Вы находитесь на странице: 1из 47

Journal of Biomaterials

Applications
http://jba.sagepub.com

Review paper: Surface Modification for Bioimplants: The Role of Laser


Surface Engineering
Anil Kurella and Narendra B. Dahotre
J Biomater Appl 2005; 20; 5
DOI: 10.1177/0885328205052974

The online version of this article can be found at:


http://jba.sagepub.com/cgi/content/abstract/20/1/5

Published by:

http://www.sagepublications.com

Additional services and information for Journal of Biomaterials Applications can be found at:

Email Alerts: http://jba.sagepub.com/cgi/alerts

Subscriptions: http://jba.sagepub.com/subscriptions

Reprints: http://www.sagepub.com/journalsReprints.nav

Permissions: http://www.sagepub.com/journalsPermissions.nav

Citations (this article cites 89 articles hosted on the


SAGE Journals Online and HighWire Press platforms):
http://jba.sagepub.com/cgi/content/refs/20/1/5

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Review paper: Surface
Modification for Bioimplants:
The Role of Laser Surface
Engineering

ANIL KURELLA1 AND NARENDRA B. DAHOTRE1,2,*


1
Department of Materials Science and Engineering
The University of Tennessee, Knoxville, Tennessee 37996, USA
2
Materials Processing Group, Metals and Ceramics Division
Oak Ridge National Laboratory
Oak Ridge, Tennessee 37831, USA

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.

KEY WORDS: biomaterials, interface, surface modification, bioimplants,


osteointegration, lasers, coating, texturing.

INTRODUCTION

I t is rare to find a material that meets all the requirements of


a given application and biomaterials are no exception. For example,

*Author to whom correspondence should be addressed. E-mail: ndahotre@utk.edu

JOURNAL OF BIOMATERIALS APPLICATIONS Volume 20 — July 2005 5


0885-3282/05/01 0005–46 $10.00/0 DOI: 10.1177/0885328205052974
ß 2005 Sage Publications

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
6 A. KURELLA AND N. B. DAHOTRE

Table 1. Some facts related to biomaterials and healthcare


in USA alone [2].
Healthcare expenditure during 2000 $1.4 trillion
Health research and development in 2001 $82 billion
Total market for medical devices in 2002 $77 billion
Total market for biomaterials in 2000 $9 billion
Hip prostheses implanted in 2002 250,000
Knee prostheses implanted in 2002 250,000
Dental implants used in 2000 910,000
Intraocular lenses used in 2003 2,500,000

a candidate implant material may have good mechanical properties but


it may be incompatible with the biological environment and vice versa.
Hence, one needs to strike a balance in choosing an optimum material.
This balancing act is frequently done between bulk and surface
properties. Changing the bulk severely limits our options in materials
selections, and often is not economically or technologically viable.
Hence, among the options available for evaluating the performance of a
biomaterial, the enhancement of the surface phenomenon holds the key.
In practical applications, the surface of a material is subjected to the
influence of various external stimuli. Often a surface-related property
of the material renders it a poor performer. Corrosion, oxidation, wear,
and fatigue are a few such material degradation phenomena, which
initiate at the surface. Every year, a large number of revision operations
are performed to restore the implant material into the system [1]. As the
population ages, this problem becomes a matter of great importance.
Implant loosening due to poor adhesion wear over a period of time,
leakage of ions, and corrosion are some of the reasons attributed to the
failure of implants inside the biological environment [1]. Table 1 shows
the statistics related to biomaterials and healthcare industry in the USA
alone [2]. Often the revision operations are complex and costly. Thus,
it has been a constant endeavor by engineers and scientists to improve
the surface-related properties of biomaterials. Surface engineering
seems to offer solutions for improved functionality and biocompatibility
of implants.

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

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 7

formulations resulted in detrimental tissue reactions and turned out to


be a failure [3], during the early years of the twentieth century. It was
not until the 1920s that, with the advent of 316 stainless steel, materials
scientists were able to find a material that was compatible with a
biological environment [3]. Currently, most artificial joints consist of a
metallic component (either titanium alloy or Co–Cr alloys) articulating
against a polymer (typically ultrahigh molecular weight polyethylene,
UHMWPE). Cr–Co alloys have excellent wear resistance and are stable
due to the formation of a passive, tenacious, self-replenishing chromium
oxide, a few atomic layers thick. Since Cr–Co alloys have good wear
resistance, there is a great deal of interest in its applicability in metal-
on-metal bearing surfaces for hip joints [3]. The low density of titanium
and its alloys drove research into their applications as implants in the
1930s [3]. A low density imparts a high strength-to-weight ratio. Apart
from this, titanium alloys are increasingly used as implant materials in
dentistry and orthopedics because of their excellent biocompatibility,
which is attributed to a passive layer of TiO2 on the surface. A
passive layer renders it inactive when placed in a physiological
environment [1,3,4]. Some of the key mechanical properties of various
metallic materials used for bioimplant applications are listed in Table 2
[1,5–7].
Ceramics that are considered for bioapplications are commonly
termed bioceramics. These are usually polycrystalline inorganic
silicates, oxides, and carbides. They are refractory in nature and possess
high compressive strength. Bioceramics can be subclassified as bio-
inert, bioactive, and biodegradable materials [1]. Bioinert ceramics like
alumina and zirconia maintain their physical and mechanical proper-
ties even in biological environments. Zirconia is highly wear resistant
and tough; it undergoes stress-induced transformation toughening. The
main application of zirconia ceramics is in total hip replacement (THR)
ball heads [8–11]. Ceramics like calcium phosphate and tricalcium

Table 2. Properties of some key metallic implant materials [1,5,6].

Cold Worked Cast


Property 316L SS Ti–6Al–4V Co–Cr–Mo (F75)
Specific gravity (g/cc) 7.9 4.5 8.3
Tensile strength (MPa) 860 860 655
Yield strength (MPa) 690 795 450
Elongation (%) 12 10 8
Reduction of area (%) 50 25 8

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
8 A. KURELLA AND N. B. DAHOTRE

Table 3. Comparison of mechanical properties of bioinert (alumina, zirconia) and


bioresorbable (hydroxyapatite) materials [1,7,12].

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

phosphate (TCP) degrade upon implantation in a biological environment


and hence are considered biodegradable or resorbable. Salts like
hydroxyapatite (HA) can be crystallized from calcium phosphate.
The mineral phase of bone and teeth is closely related to this HA,
which accounts for its high biocompatibility. The existence of HA as a
preeminent biomaterial is well established and documented [12]. The
key mechanical properties of these two major classes of bioceramics are
listed in Table 3 [1,7,12]. As can be seen from the table, the major
drawback of this HA is its poor mechanical properties. Its fracture
toughness (KIC) is <1.2 MPa m1/2. On the other hand, the fracture
toughness of human bone ranges from 2 to 12 MPa m1/2. Therefore, the
application of HA is limited to low load bearing applications, coatings, or
porous implants. The latest classes of bioceramic materials are bioactive
in nature. These materials induce a biological bonding at the interface
between the material and the tissue. Commercially available BioglassÕ
and CervitalÕ are examples of this class of materials [1,13]. Their major
application is in the coating of metal prostheses.
Polymers are considered for a wide range of biomedical applica-
tions because of their ease of manufacturability, low cost, and adequate
mechanical and physical properties. Polymers can be natural or
synthetic. These are long-chain molecules that consist of many small
repeating units. Typically, polymers are used in orthopedic, dental,
cardiovascular, and soft tissue applications. Polymers like UHMWPE are
frequently used in load-bearing applications like acetabular cup in THR,
and the tibial plateau and patellar surfaces of knee joints. However,
compared to metallic and ceramic systems, polymers tend to possess low
mechanical strength and poor wear resistance. Thus, various surface
modification techniques have been evolved to enhance the functionality
of these polymers and these are discussed later in this study. Table 4
summarizes a broad classification of biomaterials.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 9

Table 4. Broad classification of some important biomaterials.

