication and surface characterization of

porous coatings which were obtained on Titanium by Plasma Electrolytic Oxidation process

in electrolytes containing selected nitrates, what was first related partly in reference [7]. It has

to be pointed out that with use of electrochemical methods it may be possible to obtain both

nano-layers as well as micro-layers (micro-coatings).

Therefore a standard electropolishing (EP) [8-11], magnetoelectropolishing (MEP) [12-

21] or high-current density electropolishing (HDEP) [22-24] may be used to form nano-layers

on metals and alloys, whereas the micro coatings may be obtained by the Plasma Electrolytic

Oxidation (PEO) also known as Micro Arc Oxidation (MAO) [25-44]. Among the different

surface modification techniques (CVD, PVD, ion implantation, electroplating, plasma

nitriding, thermal oxidation), anodic oxidation, especially the plasma electrolytic oxidation

(PEO) process has become increasingly important since it has advantages over other methods

of surface modification [1-6, 25-44]. The PEO process creates porous coatings on titanium [2,

7, 25-33] and its alloys [2-6, 34-39], which may be enriched in bactericidal copper [45-55] as

well as in magnesium, which may accelerate the healing of wounds [56-57].

The aim of this paper is the development and SEM/EDS characterisation of PEO porous

coatings, enriched in magnesium and copper, obtained on titanium. The three primary factors

of biocompatibility on the cellular level are genotoxicity, carcinogenicity, and cytotoxicity.

The pore size and surface roughness formed by PEO play an important role in the adsorption

of proteins, adhesion of cells, and the rate of osseointegration.


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2. METHOD

The samples of CP Titanium Grade 2 with dimensions 10 10 2 mm were treated by

Plasma Electrolytic Oxidation (Micro Arc Oxidation) for the surface studies. The plasma

electrolytic oxidation (PEO) was performed at the ramp voltages from 0 up to 650 VDC. For

the studies, the electrolyte based on orthophosphoric acid H3PO4 with 500 g/L of calcium

nitrate Mg(NO3)2∙6H2O or copper nitrate Cu(NO3)2∙3H2O was used. For each run, the

electrolytic cell made of glass was used, containing up to 500 ml of the electrolyte.

Scanning Electron Microscope (SEM) FEI Quanta 650 FEG equipped with Energy-

Dispersive X-ray Spectroscopy (EDS) for surface analysis was used. The microscope

operated under the following conditions: voltage 15 kV, current 8-10 nA, beam diameter

6 μm, decreased vacuum in the chamber with the pressure of 50 Pa. The identification of

spectral lines was performed by means of a spectral decomposition using the holographic

peak deconvolution function.

3. RESULTS AND DISCUSSION

In Figures 1-3, the SEM pictures of coating formed on Titanium after PEO treatment at

ramp voltages from 0 till 650 VDC (linear polarization) in electrolyte containing of 500 g

Mg(NO3)2∙6H2O in 1 L H3PO4, are presented. The EDS spectrum of obtained coating is

shown in Figure 4. These EDS peaks of phosphorus, titanium and magnesium show that

formed PEO coating is built mainly of phosphorus-titanium-magnesium compounds, what

may suggest the existence of hydroxyapatite-like structure enriched in magnesium, which

replaced the calcium in that structure.

In the PEO coating, apart from the titanium (40.3±1.1 wt% | 29.9±0.8 at%), which is a

substrate, and which signal may partly come from matrix, phosphorus (54.9±0.7 wt% |

63.1±0.6 at%) and magnesium (4.8±0.4 wt% | 7.0±0.5 at%) were also recorded, what is

presented in Figure 5. In addition, the median and range of results were found out. Thus the

medians of magnesium, phosphorus and titanium were equal to 4.8 wt% (6.7 at%), 55 wt%

(63.1 at%) and 40.1 wt% (29.7 at%), respectively. The highest range of obtained results were

observed for titanium (2.9 wt%|2.2 at%), while the smallest one for magnesium (0.9 wt%|1.3

at %). In Figures 6-8, the SEM pictures of coating formed on Titanium after PEO treatment at

ramp voltages from 0 till 650 VDC (linear polarization) in electrolyte containing of 500 g

Cu(NO3)2∙3H2O in 1 L H3PO4, are presented. The EDS spectrum of obtained coating is shown

in Figure 9. These EDS peaks of phosphorus, titanium and magnesium show that formed PEO

coating is built mainly of phosphorus-titanium-copper compounds, what may suggest the

existence of hydroxyapatite-like structure enriched in copper, which replaced the calcium in

that structure.

