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ABSTRACT: Often hard implants undergo detachment from the host tissue
due to inadequate biocompatibility and poor osteointegration. Changing surface
chemistry and physical topography of the surface influences biocompatibility.
At present, the understanding of biocompatibility of both virgin and modified
surfaces of bioimplant materials is limited and a great deal of research is being
dedicated to this aspect. In view of this, the current review casts new light on
research related to the surface modification of biomaterials, especially materials
for prosthetic applications. A brief overview of the major surface modification
techniques has been presented, followed by an in-depth discussion on laser
surface modifications that have been explored so far along with those that hold
tremendous potential for bioimplant applications.
INTRODUCTION
Implant Biomaterials
Though gold has been used as a dental implant for ages, biomaterials
evolved dramatically during the last century. These implant biomater-
ials can be broadly classified into metallic, ceramic, polymeric, and
composite systems. Metallic biomaterials consisting of various steel
Partially
Alumina Dense Stabilized
Property (99.8% by wt) Hydroxyapatite Zirconia
Density (g/cm3) >3.93 3.156 6.1
Hardness (VHN) 2300 500–800 1300
Fracture toughness (MPa m1/2) 5–6 1.0 9.0
Compressive strength (MPa) 4500 100–900 2000
Young’s modulus (GPa) 380 70–120 290
Interface
Adsorbed
biomolecules
Extracellular
and water
fluid
Cell
Biomaterial
SURFACE ENGINEERING
Chemical Treatments
X Si X + XOH
R
X
X Si X
O O O O O
H H H O H H
(a) (b)
R R
X = leaving group X Si O Si O
O
R = functional group O H O
(c)
Figure 2. A typical silane surface modification technique: (a) hydroxylated surface is
immersed in a solution containing a silane; (b) the silane attaches to the surface by
releasing one of its groups; and (c) further reaction results in a silane network [4].
Self-assembled Monolayers
Microcontact Printing
Coatings
Figure 4. The ALP activity of human osteosarcoma cells on pure Ti, hydroxyapatite (HA),
fluorhydroxyapatite (FHA), and a control culture dish sample after 10 days of culturing.
25FHA, 50FHA, and 75FHA correspond to the specimens with FHA/HA ([F]/[OH]) ratios
of 0, 0.25, 0.5, and 0.75, respectively [23].
Figure 8. Raman spectra of (a) PO4 band and (b) OH band at three locations along the
thickness of as-sprayed coating: A – outer layer; B – midlayer; and C – inner layer [26].
Figure 9. (a) Scanning electron micrographs of HA coating cross section showing the
ribbon-like region surrounded by the relatively smooth area and (b) high-magnification
scanning electron micrograph revealing the granular ribbon-like region [28].
Texturing
Figure 10. ToF-SIMS maps of Ti–HA coatings at 40 mm, the Ti substrate is at the
left-hand side.
Laser-assisted Coatings
There exist many classes of lasers, CO2, YAG, excimer, dye, argon-ion,
diode, etc., each of which has its own unique properties and suitable
applications [35]. The factors that primarily influence laser–material
interaction are the wavelength of the beam, energy and pulse length,
properties of target material like its melting point, optical reflectivity,
and thermal diffusivity [35]. Another process referred to as ‘photo-
ablation,’ is found in organic materials when exposed to ultraviolet
radiation from sources like excimer and harmonic YAG lasers.
Zeng et al. have observed that by modulating the pressure and
composition of ambient gas, a Ca/P ratio close to initial HA target was
achieved [68]. It was observed that the presence of H2O enhanced the
crystallinity of the coating. The setup used by them for a typical pulsed
laser deposition technique is schematically shown in Figure 11. A pulsed
laser deposition system consists of three essential parts – substrate,
solid target, and laser source. The pulses from the laser evaporate the
material from the target which are then condensed on the substrate.
Lasers like Nd : YAG and excimer were successfully used in pulsed
laser deposition of HA, as reported by Clèries et al. [69,70], who showed
that the morphologies of the coatings deposited on Ti–6Al–4V by
excimer and Nd : YAG lasers were different. If the coatings obtained
from third and fourth harmonics Nd : YAG laser were granular,
the excimer laser deposited coatings appeared columnar in nature as
shown in Figure 12.
Bioresorbable polymers degrade, whilst avoiding the formation of
toxic products and thus can be used as bone substitutes. However, these
materials are not bioactive and therefore can be coated with bioactive
Figure 11. Schematic of a typical pulsed laser deposition technique [68]. Laser pulses
evaporate the target materials which later condense on the substrate forming a thin film
of the target material.
Figure 12. Scanning electron micrographs showing the cross section of HA coating on
Ti–6Al–4V deposited by (a) excimer laser and (b) Nd YAG laser [69].
