Modification of Titanium surfaces by Nano-structure creation and

Laser texturing for enhanced osseointegration of implants.

Karthik Narayan(12BEM0070)
Yesh A Shah (12BME0288)
Project ID : 248

Prof.
Prof. Geetha
Geetha
Manivasagam
Manivasagam
Project
Project Guide
Guide
School
School of
of Mechanical
Mechanical and
and Building
Building Sciences,
Sciences,
VIT
VIT University,
University, Vellore
Vellore -- 632014
632014

Contents
Introduction
Literature Review
Gaps in the Literature
Objective of the Project
Project description and goals
Technical Specifications
Design Approach and Details
Codes and Standards
Constraints and Alternatives
Schedules and Milestones of project
Project Demonstration
Summary
References

Explanation of unanswered questions from

Review 1

What is Molybdenum of a alloy of Titanium?

Ans: It is an empirical formula stated as
Mo Eq. = 1.00Mo + 0.28Nb + 0.22Ta + 0.67V + 1.6Cr + 2.9Fe - 1.00Al
All elemental compositions are in wt%.

Introduction
Titanium is widely used in biomedical applications such
as Tooth, joint implants[1].
Titanium is bio-compatible, but bio-inert [2].
Surface modifications could prove to be the game
changer [3-5].

Introduction
Ti-6Al-4V (TAV) a.ka. Work Horse is the most
commercially used alloy for implant fabrication
Vanadium is Cytotoxic, Aluminium is Neurotoxic[6-7].
Alternate alloys Ti-7.5Mo, Ti-13Nb-13Zr, etc.
Ti13Nb13Zr (Youngs mod: 64-83 Gpa) is mechanically
similar to bone mineral [8].

Literature Review
TAV toxicity and alternative of using Ti1313[9-10].
The -titanium alloys offer the highest strength to weight
ratios and appealing combinations of strength,
toughness, and fatigue resistance. [11]
Ti1313 (E= 64-83 GPa) similar to the bone (E=80GPa)
but + Ti6Al4V (E=105-120 Gpa)[11]

Literature Review
Surface modification techniques [3-5].
Advantageous of nanostructures on Ti implant interface
for enhanced cell adhesion[12].
Introduction of random micro roughness on biomaterial
surface improves osseointegration[13-14]

Gaps in the existing literature

Choice of Pattern
Use of Nanosecond over Femtosecond laser
Inconsistency in result of research conducted on
correlation between surface roughness and
hydrophilic/phobic nature.

Codes and Standards

ASTM F1713-08 : Standard Specification for Wrought Titanium-13Niobium13Zirconium Alloy for Surgical Implant Applications (UNS R58130)
ASTM B600 - 11 : Standard Guide for Descaling and Cleaning Titanium and
Titanium Alloy Surfaces
ISO 10993 - Biological Evaluation of Medical Devices, FDA 2005
ASTM D7334 - 08(2013) : Standard Practice for Surface Wettability of
Coatings, Substrates and Pigments by Advancing Contact Angle
Measurement

MEE 499 PROJECT WORK, School

of Mechanical and Building
Sciences

Objective of the Project

To alter surface characteristics, so as to enhance hydrophilic nature of the
surface.
To understand the impact of introducing micro and nano roughness on
Ti1313 samples on characteristics such as wettability, HAP precipitation and
roughness evaluation, etc.
Comparative studies to determine an efficient combination of different laser
patterns followed by anodization on Ti1313 samples.
Based on the results to choose a suitable principal orthopaedic or
orthodontic application of the preferred characterized sample

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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Project Description and Goals

Polish and clean samples.
Laser texture the samples employing a checkerboard pattern.
Optical imaging to determine the extent of Heat affected Zone.
Anodization of the patterned samples to grow nanotubes.
To analyse the surface roughness and wettability results
obtained from the modified samples and compare the results.
To determine extent of osseointergration by HAP precipitation
using SBF(Simulated body Fluid) immersion test.
MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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Progress of Project

Literature review

Project objective
& definition &
final process
parameters

Material
procurement

Wire-cut(EDM)
and sample
polishing

SEM imaging

Roughness
testing

Anodization

Laser texturing

Wettability test

SBF test on
samples

Analysis and
Report
completion

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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LASER Specifications

Laser specifications: Litron LPY674/G10 Nd-YAG solid

state laser Wavelength 532nm
Power- 150mJ
Pulse duration 10ns
Frequency 10Hz
Spot diameter - 800m
Overlap 0%.

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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Anodization Process
Electrolyte 95 % Ethylene glycol(99.9% Pure) + 3% Mili Q
water + 2% HF(40%v/v)
Cathode Ti13Nb13Zr alloy ( Textured or Plane polished)
Anode - Pt electrode
Voltage 60 V
Current 0.01 A
Duration 5hrs

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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Anodization Chemical Reactions

Formation of Titania layer
Ti2+ + 2H2O

TiO2 + 4H+ + 4e-

Dissolution of Titania in form of Flouride complex

TiO2 + 4H+ + 6F-

TiF62- + 2H2O

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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Anodization Setup
Images

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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Anodization Cleaning Protocols

Ti13Nb13Zr electrode
Pre cleaning protocol
Rinse alloy with
acetone

Ultrasonication
with acetone
(10min)

Rinse alloy with

isopropanol

Dry sample and

place in
anodization setup

Ultransonication
with isopropanol
(10min)

Rinse alloy with

double distilled
water

Post cleaning protocol

Unclip anodized
alloy into
isopropanol sol
(2min)

Rinse alloy with

isopropanol

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

Rinse alloy with

Mili Q water

Dry sample at
atmospheric
temperature

17

Anodization Cleaning Protocols

Pt Electrode
Pre cleaning protocol
Place Pt in Dil
HNO3 soln (2min)