Biomaterial Major Type


System Examples of Application Features
Metallic Steel-316 Structural Biocompatible
Co–Cr alloys: Structural Good wear resistance
Co–Cr–Mo,
Co–Cr–W–Ni,
Co–Ni–Cr–Mo–Ti
Ti alloys: CP Structural Excellent
Titanium, Ti–6Al–4V, biocompatibility
Ti–3Al–2.5V, Low strength-to-weight
Ti–6Al–7Nb ratio
Ceramics Alumina, Zirconia Structural and coatings Bioinert
Hydroxyapatite, Coatings Biodegradable
calcium phosphate
Bioactive: BioglassÕ , Structural and coatings Bioactive
CervitalÕ
Polymers Polyethylene, Structural Bioinert
silicone, Easy to manufacture
UHMWPE, PVC Low cost

Interface

The interaction between the tissue and the implant surface is a


dynamic process. Water, free biomolecules, and dissolved ions surround
the implant surface during the initial few seconds after implantation.
The healing process initiates with change in the composition of the
surrounding biofluid and adsorption of a layer of biomolecules, as shown
in Figure 1. Following this, cells reach the surface and the adsorbed
layer dictates the way the cells respond. As time progresses, the type of
cells and their activities on the surface change, resulting in a tissue
integration or fibrous capsule formation [1,14].
Osteointegration refers to the direct contact between a bone and an
implant without the intervention of a soft tissue. It has been seen that
for effective osteointegration, the surface microtexture and its chemistry
play a vital role [1]. The physical textural features at atomic, molecular,
and higher levels act as contact areas for biological units like proteins,
cells, tissues, etc. The different types of bonding associated with each of
these biological units influence the hierarchical integration of a surface
into its bonding environment. At the same time, it is important to
realize that the chemical activity of the implant surfaces also elicits

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
10 A. KURELLA AND N. B. DAHOTRE

Adsorbed
biomolecules
Extracellular
and water
fluid
Cell

Biomaterial

Figure 1. Interaction at the biomaterial surface.

responses from the biomolecules. Different levels of bonding are


initiated by different chemical species and thus affect the adhesion
properties [1,15]. A material undergoes different chemical reactions
at the surface depending on the environment and thus complicates the
understanding of the exact nature of the interactions.

SURFACE ENGINEERING

The purpose of surface modification is to retain the key bulk


properties of the material while modifying the surface to improve
biocompatibility. Typically, modifications can either alter the atoms,
compounds, or molecules on the existing surface chemically or
physically, or coating the existing surface with a different material. In
this section, some of the important surface modifications are discussed,
with a great deal of emphasis on coating and texturing operations.

Chemical Treatments

Chemical reactions can be categorized as specific and nonspecific


types. If the result of a chemical reaction is a distribution of different
functional groups on the surface, then it is a nonspecific reaction. The
oxidation of a polyethylene surface by chromic acid and radio frequency
glow discharge (RFGD) in different atmospheres are common examples
of nonspecific reactions. When a surface reaction changes one functional
group into another with few side reactions and high yield, it is called a
specific chemical reaction. Alkylations and conversion to siloxane come
under this category [4].

Ion Beam Implantation

In this process, accelerated ions are injected into the surface of


a material and the surface properties of the material are modified.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 11

Largely used for metallic biomaterials, the process involves the


implantation of the desired ion at high kinetic energies on a localized
surface zone. Applications of such a process include improvement
in hardness, wear, corrosion, toughness, and bioreactivity. The corro-
sion resistance of Ti–6Al–4V alloy has been shown to improve after
implantation of irridium ions. Similarly, silver ions implanted into
polystyrene allow cell attachment on the surface [4].

Silanization and Langmuir–Blodgett Deposition

Silanization is a simple and low-cost operation involving a liquid-


phase chemical reaction. The process is shown in Figure 2. These
silanized surfaces have diverse applications like cell attachment,
biomolecule and polymer immobilization, nonfouling surfaces, bio-
mineralization [4], etc. The Langmuir–Blodgett (LB) deposition involves
coating the surface with one or more highly ordered layers of surfactant
molecules. Each of these assembled molecular layers consists of polar
and nonpolar groups. Films deposited by this method show a high degree
of uniformity and order [4].

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].

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
12 A. KURELLA AND N. B. DAHOTRE

Self-assembled Monolayers

When a surface film or a monolayer spontaneously forms highly


ordered structures on a certain substrate, it is referred to as a self-
assembled monolayer (SAM). Such ordered arrangements require
exothermic absorption and significant van der Waals forces. Well-
known examples are alkanethiols and disulphides on coinage metals,
and phosphates on titanium. With the adsorption of sites on the surface,
the chains get closer to each other under the influence of the weaker
van der Waals forces, leading to a crystallization of the alkyl groups.
These SAMs are easy to form and are stable compared to LB films.
Also the SAMs provide an opportunity to change the outermost group
that interacts with the external environment. Successful SAMs for
creating a functional biosurface include anhydrides, perfluoro groups,
ethylene glycol oligomers, and biotin [4].

Microcontact Printing

Whitesides et al. have developed a technique to create micro- and even


nanoscale patterns over large surface areas called microcontact printing
(mCP). The process involves generating a pattern on a master silicon
template by using conventional photolithographic and etching opera-
tions. The next step involves pouring a curable silicone elastomer
onto the template followed by curing. This, when peeled off, serves as a
rubber stamp that can be inked in thiols, proteins, silanes, or polymers.
The sequence of operations involved in MCP is shown in Figure 3.
mCP can be used to pattern curved and flat surfaces [4].

Coatings

Calcium phosphate-based ceramics show a great deal of biocompat-


ibility but their undesirable mechanical properties like brittleness, low
strength, and low fracture toughness have limited their applications in
load-bearing cases. Hence, they are explored as coating systems on
Ti and its alloys as well as ceramics like zirconia and alumina. Various
techniques were explored for coating the surfaces of Ti alloys like
liquid immersion, thermal spray, plasma spray, electrocrystallization,
and electrophoretic process [16–22]. In the next few paragraphs, we
will discuss some of the important results corresponding to these
processes reported in literature.
Kim et al. have developed a sol–gel-based approach to coat Ti
substrate with HA and fluorhydroxyapatite (FHA) layers [22,23].

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 13

Figure 3. Microcontact printing process illustrated in the sequence of steps a–g.


PDMS refers to poly(dimethyl siloxane) [4].

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].

During the process, different F ion concentrations were incorporated


into the apatite structure. The functional activity of the proliferated
cells was studied by observing the alkaline phosphatase (ALP) activity.
As can be seen from Figure 4, HA and FHA coatings show higher

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
14 A. KURELLA AND N. B. DAHOTRE

alkaline ALP activity compared to pure Ti suggesting that coated


substrates exhibit enhanced bioactivity and functionality.
In an electrophoretic deposition, an electric field is applied to a
colloidal suspension resulting in the movement of charged particles and
subsequent deposition on the substrate [24,25]. Mondragón-Cortez and
Vargas-Gutiérrez have studied the influence of applied voltage and time
on deposition of HA on stainless steel 316L [16]. Their results at various
voltages are depicted in Figure 5. They have concluded that by applying
high voltages like 800 V for 5 s, it is possible to develop submicron
particle coatings as shown in Figure 6. In order to make the coating
particles sinter and bond to the substrate, the coating was heat treated
at 800 C for 2 h to produce a homogeneous crystalline crack-free
structure (refer to Figure 7). But many of these techniques discussed
above are associated with problems like absence of good bonding
between substrate and coating, lack of homogeneity of the coatings,
complicated preparation processes, and formation of multiple phases
[26–28]. Yan et al. have tried to characterize the chemical homogeneity
of plasma-sprayed HA on Ti–6Al–4V substrates using micro-Raman
spectroscopy (MRS). They observed that there was a chemical gradient
along the thickness direction and noted that crystallinity decreases from
the top surface to the interface. The characteristic curves of OH and PO4

Figure 5. Variation of deposited weight as a function of deposition time at different


applied voltages: (a) 200; (b) 400; and (c) 800 V [16].

