Effect of different surface treatments on bioactivity of porous titanium implants

doi:10.1016/j.jmst.2018.10.004

Abstract

Abstract:

The work aims to characterize the structure and to evaluate in vitro the effect of different surface treatments on the bioactivity of medical grade Ti6Al7Nb alloy implants manufactured by selective laser melting. In order to improve the bioactivity of these samples, they were subjected to heat treatment, chemical treatment, and impregnation with bioactive materials. To evaluate the apatite forming ability, the samples were immersed in simulated body fluid solution) and characterized before and after immersion by scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The composition and the texture of the surfaces after the applied treatments have a selective effect on apatite layer development on the surface of samples.

Key words: Ti6Al7Nb alloy, Laser processing, Composite materials, Surface properties, Bioactivity

M. Todea, A. Vulpoi, C. Popa, P. Berce, S. Simon. Effect of different surface treatments on bioactivity of porous titanium implants[J]. J. Mater. Sci. Technol., 2019, 35(3): 418-426.

Figures/Tables 23

Fig. 1. SEM images of manufactured Ti6Al7Nb control implants at different magnificence (scale bars: 500?μm of left image, 100?μm of right image).

Fig. 2. SEM images of Ti6Al7Nb implants surfaces for (a) control, (b) heat treated, (c) chemically treated, (d) TiO2-SiO2 infiltrated, (e) CaPpH=4.5 infiltrated and (f) CaPpH=10 infiltrated (scale bars: 5?μm).

Table 1 Chemical composition of Ti6Al7Nb samples obtained from EDX analysis.

Elements → Sample↓	O	Ti	Al	Nb	Si	Ca	P	Ca/P
Theoretical composition of Ti6Al7Nb		85.8	10.4	3.8
SLM derived control sample	10	78.3	9	2.7
Thermally treated	21.1	65.1	11.1	2.7
Chemically treated	38.9	51.6	7.1	2.4
Infiltrated with SiO₂-TiO₂	39.7	48.3	7.7	2.1	2.3	-	-
Infiltrated with CaP_pH=4.5	51.9	24	3.1	1	-	13.1	6.9	1.96
Infiltrated with CaP_pH=10	42.3	35.8	4.2	1.4	-	8.8	7.6	1.16

Fig. 3. XRD patterns of the titanium samples obtained after different surface treatments.

Table 2 Elemental composition (at.%) of titanium alloy samples obtained from XPS analysis, wherein the carbon content was neglected.

Samples	O	Ti	Al	Nb	Na	Cl	Si	Ca	P	Ca/P
Theoretical composition of Ti6Al7Nb		85.8	10.4	3.8
SLM derived control sample	63.9	13.6	22.1	0.4
Thermally treated	67.9	17.0	14.8	0.3
Chemically treated	67.2	23.5	2.0	1.3	5.6	0.4
Infiltrated with SiO₂-TiO₂	66.4	14.0	8.1	0.5			11
Infiltrated with CaP_pH=4.5	59.5	3.0	1.9	0.4				23.3	11.9	1.96
Infiltrated with CaP_pH=10	57.7	4.2	6.8	0.5				16.9	13.9	1.22

Fig. 4. Survey spectra of the titanium samples with different surface treatments.

Fig. 5. C 1s high-resolution spectra of the titanium samples with different surface treatments.

Fig. 6. Ti 2p high-resolution spectra of the titanium samples with different surface treatments.

Fig. 7. Al 2p high-resolution spectra of the titanium samples with different surface treatments.

Fig. 8. Nb 3d high-resolution spectra of the titanium samples with different surface treatments.

Fig. 9. High resolution O 1s spectra of the titanium samples with different surface treatments.

Table 3 Fractions (f) of the components with different binding energies (B.E.) obtained by deconvolution of O 1s core level spectra.