Figure 13. Ca/P ratio as function of laser fluence determined from EDAX analysis [71].
Figure 14. Scanning electron micrograph of coating surface at a fluence of 9 J/cm2 from
an HA target of 95% density [71].
particles of different sizes held onto the surface as shown in Figure 14.
In vitro testing was carried out by culturing human oestoblasts
on uncoated and calcium phosphate-coated surfaces for 48 h. Using
a colorimetric method, the protein content of the uncoated and coated
samples was determined as a function of DNA content as shown in
Figure 15.
Laser Texturing
Figure 15. Protein content of oestoblasts cultured on uncoated and coated polymers:
poly(L-lactide) (PLA) and poly("-caprolactone) (PCL). The protein content is expressed as
a proportion of the DNA content. The polymer samples coated at different fluences show
higher protein content than uncoated samples [71].
Figure 16. Relationship between and the microstructures of the untreated and CO2-laser-
treated MgO–PSZ surface at various power densities with cell adhesion and the cos for
glycerol contact angle, the roughness, the O2 content, and the polar component of surface
energy [72].
Figure 17. (a) Variation of cell attachment with the surface energy and (b) variation
of cell attachment and surface energy with power density [72].
Figure 18. Schematic of Q-switching operation. A trigger laser is positioned such that the
light is reflected from the rotating reflector onto a detector. This triggers the flashlamp
prior to the alignment of the reflector [62].
Figure 20. Surface profiles of laser-induced morphologies at a pulse energy of 7.8 mJ and
a target–lens distance of: (a) 91; (b) 96; (c) 98; (d) 100; (e) at 100 mm with a laser pulse
energy of 5.7 mJ; and (f ) 9.0 mJ [76].
Figure 21. The kinoform splits the laser beam into an array of 290 spots [77].
Figure 22. (a) Scanning electron micrograph of the screw-shaped implant and
(b) micropattern generated on the flanks of the screw using the kinoform-based laser
patterning technique [77].
Figure 23. Craters formed after excimer laser treatment. During laser ablation,
the substrate material vaporizes and forms a crater. Depending on thermo-fluidic
properties of the material, a resolidified material forms a rim along the periphery of the
crater [35].
Figure 24. Variation of roughness with energy density per pulse [35].
Figure 25. During laser ablation process, a plume forms over the surface. This plume
comprises substrate molecules, ions, and ambient gas and shields the substrate from
the incoming laser beam. At higher laser intensities, this plume explodes and ripples are
formed on the surface.
Figure 26. Schematic of the experimental setup used by Duncan et al. The image of
the mask is projected and etched onto the surface of the sample (S) after the KrF laser
beam travels through the homogenizer (H), the field lens (F), the mask (M), and the
projection lens (P) [50].
Figure 27. (a) Electron micrographs of laser-modified PET having parallel surface
grooves with a spacing of 30 mm, a width and depth of 30 and 1 mm, respectively and
(b) showing confocal micrograph of the same sample [50].
Figure 28. (a) Cross section profile of the laser-modified polymer surface with parallel
microgrooves with a spacing of 30 mm, a width and depth 30 and 1 mm, respectively and
(b) showing the electron micrograph of oestoprogenitor cells placed on the microtextured
surface after 7-day seeding [50].
Figure 30. Schematic of SIS technique where the laser passes through the mask and
patterns a moving workpiece [84].
Figure 32. Schematic illustrating the transfer of a thin film onto an acceptor substrate
using a laser. The technique is referred to as laser-induced forward transfer (LIFT) [87].
Figure 34. ESI mass spectra of three PEG films processed by: (a) MAPLE; (b) drop-cast;
and (c) pulsed laser deposition (PLD). m/z is the mass-to-charge ratio; Mw, is the molecular
weight average; and Mn is the number average molecular weight [90].
EVOLVING CONCEPTS
Figure 36. Schematic of the laser-textured coating operation. Textured coating is evolved
by modulating the laser processing parameters.
For that, apart from improving the physics behind lasers, it is impor-
tant to explore the fundamentals of the laser–substrate interactions.
So far, studies on solid-state phase transformations and topographical
modifications produced by laser surface engineering are limited
[106,107]. In fact, excimer laser studies on Ti alloys are further limited
[108]. Such studies are of great vitality with respect to excimer lasers
due to the high absorbability and control over the features produced.
Effective manipulation of short pulses from laser irradiation on material
surfaces generates high cooling rates that can generate interesting
metastable phases providing a good blend of physical features along
with chemical activity.
CONCLUSIONS
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BIOGRAPHICAL SKETCHES
Anil Kurella
Narendra B. Dahotre