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 15

Figure 6. Scanning electron micrographs of the electrophoretic processed coatings


obtained at 800 V with different applied times: (a) 0.5; (b) 2; and (c) 3 s [16].

shown in Figure 8 indicate that at the interface between the HA coat-


ing and substrate, amorphous calcium phosphate dominates and thus
crystallinity decreases as we go toward the interface [26]. These
observations were consistent with those made by LeGeros et al. that
the absence and discontinuities in crystallinity result in easy dissolution
of coating, a feature detrimental for bioapplications [27].
In another effort, by Wen et al., the chemical nature of the plasma-
sprayed HA coating was analyzed using time-of-flight secondary ion
mass spectroscopy (ToF-SIMS) and micro-Raman spectroscopy [28].
The cross sections of the plasma-sprayed coatings consisted of two
areas as shown in Figure 9: a smooth area along with a ribbon-like
granular region. SIMS showed no appreciable difference in chemical
compositions between the two regions. But the Young’s modulus of
region B (128 GPa) was higher than that of region A (83 GPa). With
the help of micro-Raman spectra, they have concluded that region B is of
crystalline and region A is of amorphous calcium phosphate. From ToF-
SIMS maps (Figure 10) and micro-Raman spectral analysis, Wen et al.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
16 A. KURELLA AND N. B. DAHOTRE

Figure 7. Scanning electron micrographs of HA sintered at 800 C for 2 h and originally


electrophoretically synthesized at 800 V for (a) 0.5 and (b) 3 s [16].

predicted that HA might have transformed to tricalcium phosphate and


oxyhydroapatite phases. The intensity of chemical element signals
is proportional to the brightness. These phases are more likely to
exist close to the interface between the titanium substrate and the
coating. This chemical inhomogeneity and lack of crystallinity affects
the mechanical stability and bioactivity of the coatings adversely. On
the contrary, the high energy density laser-based coating processes
appeared to hold tremendous promise in addressing these process
and materials limitations and producing potentially sound coatings. HA
coatings with a high degree of crystallinity and adhesion were developed
using KrF and ArF lasers [29–34]. The applications of the above-
mentioned lasers are discussed in greater detail in later sections.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 17

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

Texturing generally refers to the physical modification of the


functional properties of the surface of an object by surface engineering.
The properties and the reasons for changing them may be many and
varied. There may be a requirement to reduce (or even increase) the
friction between mating parts, to improve the formability of a metal
sheet, to increase the surface area of a substrate (perhaps to improve
the adhesion of a coating), or to enhance its decorative appeal and
reduce its sensitivity to surface scratches. Textured surfaces are found
in everyday products, from steel body panels and bearings to book covers
[35]. A gamut of biomaterial surface properties involving tribological,

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
18 A. KURELLA AND N. B. DAHOTRE

Figure 10. ToF-SIMS maps of Ti–HA coatings at 40 mm, the Ti substrate is at the
left-hand side.

mechanical, and chemical ones, influence the biocompatibility and


functionality of the implants. As discussed earlier, a control of the
surface morphology is of primordial importance. It has been well
established that physical structure plays a key role in determining
the cellular responses and hence the range of biomaterial applications.
Curtis and Wilkinson have discussed various issues relating to
topological control of cells on substrates in their review [36]. The
interactions of cells to surfaces occur at various length scales from
microscale to nanoscale [37]. The protein molecule interactions
associated with cell signaling occur at the nanoscale. This regulates
cell adhesion, proliferation, and differentiation. The combined effects
of configurationally hydrophobic/hydrophilic or capillary forces might be
responsible for self-organization of protein molecules and cell attach-
ment. The interactions between microsize features (e.g., grooves) with
cells take place at the microscale. Finally, the interaction of tissues with

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 19

porosity occurs at the macroscale. This knowledge has driven research


at the micrometer and the nanometer scale features of the implant
surfaces. Materials textured at the microscale or the nanoscale have all
showed improved performance. But so far the ideal surface textured
has not been established. Most of these studies were concentrated on
characterization of cell or protein adhesion to surfaces from a biological
perspective. A great deal of interest was given to surface energy
and charge, and hydrophilic/hydrophobic features [36,38,39]. Different
features like grooves, ridges, cliffs, dots, spikes, pits, and mesh, were
experimented with [40]. The phenomenon that substrate topography
influences the cellular behavior is referred to as ‘contact guidance’ [41].
The phenomenon by which cells adapt and orient to the surface
microtopography is influenced by contact guidance. Curtis et al. found
out that microgroove depth was more important for contact guidance
than microgroove width [36]. On the other hand, chemistry of the
surface influences cell signaling and the way cell surface receptors
respond. Once cell surface signaling is established, the cells try to orient
by achieving a biomechanical equilibrium alignment provided by contact
guidance of the topography.
Over the years, many efforts were dedicated to studying this
phenomenon using various cell systems like fibroblasts, epithelial
cells, neurons, neutrophils, etc. [36,40,42,43]. Although these studies
varied in surface features, surface compositions, and the cell type used,
the results clearly showed that fine features (2 m) have orientation
effect on both cytoskeleton elements and cell body. Surface texturing is
generally carried out to modify the surface for better osteointegration.
Specifically for hard tissue replacements with metallic implants, it is
necessary to have three crucial characteristics: namely cleanliness,
stable oxide layer, and microscale morphology [44]. The surface
contamination may originate from bulk material of the implant
but generally it occurs during surface engineering of the implant. The
second feature is the microscale morphology or the texture of the
surface. In their vivo experiments on rabbits, Karacs et al. have reported
that the torque removal force was higher for sandblasted and laser-
treated samples compared to smoothly machined ones. This could be
attributed to the in-growth of bone into the microscale features and
thus providing micromechanical retention [44]. Originally, enhance-
ment of osteointegration was carried out using blast-textured surfaces
with random and irregular topography [45–47]. However, with such
random topologies resulting from blasted surfaces, it was difficult to
conduct basic studies of the effect of texture on osteointegration and
hence, many patterning techniques evolved. Some of these prominent

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
20 A. KURELLA AND N. B. DAHOTRE

Table 5. List of various surface texturing processes.

Surface Texturing Process Features


Sandblasting [45–47] Random surface textures
Difficult to control the depth and
regularity of features
Process not clean
Electron beam texturing [48] Precise control, nanofeatures
Process requires vacuum
Photolithography [40,49] Well-controlled features
Problems with spin coaters, photoresists,
and organic solvents [50]
Ion beam texturing [6] Accelerating ions bombard surface and
result in texturing
Requires vacuum
Electric arc texturing [35] For conductive materials
Less control over the process
Laser texturing/micromachining [50] Precise control of complex features
Noncontact, fast, and clean process

technologies are listed in Table 5. Although, this field is still nascent,


the range of technologies are evolving at a rapid pace and encompasses
laser processing, photolithography, electron beam processing, ion beam
processing, etc. [40,48,49]. Electron and ion beam processing find
their limitations needing vacuum chambers as processing environments
which means limitations on shape and size of the component to be
processed. Also these techniques remain confined to batch processing
and hence are expensive. Photolithography, although free from the
requirement of a vacuum chamber, is an extremely time-consuming
multistage process. On the contrary, laser processing can be conducted
in ordinary air at extremely rapid speed with high precision and
repeatability [50]. Thus the next part of this review emphasizes
the developments that have taken place in the use of lasers for bioappli-
cations with an endnote on the potential applications and suggestions.