Sample	Component (1)		Component (2)		Component (3)		Component (4)
Sample	B.E. (eV)	f (%)	B.E. (eV)	f (%)	B.E. (eV)	f (%)	B.E. (eV)	f (%)
Control	530.1	60.0	531.5	25.2	532.5	14.8
Heat treated	529.6	65.3	531.0	21.4	532.1	13.3
Chemically treated	529.5	35.4	531.3	42.4	532.2	11.6	533.4	10.6
Infiltrated with SiO₂-TiO₂	529.3	56.0	531.2	29.0	532.3	15.0
Infiltrated with CaP_pH=4.5	529.5	29.7	531.2	58.0	532.4	12.3
Infiltrated with CaP_pH=10	530.2	25.1	531.3	60.3	532.4	14.6

Fig. 10. Ca 2p high-resolution spectra of titanium samples after infiltration with calcium phosphate CaPpH=4.5 and CaPpH=10.

Fig. 11. P 2p high resolution spectra of titanium samples after infiltration with calcium phosphate CaPpH=4.5 and CaPpH=10.

Fig. 12. Si 2p high resolution spectrum of the sample infiltrated with SiO2-TiO2 sol-gel.

Fig. 13. SEM images of Ti6Al7Nb implants surfaces after 14 days of SBF immersion for (a) control, (b) heat treated, (c) chemically treated, (d) TiO2-SiO2 infiltrated, (e) CaPpH=4.5 infiltrated and (f) CaPpH=10 infiltrated (scale bars of (a-c, e, f): 5?μm, scale bar of (d): 20?μm).

Table 4 Chemical composition of Ti6Al7Nb samples obtained from EDX analysis after 14 days immersion in SBF.

Elements → Sample↓	O	Ti	Al	Nb	Si	Ca	P	Cl	Na	Mg	Ca/P
SLM derived control sample	10.3	72.5	13.3	3.4		0.1	0.4				0.25
Thermally treated	13.1	69.4	13.8	3.6		0.02	0.1				0.2
Chemically treated	33.1	57.8	3.9	1.5		0.7	0.4	0.7	1.9		1.75
Infiltrated with SiO₂-TiO₂	39	48.1	3.2	1.3	3.2	3.4	0.3	0.4	1.1		11.33
Infiltrated with CaP_pH=4.5	45.3	37.6	5.7	1.8	-	3.1	2.7	0.8	3.0		1.15
Infiltrated with CaP_pH=10	50.7	11.3	0.6	0.2	-	19.4	14.8	0.7	1.3	1.0	1.31

Table 5 Elemental composition (at %) of titanium alloy samples from XPS analysis obtained after 14 days immersion in SBF, wherein the carbon content was neglected.

Elements → Sample↓	O	Ti	Al	Nb	Si	Ca	P	Ca/P
SLM derived control sample	62.6	21.3	8.9	0.6	-	2.6	4.0	0.65
Thermally treated	66.5	18.1	7.4	0.7	-	4.7	2.6	1.81
Chemically treated	69.2	20.8	1.2	1.3	-	4.0	3.5	1.14
Infiltrated with SiO₂-TiO₂	65.7	11.5	2.4	0.2	11.2	4.6	4.4	1.05
Infiltrated with CaP_pH=4.5	60.8	3.6	2.1	0.3	-	20.5	12.7	1.61
Infiltrated with CaP_pH=10	58.2	2.6	2.4	0.3	-	19.7	16.8	1.17

Fig. 14. XPS survey spectra recorded after samples immersion for 14 days in SBF.

Fig. 15. High resolution Ca 2p XPS spectra recorded after samples immersion for 14 days in SBF.

Fig. 16. High resolution P 2p XPS spectra recorded after samples immersion for 14 days in SBF.

Fig. 17. High resolution O 1s XPS spectra recorded after samples immersion for 14 days in SBF.

Table 6 Fractions (f) of the components with different binding energies (B.E.) obtained by deconvolution of O 1s core level spectra recorded after samples immersion for 14 days in SBF.

Sample	Component (1)		Component (2)		Component (3)
Sample	B.E. (eV)	f (%)	B.E. (eV)	f (%)	B.E. (eV)	f (%)
Control	529.8	48.3	531.4	27.1	532.6	24.6
Heat treated	529.7	65.5	531.2	21.6	532.6	12.9
Chemically treated	530	69.8	531.3	18.4	532.6	11.8
Infiltrated with SiO₂-TiO₂	529.9	44	531.3	31.8	532.6	24.2
Infiltrated with CaP_pH=4.5	529.5	22.3	531.3	48	532.6	29.7
Infiltrated with CaP_pH=10	529.6	27.2	531.3	57.5	532.6	15.3

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