Titanium Nitride–Hydroxyapatite Coating on PEEK

for Dental Implants by co-axis Target Magnetron Sputtering

D. Boonyawan Chiang Mai University

Outline

• Titanium nitride and hydroxyapatite composite coatings on polyether-ether-ketone (PEEK) by reactive pulsed dc magnetron sputtering system.

• Characterize the proper

plasma conditions for deposition of titanium nitride-hydroxyapatite (TiN-HA) film.

• Some results and conclusions.

Compendium, Jul/Aug 2012, Volume 33, Issue 7

Ambitiousness

• Deposite TiN-HA on dental implant materials as PEEK by magnetron sputtering, which can provide desired film-thickness and good adherence.

• Titanium-composite

implants showed significantly higher bone-implant contact (BIC) rates.

Int. J. Mol. Sci. 2014, 15(4), 5426-5445

System setup

• Base Pressure

7.6 e-6 Torr

• Oper. Pressure

6.1 e-3 Torr

• Sputter time

30 min

Ti-HA & Plasma

HA = Ca5(PO4)3(OH)

Ti HA

Plasma species : N2 : OP

0.3 0.6 0.9

0

5000

10000

Inte

ns

ity

(a

.u.)

N intent (sccm)

PI 469

CaI 307.1

N2 391.4

Ti 451

Ar 750.4

2 4 6 8 100

2000

4000

6000

8000

10000

Inte

ns

ity

(a

.u.)

pressure (mTorr)

N2 391.4

Ti 451

Ar 750.4

N2 357.7

Ar 696.5

Ti 363

Electron temperature

3 6 9

4

6

8

10

Ele

ctr

on

te

mp

era

ture

(e

V)

Pressure (mTorr)

N0.01 Asym90.5.30

N0.03 Asym90.5.30

N0.03 Asym75.5.30

0.2 0.4 0.6 0.8 1.0

4

8

12

Ele

ctr

on

te

mp

era

ture

(e

V)

N content (sccm)

3 mTorr

5 mTorr

7 mTorr

10 mTorr

Results: Ti-HA film

PEEK

Ti-HA PEEK

Contact angle

• PEEK • Ti-HA on PEEK

AFM analysis

• Thickness: 20 nm, • Roughness: 0.1 nm, • Young’s modulus: 60 GPa.

The XPS-1

1200 1000 800 600 400 200 0

0

20000

40000

60000

80000

100000

120000

140000

160000

180000

200000

P 2

pC 1

sCa

2p

Ti 2

p

O 1s

Cr

2p

Inte

nsity

( cp

s )

Binding Energy ( eV )

Si

Polymer

Fe 2

p

O 1s

530.1 : TiO2

531.3 : P=O- group

532.8 : -OH group

Ca 2p

347.2 : Ca 2p3/2

350.7 : Ca 2p1/2

520 530 540 550

531.3

Inte

ns

ity

(c

ps

)

Binding Energy ( eV )

Polymer

Si530.1

343 350 357

350.7

Inte

ns

ity

(c

ps

)

Binding Energy ( eV )

Polymer

Si347.2

The XPS-2

P 2p

133.9 : was deconvoluted into 2 peaks for p1/2 and p3/2 levels

Ti 2p

458.7 : Ti 2p3/2 in TiO2

464.4 : Ti 2p1/2

126 133 140

1600

2400

3200

4000

Inte

ns

ity

(c

ps

)

Binding Energy ( eV )

Polymer

Si

133.9

450 460 470

Inte

ns

ity

(c

ps

)

Binding Energy ( eV )

Polymer

Si

458.7

464.4

The XPS-3

Molar conc. ratios of Ti-HA film

PEEK Si ideal HAp:

Ca10(PO4)6(OH)2

Ca / P O 530 / P Ti / O Ti / N

2.42 11.6 0.05

N not detect

3.78 18.4 0.05

N not detect

1.67 4.33

- -

Bio. analysis: MTT assay

%proliferation rate result of the synthesized HA-Ti films.

Conclusions

• The setup was optimized for Ti-HA films on PEEK.

• Ti-HA composite film found to reduce the surface contact angle to as low as 10°.

• Nano-pore or nano-roughness is a goal for bioactive PEEK implants.

Acknowledgement

• Thanks to P. Waruriya, P. Premphet, M. Prasoetsri and K. Leksakul for their devoted efforts and all contributions in this work.

• DB also thank CoE in Materials Science, Chiang Mai University for the project fund.

Thank you Q&C