LASER SURFACE ENGINEERING FOR BIOSURFACES

Light amplification by stimulated emission of radiation (LASER) is a


source of coherent electromagnetic radiation. Over the years, lasers
have found numerous applications in electronic, communication,
and health industries. In the following section, some of the important
laser processing operations with respect to their applicability to surface

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 21

engineering of biomaterials are reviewed. Laser surface engineering


(LSE) is a material processing method, which utilizes the high power
density available from focused and localized laser sources to melt, heat,
or modify the material on and near the surface [35]. Depending upon the
particular material system and process parameters, it may involve only
modification of microstructure, grain refinement, phase transforma-
tions, alloying and mixing of multiple materials, and mixing and
formation of composite system on the surface without actually affecting
the bulk material itself. The focused and short duration energy input
from the laser in a small region establishes steep thermal gradients
between the liquid pool and the relatively cold substrate underneath,
which act as a heat sink. The thermal gradient of great magnitude
coupled with the conduction mode of heat transfer can establish a
cooling rate as high as 1011 K/s. Owing to its high cooling rate (almost
always >103 K/s), they often freeze into nonequilibrium microstructural
features [51–54].
Laser parameters, such as power input determine the maximum
temperature attained and the cooling rate; and the duration of
interaction determines the reactions among phases. As the heating
and cooling rates are very rapid, a refined microstructure, extended solid
solubility, incomplete surface chemical reactions, etc., may be present
in the microstructure. Such refinement shall affect the mechanical
properties significantly. Also, interfacial phenomena between substrate
and coating are a strong function of temperature. The interface bonding
may be frozen due to low temperature during such rapid cooling. These
interface bonds, along with other microstructural features, shall affect
the mechanical property of the local volumes [55–62]. Lasers are widely
used in medical, microelectronic, optical, and data storage applications
[63]. Laser-based techniques like removal of contaminants on micro-
device surfaces and surface texturing of magnetic devices are well
established. As the technology evolves toward faster data recording
capabilities and nanoscale features, lasers along with electron beam
are expected to play a pivotal role in device fabrication. The smallest
achievable feature by optical lithography is limited by the wavelength
of the source. Therefore, excimer lasers like KrF (248 nm) and ArF
(193 nm) are being used to produce submicron features on the surfaces.
Efforts being made to apply shorter wavelength laser sources like
Vacuum Ultraviolet (F2 157) for features around 65 nm by the year 2005
[63]. In fact Extreme Ultraviolet (13 nm) source is set to produce 20 nm
features by the year 2010. Laser surface nanopatterning involves a
simple setup; high speed, easy processing compared to electron beam or
focused ion beam techniques.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
22 A. KURELLA AND N. B. DAHOTRE

Based on these premises, LSE of biomaterials is evolving rapidly on


two different fronts. One is the laser-assisted surface coating on implant
materials. Typically HA, zirconia, or other bioglasses are coated on
substrates like Ti alloys [64]. During laser irradiation, the objective
is to induce the formation of new chemical species, which in turn
could improve the interactions between the biological medium and the
surface. Another area of interest is the laser surface texturing of
biomaterial surfaces to pattern surfaces with features. Laser micro-
machining to achieve 3-D structures on micrometer and submicrometer
scales is fast proving to be a good alternative to a standard
photolithographic process [50,65]. When the substrate material is
difficult to be removed or when the surface geometry is complex,
lasers seem to be the ideal solution. Micromachining and laser
microtexturing have been carried out to produce relatively uniform
microgrooves on a range of materials [35,65,66]. The use of a laser for
texturing surfaces presents many advantages; for instance, it is rapid
and extremely clean. Lasers are useful for the selective modification of
the surfaces. They have the ability to generate extremely complex
microstructures/features with high resolution. If a laser beam is coupled
with a noncontact mask and optical systems, it is possible to produce
submicrometer features. Laser ablation can be used for varied surfaces
[35,67]. Conventional lithographic techniques involve the need of
photoresists and thin film resists. These are time-consuming steps and
the use of resist development and other solvents alter the polymer
surface texture, chemistry, etc. On the contrary, laser-based techniques
do not require organic solvents that modify the structure of the polymer-
treated surface or denature proteins present in the surface. In fact,
microlithographic techniques require class 100 clean rooms, dark
rooms, spin coaters, photoresist, and optimization techniques to coat
and develop specific systems and their removal systems. Laser helps
circumvent all these steps [50]. Furthermore, the common disadvantage
among other conventional techniques like anodizing, chemical etching,
and mechanical scratching is that they are incapable of local texturing,
and they lack good control over the resulting roughness [35]. Lasers are
useful in the generation of short pulses of light of single wavelength,
which allow them to focus a great amount of energy in one spot.

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

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 23

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.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
24 A. KURELLA AND N. B. DAHOTRE

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].

calcium phosphates to overcome this drawback. During pulsed laser


deposition of calcium phosphate on two polymers poly(L-lactide) (PLA)
and poly("-caprolactone) (PCL), Antonov et al. have observed that at
higher fluences around 9 J/cm2, the coating composition was close to
that of the initial composition of the target (Ca/P ¼ 1.67) as shown in
Figure 13 [71]. The coatings were smooth and dense with ejected

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 25

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

For texturing applications, various lasers are used depending on


the feature to be fabricated and the type of material to be processed.
Texturing based on the type of laser source is discussed here.

CO2 Laser Texturing


CO2 lasers that can be typically operated in a power range of 1.5–3 kW
are used to process metallic and ceramic materials. In such a power
range, the maximum beam intensity on the surface can be 10 MW/cm2.
When operated in pulse mode, pulses of 10–50 ms with frequencies of
25–45 kHz are possible. These lasers are used for roll surface texturing
[35]. Using lens of short focal length, the beam can be made to focus into
a spot of 100 mm. However, this laser causes surface oxidation and brittle
rim. This in turn lowers the lifetime of the surface topography. Hao et al.
have used CO2 laser surface engineering to change the roughness
and surface energy of bioinert ceramic-like stabilized zirconia [72].

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
26 A. KURELLA AND N. B. DAHOTRE

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].

Since wettability is important for cell adhesion, parameters that deter-


mine the surface energy like roughness, contact angle, and oxygen
content were studied with the variation in power density as shown
in Figure 16. They have reported that the wettability was influenced
more by microstructural changes on the surface and oxygen content
than by surface roughness. Microstructural observations of the surfaces
revealed that at low laser powers, reorientation of the crystal structure
took place followed by evolution of a hexagonal structural arrangement.
For samples treated at 1.6 kW/cm2, cell formation starts with the onset
of melting at the surface. This state corresponding to the maximum
surface energy was followed by lowering of surface energy due to the
evolution of a uniform cellular structure. Attachment of human skin
fibroblast cells as function of surface energy and applied power densities
is shown in Figure 17.