Rinse Pt with Milli

Q water

Post cleaning protocol

Rinse Pt with
isopropanol

Immerse Pt in dil
HNO3 sol (2min)

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

Rinse Pt with
Isopropanol

Dry sample and

place in
anodization setup

Rinse Pt with Mili

Q water

Ultrasonication
with ethanol
(10min)

Ultrasonication
with acetone
(10min)

Dry sample in
atmospheric
tempertaure

18

Anodization Results
FE-SEM Images 4 Hours Anodising

Fig 1. Nanotube growth on Ti alloy surface (4hr

protocol)

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

Fig 2. Cluster of nanotubes formed on Ti alloy

surface (4hr protocol)

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Anodization Results
FE-SEM Images 5 Hours Anodising

Fig 3. Nanotube growth on Ti alloy surface (5hr

protocol)

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

Fig 4. Visible growth of individual nanotubes with

individual cell wall (5hr protocol)

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Constraints & Challenges Encountered

Black deposition on Pt electrode upon anodization
Pitting and galvanic corrosion of Ti13Nb13Zr alloy
upon anodization
Numerous trial and errors to obtain final anodization
parameters.
Excess leaching of textured surface during
anodization
Unable to measure nanotube length due to sample
orientation
MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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Constraints & challenges encountered

Images

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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Schedule and Milestones of the Project

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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Project Demonstration

Fig 1. Ultransonication with

isopropanol (10min)
MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

Fig 2. Litron LPY674/G10 (NdYAG

Laser)
24

Project Demonstration

Fig 3. 2mm laser pattern

Fig 5. Laser textured sample surface

Fig 4. 2.5mm laser pattern

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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Project Demonstration

Fig 6. 0% Overlap pulse

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

Fig 7. Unaffected Area

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Project Demonstration
Surface Roughness
Laser Textured(2mm) - Ra = 0.4696 m
Laser Textured(2.5mm) - Ra = 0.3415 m
Polished sample
- Ra = 0.080 m

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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Summary
Significant impact on surface roughness due to
Laser texturing.
Checkerboard pattern results in both rough and
smooth regions.
Laser texturing induces localised melting and
solidification.

MEE 499 PROJECT WORK, School of Mechanical and Building Sciences

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References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.

Ratner, B. D. Biomaterials Science : An Introduction to Materials in Medicine. 2nd ed.

Amsterdam ; Boston: Elsevier Academic Press, 2004.
Gyanesh Trivedi , vishv bhatt Nanotexturing on Ti alloys.School of mechanical and building sciences. 2015
Uchida, M., H. M. Kim, T. Kokubo, S. Fujibayashi, and T. Nakamura. "Structural Dependence of Apatite Formation on Titania Gels in a Simulated Body Fluid." J
Biomed Mater Res A 64, no. 1 (2003): 164-70
Ducheyne, P., W. Van Raemdonck, J. C. Heughebaert, and M. Heughebaert. "StructuralAnalysis of Hydroxyapatite Coatings on Titanium." Biomaterials 7, no. 2
(1986): 97-103.
Cooley, D. R., A. F. Van Dellen, J. O. Burgess, and A. S. Windeler. "The Advantages of Coated Titanium Implants Prepared by Radiofrequency Sputtering from
Hydroxyapatite." J Prosthet Dent 67, no. 1 (1992): 93-100.
Bondy, et. al. (2001). Differential effects of aluminum salts in neuronal and glial cell lines: Implications for. Neurotoxicology, 22, 63-71.
U KAMACHI MUDALI, et. al. (2003). Corrosion of bio implants. Sadhana Vol. 28, Parts 3 & 4,, 601-637.
Biofunctionalization of Ti13Nb13Zr alloy surface by plasma electrolytic oxidation. Part I ARTICLE in SURFACE AND COATINGS TECHNOLOGY AUGUST
2015
T.-D.T. Nguyen, I.-S. Park, M.-H.Lee, T.-S. Bae, Enhanced biocompatibility of a precalcified nanotubular TiO2 layer on Ti6Al7Nb alloy, Surf. Coat. Technol. 236
(2013) 127- 134.
K. Satoh, N. Ohtsu, S. Sato, K. Wagatsuma, Surface modification of Ti6Al4V alloy using an oxygen glow-discharge plasma to suppress the elution of toxic
elements into physiological environment, Surf. Coat. Technol. 232 (2013) 298-302.
S. Bauer, P. Schmuki, K. von der Mark, J. Park, Engineering biocompatible implant surfaces: Part I: Materials and surfaces, Progress in Materials Science, 58
(2013) 261-326.
Webster, T. J., R. W. Siegel, and R. Bizios. "Osteoblast Adhesion on Nanophase Ceramics." Biomaterials 20, no. 13 (1999): 1221-7.
Buser D, Schenk RK, Steinemann S, Fiorellini JP, Fox CH, Stich H. Influence of surface characteristics on bone integration of titanium implants. A
histomorphometric study in miniature pigs. Journal of Biomedical Materials Research 1991;25(7):889e902.
Sato N, Kubo K, Yamada M, Hori N, Suzuki T, Maeda H, et al. Osteoblast mechanoresponses on Ti with different surface topographies. Journal of Dental
Research 2009;88(9):812e6
Oh, S., C. Daraio, L. H. Chen, T. R. Pisanic, R. R. Finones, and S. Jin. "Significantly Accelerated Osteoblast Cell Growth on Aligned Tio2 Nanotubes." J Biomed
MaterRes A 78, no. 1 (2006): 97-103.

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