In the PEO coating behind the titanium (52.3±4.9 wt% | 45.4±4.9 at%), which is a

substrate, and which signal may partly come from matrix, phosphorus (34.2±4.0 wt% |

45.7±4.5 at%) and copper (13.5±2.2 wt% | 8.8±1.4 at%) were also recorded, what is presented

in Figure 10. Thus the medians of copper, phosphorus and titanium were equal to 13.8 wt%

(8.9 at%), 33.4 wt% (44.7 at%) and 53.3 wt% (46.7 at%), respectively. The highest range of

obtained results were observed for titanium (11.6 wt%|11.1 at%), while the lowest one for

copper (4.7 wt%|3.3 at%).


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Fig. 1. SEM picture of coating formed on Titanium after PEO treatment at ramp voltages

from 0 till 650 VDC in electrolyte containing of 500 g Mg(NO3)2∙6H2O in 1 L H3PO4.

Magnification 2 500 times

Fig. 2. SEM picture of coating formed on Titanium after PEO treatment at voltages from 0 till

650 VDC in electrolyte containing of 500 g Mg(NO3)2∙6H2O in 1 L H3PO4.



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650 VDC in electrolyte containing of 500 g Mg (NO3)2∙6H2O in 1 L H3PO4.



650 VDC in electrolyte containing of 500 g Mg(NO3)2∙6H2O in 1 L H3PO4


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Fig. 5. Comparison of mean values of EDS results of coating formed on Titanium after PEO

treatment at voltages from 0 till 650 VDC in electrolyte containing

of 500 g Mg(NO3)2∙6H2O in 1 L H3PO4


650 VDC in electrolyte containing of 500 g Cu(NO3)2∙3H2O in 1 L H3PO4.



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Fig. 9. EDS result of coating formed on Titanium after PEO treatment at voltages from 0 till

650 VDC in electrolyte containing of 500 g Cu(NO3)2∙3H2O in 1 L H3PO4

Fig. 10. Comparison of mean values of EDS results of coating formed on Titanium after PEO

treatment at voltages from 0 till 650 VDC in electrolyte containing of 500 g Cu(NO3)2∙3H2O

in 1 L H3PO4


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To characterize the metal surface after PEO treatment, the two ratios (Figure 11), i.e.

Mg/P and Cu/P, which were equal to 0.09±0.01 (by wt%) | 0.11±0.01 (by at%) and 0.40±0.08

(by wt%) | 0.19±0.04 (by at%), were calculated. Based on the experimental results it may be

concluded that in hydroxyapatite-like structures obtained, there is about two times more atoms

of copper than those ones of magnesium forming a similar structure.

Fig. 11. Mg/P and Cu/P ratios of EDS results of coating formed on Titanium after PEO

treatment at voltages from 0 till 650 VDC in electrolyte containing of 500 g MgNO3)2∙6H2O or

CuNO3)2∙3H2O in 1 L H3PO4

4. CONCLUSIONS

At this stage of the PEO studies, the following conclusions may be drawn:

during the PEO process with use of a liner polarization (ramp voltage) from 0 till 650

VDC, it is possible to obtain the porous surface enriched in calcium and phosphorus in

electrolyte containing 500 g Mg(NO3)2∙6H2O and/or 500 g Cu(NO3)2∙3H2O in 1 L

H3PO4

the Mg/P and Cu/P ratios by atomic concentration are the same and equal to 0.09±0.01

(by wt %) | 0.11±0.01 (by at %) and 0.40±0.08 (by wt %) | 0.19±0.04 (by at %),

respectively; such a composition of porous coating suggests the hydroxyapatite-like

structure consisting with Mg-Ti-PO43–

and/or Cu-Ti-PO43–

.


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This way it is proved the PEO has been becoming a promising technique for surface

modifications.

Acknowledgements

This work was supported by subsidizing by Grant OPUS 11 of National Science Centre, Poland, with

registration number 2016/21/B/ST8/01952, titled "Development of models of new porous coatings obtained on

titanium by Plasma Electrolytic Oxidation in electrolytes containing phosphoric acid with addition of calcium,

magnesium, copper and zinc nitrates".

Assoc. Prof. Jan Valíček and Dr Dalibor Matýsek from Vysoká škola báňská - Technická univerzita Ostrava -

VŠB-TUO, Czech Republic, are given thanks for providing access to the SEM/EDS apparatus allowing to

perform the studies.

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( Received 10 June 2017; accepted 02 July 2017 )

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