Nd : YAG Laser Texturing


Nd : YAG texturing application range from hard disk surfaces to
biomaterial implant surfaces. The pulse repetition rate of Nd : YAG laser
can be controlled electronically, and hence, predetermined patterns can
be produced accurately. Usually a Q-switched Nd : YAG laser is used for
such texturing operations (shown in Figure 18). Q-switching results in
continuous wave generation due to reflection of laser beam into a laser

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 27

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].

cavity. While the beam is translated, a continuous surface melting


results. A topography consisting of craters superimposed on melt
tracks can be produced with the application of pulses on a continuous
wave background. The beam from an Nd : YAG laser can be focused to a
smaller spot size because of shorter wavelength when compared to a
CO2 laser. The demand for high tolerances coupled with miniaturization
of medical components has pushed the width of laser cuts to lower levels.
To cut thick materials with fine precision, a pulsed Nd : YAG slab laser
with its rectangular laser crystal is used. The thermal lensing effect is
compensated by the rectangular crystal of the YAG laser. Evaporation-
based material removal due to short pulse with high beam intensity
is seen in Nd : YAG texturing. The action of CO2 and Nd : YAG lasers is
generally a thermal process, the focusing optics direct a predetermined

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
28 A. KURELLA AND N. B. DAHOTRE

Figure 17. (a) Variation of cell attachment with the surface energy and (b) variation
of cell attachment and surface energy with power density [72].

energy density into a focused spot on the workpiece. Prior to ablation


of a material, the absorption of radiation at the surface raises its
temperature; this results in melting at the surface. As the temperature
continues to rise, vaporization of the material occurs, and finally
it solidifies when the temperature comes down. Thus melting, melt
motion, evaporation, and solidification are the series of steps involved in
the generation of new surface topography when a focused laser
beam interacts with a material surface. Competing processes like melt
ejection and evaporation determine the material removal and final
crater creation. Pulsed laser ablation was carried on different materials
like titanium [73], molybdenum [74], aluminum, and copper [75].

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 29

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].

György et al. have investigated the influence of laser intensity on


the surface morphology of titanium [76]. Scanning electron microscopy
and profilometric analysis, shown in Figures 19 and 20, were carried
out to study the interaction between Nd : YAG ( ¼ 1064 nm) laser
radiation and Ti surface. All the scanning electron micrographs shown
in Figure 19 were recorded at a sample tilt of 50 and at the same
magnification. They have found that at around 1  108 W/cm2 laser
intensity, melting of the surface layer without vaporization and major
liquid displacements occur along the edges. Increased liquid displace-
ments due to vaporized plasma recoil pressure and air breakdown result
in enhanced surface roughening of the order of several micrometers at
higher laser intensities. Hallgren et al. patterned Ti implants using a
532 nm Nd : YAG laser. Patterning was done by splitting the beam using
a kinoform as shown in Figure 21. Figure 22 shows the screw-shaped
implant whose flanks were patterned using the kinoform technique.
These patterned screw implants under in vivo testing showed higher
torque removal forces and thus exhibited better fixation into the
bone [77].

Excimer Laser Texturing


Although Nd : YAG lasers operating at 1064 nm are used for micro-
machining of metallic materials, polymers cannot be machined precisely

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
30 A. KURELLA AND N. B. DAHOTRE

Figure 19. Scanning electron micrographs of the laser-induced morphologies obtained


with a pulse energy of 7.8 mJ and a target–lens distance of: (a) 91; (b) 94; (c) 96; (d) 98;
(e) 100; and (f ) at 100 mm with a laser pulse energy of 5.7 mJ [76].

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].

by infrared light. UV lasers, operating at <400 nm, are useful in this


case. During machining submicron features, UV lasers photoablate
polymers by breaking the molecular bonds at the surface [78]. When
coupled with mask projection techniques, the excimer lasers allow the

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 31

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].

combination and superimposition of planar microstructures with curved


shapes to produce complex 3D structures [79,80]. Excimer lasers
also enable micromachining when geometry is complex or when the
substrate material cannot be removed by etching. Excimer laser
pulses have beam intensity of around 108–109 W/cm2. During ablation,
the surface of the material absorbs the radiation leading to a rapid rise

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
32 A. KURELLA AND N. B. DAHOTRE

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].

in its surface temperature followed by evaporation or ionization of


the vapor and finally the material is removed as shown by the crater
formation in Figure 23. It has been reported that surface roughness
increases during excimer laser [35] texturing according to a trend
shown in Figure 24. Another feature of excimer laser is that they show
low thermal effects during photoablation. Above a critical fluence
of irradiation from the excimer source, the surface of the substrate
starts to melt. A rapid solidification process ensues after remelting
and a refined structure is observed. At this range of irradiation, nano-
crystalline materials with good wear and corrosion resistance can be
synthesized [35]. With an increase in laser intensity, a vapor plume,
as shown in Figure 25, forms over the substrate and the laser vapor
interactions result in the formation of an ionized zone consisting of ions,
atoms, molecules, and electrons. As the intensity of the laser is further

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 33

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.

increased, plasma forms and starts absorbing the laser irradiation.


At much higher intensities, the plasma plume becomes unstable and
generates a shock wave. This would result in the formation of wavy
topography. On subsequent repeated exposure of the same area, laser
texturing/patterning can be achieved [35]. In a recent study, Duncan
et al. have reported a method (shown in Figure 26) that involves the
combination of microlithography and excimer laser process to produce
well-defined surface features for cell culture [50]. Photoablation of
the polymeric surfaces was carried out to produce repeatable micro- and
submicroscale features as shown in Figure 27. Figure 28 shows the
electron micrograph of the oestoprogenitor cells on the microtextured
surface after 7 days of cell culture.
Recent developments in pulsed, diode pump solid state lasers available
at 1064 nm but capable of reaching much lower wavelengths are
offering an interesting alternative to excimer lasers. Features like
a compact solid-state design supported by TEM00 beam can make it
ideal for future applications. Research is underway to tap the potential
of Ti : sapphire ultrashort lasers for micromachining of biomaterials
[81–83]. The formation of melt phase followed by sublimation can be
suppressed to a greater extent by using these ultrashort pulse
Ti : sapphire lasers [83].

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
34 A. KURELLA AND N. B. DAHOTRE

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].

ADVANCES IN LASER PROCESSING WITH POTENTIAL


FOR BIOAPPLICATIONS

Advancements like bow tie scanning (BTS) of a laser beam


synchronized with image scanning (SIS) techniques are enabling
the fabrication of finer features with a great deal of accuracy, efficiency,
and speed [84,85]. BTS has been successfully implemented on large
substrates like flat panels and solar panels through the improvements
in stages and galvanometer mirror scanner systems. It involves the
combination of substrate motion and laser beam scanning, as shown
in Figure 29. Synchronized image scanning (SIS) involves synchronized
movement of a substrate with respect to a laser beam, which is projected

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 35

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].

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
36 A. KURELLA AND N. B. DAHOTRE

Figure 29. Schematic of BTS technique [84].

Figure 30. Schematic of SIS technique where the laser passes through the mask and
patterns a moving workpiece [84].

Figure 31. Optical setup for laser interference patterning [86].

through a mask as shown in Figure 30. For further details of these


concepts, readers are directed to [84].
A laser texturing technique based on interference of two or more laser
beams to form complex patterns is shown in Figure 31. Favret et al.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 37

have effectively used this technique in micropatterning copper alloys


[86]. Using a beam splitter, a high pulse laser like Nd : YAG is split
into two beams and later combined to produce an interference pattern.
Modulating the wavelength as well as the angle between the split beams
can result in patterns. This process can be used to produce complex
features on biomaterial surfaces. Although this has been presently
demonstrated for copper alloys, this process has the potential for
fabricating complex features on biomaterials.
A novel technique called laser-induced forward transfer (LIFT) is
also gaining a great deal of recognition because of its simplicity, high
deposition rates, and ability to provide selective texturing [87–89].
The process basically involves ablation of transparent donor pre-coated
substrate followed by the transfer and deposition of the removed
material onto an acceptor substrate as shown in Figure 32. Submicron
dots, lines, and other features can be produced via this technique.
A problem associated with LIFT using nanosecond pulses is the
remelting of transferred material. Instead, an ultrashort pulsed LIFT
technique is used to produce good pattern quality. Researchers are
studying pico- and femtosecond lasers for effective application of LIFT
[87–89]. Matrix-assisted pulsed-laser evaporation direct write (MAPLE
DW) was used by Wu et al. in depositing patterning biomaterial thin
films [90]. This process involves the combination of LIFT and MAPLE,
where a sacrificial material absorbs the laser radiation and releases
the material to be coated as shown in Figure 33 [90,91]. In LIFT, the
pulsed laser beam is used to vaporize a thin film, which then condenses
onto a substrate placed close to it. The LIFT technique is not compatible
with polymers on the other hand; the MAPLE DW technique allows
the direct transfer of polymeric materials. For example, polyethylene
glycol (PEG), a biomedical polymer used for tissue engineering and drug

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].

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
38 A. KURELLA AND N. B. DAHOTRE

Figure 33. Schematic of MAPLE DW technique [91].

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].

delivery coatings, requires the preservation of chemical structure during


any deposition operation [92–94]. Using MAPLE, Wu et al. have pro-
duced a PEG film, which preserved the chemical and structural integrity
of the starting material [90]. The electron spectroscopic imaging (ESI)
spectrum, which reinforces this fact, is shown in Figure 34. As can be
observed, the MAPLE-deposited film (Figure 34(a)) shows better frag-
mentation semblance compared to the starting material (Figure 34(b))
or pulsed laser deposited (PLD) film (Figure 34(c)).

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 39

Figure 35. Laser–scanning tunneling microscope nanotexturing. Strong electromagnetic


fields are setup at a spot under the influence of a scanning tunneling microscope and
laser [96].

Further miniaturization of the surface-textured pattern can be


achieved by patterning of lines as small as 30 nm wide by using the
combination of laser with a scanning tunneling microscope (STM). Using
the tip of STMs and a laser beam as shown in Figure 35, it is possible to
induce strong electromagnetic fields at a point in the scale of a few
nanometers. This in turn can result in the etching of substrates. Various
patterns with resolutions smaller than 100 nm can be generated by this
technique. Different kinds of materials can be nanotextured in this way.
Thus, this process can be explored for texturing the surfaces of
biomaterials. These nanoscale features can provide a template to produce
periodic structures, which can be later used to understand the inter-
actions of implant surfaces with protein molecules [95,96]. Gerardino
et al. have adopted laser-induced vaporizing followed by electron beam
deposition technique to pattern biomolecules on silicon substrates [97].

EVOLVING CONCEPTS

Using different processing techniques, various materials were surface


engineered for better biocompatibility [29–37,98–101]. In spite of many
investigations on cell–surface interactions, an intrinsic understanding
of the attachment of cells to biomedical surfaces is still limited [1,102].
The main reason hindering the development of such a basic under-
standing lies in the fact that interactions occur at various length scales
[1,37]. At the nanometer level, the attachment of the cells and self-
organization of proteins are important. The interactions involving
the underlying substrate and the cell constituents dominate at the
submicron level while at the micron level, the microgrooves interact

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
40 A. KURELLA AND N. B. DAHOTRE

with cells. Finally, at higher scales, a group of cells interact either


with porosity or the implant surface [102]. From the above discussion,
it is clear that surfaces with multiscale organization bear close
resemblance to the way things are organized in nature, on multiple
length scales [103,104]. Thus the latest area of interest in biomaterial
surface engineering seems to adopt a hierarchical approach to mimic
natural materials [37]. Therefore, the goal of researchers is to produce
bioactive surfaces with organized structures with features controllable
at both the micro- and nanometer levels.
In such a scenario, a novel concept involving simultaneous coating
and physical texturing using a laser source is envisaged. A successful
implementation of this concept of ‘simultaneous coating and texturing’
would not only improve the biocompatibility of the implants but will
also help in improving the mechanical properties (typically the
wear characteristics). For example, Ti substrate can be coated with
a wear- and corrosion-resistant biocompatible coating and textured
simultaneously. Recently, the authors have conducted preliminary
experiments on this concept by coating a yttria stabilized zirconia
onto a Ti–6Al–4V substrate and simultaneously texturing it with a
25 W pulsed Nd : YAG laser, operating at a speed of 400 mm/s [105].
The process is schematically shown in Figure 36. The preliminary
observations shown in Figure 37 revealed a hierarchically integrated
feature ranging from micron to submicron levels. The authors intend to
study these in greater detail to finally produce a bioactive multiscaled
textured surface.
Lasers with their unique properties seem to offer solutions for
processing functionally integrated, hierarchically structured materials.

Figure 36. Schematic of the laser-textured coating operation. Textured coating is evolved
by modulating the laser processing parameters.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 41

Figure 37. Scanning electron micrographs showing multiscale features on laser-textured


zirconia coating on Ti–6Al–4V [105].

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

With the increasing interest in development of miniature devices and


stable and functionally improved bioimplants, lasers are expected to play
a major role in surface engineering and processing of these components.
The applications likely to range from laser cutting in stents to laser

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
42 A. KURELLA AND N. B. DAHOTRE

coatings and texturing of bioimplants. The advent of laser-based


systems with smaller wavelengths and shorter pulses, with reduced
heat input and finer spot sizes would provide new opportunities for
future biomaterial applications. New developments like LIFT and
MAPLE are expected to play a big role in the processing of biomaterials
in the most desirable way for microscale to nanoscale surface features.
One of the major goals of bioimplants has been their proper osteo-
integration into a bioenvironment. This requires a proper under-
standing of the attachment of cells into the textured surface. With the
current interest in development of a hierarchically controlled micro- to
nanotextured surfaces, better fabrication techniques are required to
produce complex patterns consistently. However, surface modifications
like ‘texturing’ on any scale is likely to result in changes in surface
chemistry on the macro to the atomic scale. These effects are not easy to
measure and it is important to understand that this too may influence
biological response. Amongst the many surface engineering techniques
experimented with, lasers seem to fit the bill because of their features
like: noncontact micromachining and hence high degree of purity, high-
precision coherent beam of energy, processing diverse materials, and
high speeds.
A profound understanding/knowledge of thermodynamics and phase
transformations during laser processing to enhance the functionality
of the laser-enhanced coatings is to be achieved. Problems associated
with laser processing like microcracks and heat-affected zones are to be
minimized. Apart from this, proper in situ monitoring and controlling
of the laser surface engineering is to be incorporated into the setup for
effective feedback analysis of the operations.
An intrinsic understanding of the laser–materials and laser–plume
interactions through the developments of modeling techniques for
quantitative prediction of process parameters is to be achieved. Better
understanding of the adhesion of cells to textured biomaterials like
Ti alloys is to be achieved at multiple length scale features.

REFERENCES

1. Park, J.B., Bronzino, J.D. and Kim, Y.K. (2003). Metallic Biomaterials,
Ceramic Biomaterials, In: Park, J.B. and Bronzino, J.D. (eds), Biomaterials
Principles and Applications, pp. 1–45, CRC Press, Boca Raton, USA.
2. Ratner, B.D., Hoffman, A.S., Schoen, F.J. and Lemons, J.E. (2004).
Biomaterials Science: A Multidisciplinary Endeavor, Classes of Materials
Used in Medicine, In: Ratner, B.D., Hoffman, A.S., Schoen, F.J. and
Lemons, J.E. (eds), Biomaterials Science, 2nd edn, pp. 1–209, Elsevier
Academic Press, San Diego, California, USA.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 43

3. Pilliar, R.M. and Weatherly, G.C. (1984). Developments in Implant Alloys,


CRC Crit. Rev. Biocompatibility, 1: 371–403.
4. Ratner, B.D., Hoffman, A.S. and Schoen, F.J. (2004). Physicochemical
Surface Modification of Materials Used in Medicine, In: Ratner, B.D.,
Hoffman, A.S., Schoen, F.J. and Lemons, J.E. (eds), Biomaterials
Science, 2nd edn, pp. 201–218, Elsevier Academic Press, San Diego,
California, USA.
5. Wang, K. (1996). The Use of Titanium for Medical Applications in the
USA, Mater. Sci. Eng., 213: 134–137.
6. Sioshansi, P. and Tobin, E.J. (1996). Surface Treatment of Biomaterials
by Ion Beam Process, Surf. Coat. Technol., 83: 175–182.
7. Bhushan, B. and Gupta, B.K. (1991). Metals and Ceramics, In: Bhushan, B.
and Gupta, B.K. (eds), Handbook of Tribology: Materials, Coatings and
Surface Treatments, p. 4.57, McGraw-Hill, Inc., New York.
8. Piconi, C. and Maccauro, G. (1999). Zirconia as a Ceramic Biomaterial,
Biomaterials, 20: 1–25.
9. Chevalier, J.J., Deville, S., Münch, E., Jullian, R. and Lair, F. (2004).
Critical Effect of Cubic Phase on Aging in 3 mol% Yttria-stabilized
Zirconia Ceramics for Hip Replacement Prosthesis, Biomaterials, 25:
5539–5545.
10. Christel, P., Meunier, A. and Dorlot, J.-M. (1988). Biomechanical
Compatibility and Design of Ceramic Implants for Orthopaedic Surgery,
Ann. N.Y. Acad. Sci., 523: 234–256.
11. Yang, Y., Ong, J.L. and Tian, J. (2003). Deposition of Highly Adhesive ZrO2
Coating on Ti and CoCrMo Implant Materials using Plasma Spraying,
Biomaterials, 24: 619–627.
12. Suchanek, W. and Yoshimura, M. (1998). Processing and Properties of
Hydroxyapatite-based Biomaterials for use as Hard Tissue Replacement
Implants, J. Mater. Res., 13: 94–117.
13. Lossdörfer, S., Schwartz, Z., Lohmann, C.H., Greenspan, D.C., Ranly, D.M.
and Boyan, B.D. (2004). Osteoblast Response to Bioactive Glasses
In vitro Correlates with Inorganic Phosphate Content, Biomaterials, 25:
2547–2555.
14. Healy, K.E. and Ducheyne, P. (1992). Hydration and Preferential Molecular
Adsorption on Titanium In vitro, Biomaterials, 13: 553–561.
15. Lemons, J.E. (1996). Ceramics: Past, Present, and Future, Bone, 19:
S121–S128.
16. Mondragón-Cortez, P. and Vargas-Gutiérrez, G. (2004). Electrophoretic
Deposition of Hydroxyapatite Submicron Particles at High Voltages, Mater.
Lett., 58: 1336–1339.
17. Chu, P.K., Chen, J.Y., Wang, L.P. and Huang, N. (2002). Plasma-surface
Modification of Biomaterials, Mater. Sci. Eng. R, 36: 143–206.
18. Kweh, S.W., Khor, K.A. and Cheang, P. (2002). High Temperature In-situ
XRD of Plasma Sprayed HA Coatings, Biomaterials, 23: 381–387.
19. Kim, H.-W., Kim, H.-E., Salih, V. and Knowles, J.C. (2004). Dissolution
Control and Cellular Responses of Calcium Phosphate Coatings on Zirconia
Porous Scaffold, J. Biomed. Mater. Res., 86(A): 522–530.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
44 A. KURELLA AND N. B. DAHOTRE

20. Metikos-Hukovic, M., Tkalcec, E., Kwokal, A. and Piljac, J. (2003). An


In-vitro Study of Ti and Ti-alloys Coated with Sol-gel derived
Hydroxyapatite Coatings, Surf. Coat. Technol., 165: 40–50.
21. Oliveira, A.L., Mano, J.F. and Reis, R.L. (2003). Nature-inspired Calcium
Phosphate Coatings: Present Status and Novel Advances in the Science of
Mimicry, Curr. Opinion Solid State Mater. Sci., 7: 309–318.
22. Kim, H.-W., Koh, Y.-H., Li, L.-H., Lee, S. and Kim, H.-E. (2004).
Hydroxyapatite Coating on Titanium Substrate with Titania Buffer Layer
Processed by Sol–Gel Method, Biomaterials, 25: 2533–2538.
23. Kim, H.-W., Kim, H.-E. and Knowles, J.C. (2004). Fluor-hydroxyapatite
Sol–Gel Coating on Titanium Substrate for Hard Tissue Implants,
Biomaterials, 25: 3351–3358.
24. Yamashita, K., Yonehara, E., Ding, X., Nagai, M., Umegaki, T. and
Matsuda, M. (1998). Electrophoretic Coating of Multilayered Apatite
Composite on Alumina Ceramics, J. Biomed. Mater. Res. Appl. Biomater.,
43: 46–53.
25. Wei, M., Ruys, A.J., Swain, M.V., Kim, S.H., Milthorpe, B.K. and
Sorrell, C.C. (1999). Interfacial Bond Strength of Electrophoretically
Deposited Hydroxyapatite Coatings on Metals, J. Mater. Sci., Mater. Med.,
10: 401–409.
26. Yan, L., Leng, Y. and Weng, L.-T. (2003). Characterization of Chemical
Inhomogeneity in Plasma-sprayed Hydroxyapatite Coatings, Biomaterials,
24: 2585–2592.
27. LeGeros, J.P. and LeGreos, R.Z. (1991). Characterization of
Calcium Phosphate Coatings on Implants, In: Proceedings of the 17th
Annual Meetings of the Society for Biomaterials, p. 192, Scotsdale, AZ, USA.
28. Wen, J., Leng, Y., Chen, J.Y. and Zhang, C.G. (2000). Chemical Gradient in
Plasma-sprayed HA Coatings, Biomaterials, 21: 1339–1343.
29. Singh, R.K., Qian, F., Nagabushanam, V., Damodaran, R. and Moudgil, B.M.
(1994). Excimer Laser Deposition of Hydroxyapatite Thin Films,
Biomaterials, 15: 522–528.
30. Sardin, G., Varela, M. and Morenza, J.L. (1994). Deposition of
Hydroxyapaptite Coatings by Laser Ablation, In: Brown, P.W. and
Constanz, B. (eds), Hydroxyapatite and Related Materials, pp. 225–230,
CRC Press, London.
31. Antonov, E.N., Bagratashvili, V.N., Popov, V.K., Sobol, E.N., Davies, M.C.,
Tendler, S.J.B., Roberts, C.J. and Howdle, S.M. (1997). Atomic Force
Microscopic Study of the Surface Morphology of Apatite Films Deposited
by Pulsed Laser Ablation, Biomaterials, 18: 1043–1049.
32. Cotell, C.M. (1993). Pulsed Laser Deposition and Processing
of Biocompatible Hydroxyapatite Thin Films, Appl. Surf. Sci., 69:
140–148.
33. Jelı́nek, M., Olan, V., Jastrabı́k, L., Studnicka, V., Hnatowicz, V., Kvı́tek, J.,
Havránek, V., Dostálová, T., Zergioti, I., Petrakis, A., Hontzopoulos, E.
and Fotakis, C. (1995). Effect of Processing Parameters on the Properties
of Hydroxyapatite Films Grown by Pulsed Laser Deposition, Thin Solid
Films, 257: 125–129.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 45

34. Fernández-Pradas, J.M., Clèries, L., Martı́nez, E., Sardin, G., Esteve, J.
and Morenza, J.L. (2001). Influence of Thickness on the Properties of
Hydroxyapatite Coatings Deposited by KrF Laser Ablation, Biomaterials,
22: 2171–2175.
35. Semak, V.V. and Dahotre, N.B. (1998). Laser Surface Texturing, In:
Dahotre, N.B. (ed.), Lasers in Surface Engineering, Surface Engineering
Series, pp. 35–67, ASM International, Materials Park, OH, USA.
36. Curtis, A. and Wilkinson, C. (1997). Topographical Control of Cells,
Biomaterials, 18: 1573–1583.
37. Tan, J. and Saltzman, W.M. (2004). Biomaterials with Hierarchically
Defined Micro- and Nanoscale Structure, Biomaterials, 25: 3593–3601.
38. Schwartz, Z. and Boyan, B.D. (1994). Underlying Mechanisms at the
Bone–Biomaterial Interface, J. Cell Biochem., 56: 340–347.
39. Tambasco de Oliveira, P. and Nanci, A. (2004). Nanotexturing of
Titanium-based Surfaces Upregulates Expression of Bone Sialoprotein
and Osteopontin by Cultured Osteogenic Cells, Biomaterials, 25:
403–413.
40. Flemming, R.G., Murphy, C.J., Abrams, G.A., Goodman, S.L. and
Nealey, P.F. (1999). Effects of Synthetic Micro- and Nano-Structured
Surfaces on Cell Behavior, Biomaterials, 20: 573–588.
41. Zhu, B., Zhang, Q., Lu, Q., Xu, Y., Yin, J., Hu, J. and Wang, Z. (2004).
Nanotopographical Guidance of C6 Glioma Cell Alignment and Oriented
Growth, Biomaterials, 25: 4215–4223.
42. Wilkinson, C.D.W., Riehle, M., Wood, M., Gallagher, J. and Curtis, A.S.G.
(2002). The use of Materials Patterned on a Nano- and Micro-Metric Scale in
Cellular Engineering, Mater. Sci. Eng. C, 19: 263–269.
43. Craighead, H.G., James, C.D. and Turner, A.M.P. (2001). Chemical and
Topographical Patterning for Directed Cell Attachment, Current Opinion in
Solid State and Materials Science, 5: 177–184.
44. Karacs, A., Fancsaly, A.J., Divinyi, T., Peto, G. and Kovách, G. (2003).
Morphological and Animal Study of Titanium Dental Implant Surface
Induced by Blasting and High Intensity Pulsed Nd-Glass Laser, Mater. Sci.
Eng. C, 23: 431–435.
45. Martin, J.Y., Schwartz, Z., Hummert, T.W., Schraub, D.M., Simpson, J.,
Lankford, J., Jr., Dean, D.D., Cochran, D.L. and Boyan, B.D. (1995). Effect
of Titanium Surface Roughness on Proliferation, Differentiation, and
Protein Synthesis of Human Osteoblast-like Cells (MG63), J. Biomed.
Mater. Res., 29: 389–401.
46. Groessner-Screiber, B. and Tuan, R.S. (1992). Enhanced Extracellular
Matrix Production and Mineralization by Osteoblasts Cultured on Titanium
Surfaces In vitro, J. Cell Sci., 101: 209–217.
47. Gaggl, A., Schultes, G., Müller, W.D. and Kärcher, H. (2000). Scanning
Electron Microscopical Analysis of Laser-treated Titanium Implant
Surfaces – A Comparative Study, Biomaterials, 21: 1067–1073.
48. Rajnicek, A.M., Britland, S. and McCraig, C.D. (1997). Contact Guidance
of CNS Neurites on Grooved Quartz: Influence of Groove Dimensions,
Neuronal Age and Cell Type, J. Cell Sci., 110: 2905–2913.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
46 A. KURELLA AND N. B. DAHOTRE

49. Clark, P., Connolly, P., Curtis, A.S.G., Dow, J.A.T. and Wilkinsin, C.D.W.
(1990). Topographical Control of Cell Behavior – II Multiple Grooved
Substrata, Development, 108: 635–644.
50. Duncan, A.C., Weisbuch, F., Rouais, F., Lazare, S. and Baquey, C. (2002).
Laser Microfabricated Model Surfaces for Controlled Cell Growth,
Biosensors Bioelectronics, 17: 413–426.
51. Steen, W.M. (1991). Background and General Applications, In: Steen, W.M.
(ed.), Laser Material Processing, pp. 7–37, Springer-Verlag, London, UK.
52. Agarwal, A. and Dahotre, N.B. (2000). Mechanical Properties of Laser
Engineered Composite Boride Coating on Steel: A Nanoindentation
Approach, Metall. Mater. Trans. A, 31A: 401–407.
53. Dasari, A., Nayak, S., Misra, R.D.K., Popoola, O.O. and Dahotre, N.B.
(2002). Evaluation of Laser Surface Engineered Iron Oxide Coatings
on Cast Aluminum Alloy for Wear Application, Mater. Sci. Technol.,
18: 11–18.
54. Kuiry, S.C., Wannaparhun, S., Dahotre, N.B. and Seal, S. (2004). In-situ
Formation of Ni-Alumina Nanocomposite During Laser Processing, Scripta
Materialia, 50: 1237–1240.
55. Nayak, S. and Dahotre, N.B. (2002). The Laser Induced Combustion
Synthesis of Iron Oxide Nanocomposite Coating on Aluminum, J. Miner.
Metals Mater. Soc., 54: 39–41.
56. Dahotre, N.B., McCay, T.D. and McCay, M.H. (1989). Laser Processing of a
SiC/Al-alloy Metal Matrix Composite, J. Appl. Phys., 65: 5072–5077.
57. Dahotre, N.B., Nayak, S. and Popoola, O.O. (2001). Laser Assisted
Iron Oxide Coating on Cast Al Alloy for Automotive Engine Application,
Journal of Minerals, Metals and Materials Society (JOM), 53: 44–46.
58. Nayak, S., Reister, L., Meyer, III, H.M. and Dahotre, N.B. (2003). Micro-
Mechanical Properties of Laser Induced Iron Oxide-Aluminum Matrix
Composite Coating, J. Mater. Res., 18: 833–839.
59. Agarwal, A. and Dahotre, N.B. (2000). Elevated Temperature Oxidation
of Laser Engineered Composite Boride Coating on Steel, Metall. Mater.
Trans. A, 31A: 461–473.
60. Godavarty, A., Agarwal, A. and Dahotre, N.B. (2000). Neural Networks
in Studies on Oxidation Behavior of Laser Surface Engineered Composite
Boride Coating, Appl. Surf. Sci., 161(1–2): 129–136.
61. Kadolkar, P. and Dahotre, N.B. (2003). Effect of Processing Parameters on
the Cohesive Strength of Laser Surface Engineered Ceramic Coatings on
Aluminum Alloys, Mater. Sci. Eng. A, 342: 183–191.
62. O’Shea, D., Callen, R.W. and Rhodes, W.T. (1977). Modifying the
Laser Output, In: O’Shea, D., Callen, R.W. and Rhodes, W.T. (eds), An
Introduction to Lasers and Their Applications, 2nd Printing, pp. 107–124,
Addison-Wesley Publishing Company, Inc., Philippines.
63. Hong, M.H., Huang, S.M., Luk’yanchuk, B.S. and Chong, T.C. (2003).
Laser Assisted Surface Nanopatterning, Sensors Actuators A: Physical, 108:
69–74.
64. D’Alessio, L., Teghil, R., Zaccagnino, M., Zaccardo, I., Ferro, D. and
Marotta, V. (1999). Pulsed Laser Ablation and Deposition of Bioactive

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 47

Glass as Coating Material for Biomedical Applications, Appl. Surf. Sci.,


138–139: 527–532.
65. Reimers, H., Gold, J., Kasemo, B. and Chakarov, D. (2003). Topographical
and Surface Chemical Characterization of Nanosecond Pulsed-Laser Micro-
machining of Titanium at 532 nm Wavelength, Appl. Phys. A, 77: 491–498.
66. Nakayama, Y. and Matsuda, T. (1995). Surface Microarchitectural Design
in Biomedical Applications: Preparation of Microporous Polymer Surfaces
by an Excimer Laser Ablation Technique, J. Biomed. Mater. Res., 29:
1295–1301.
67. Pique, A., Auyeung, R.C.Y., Stepnowski, J.L., Weir, D.W., Arnold, C.B.,
McGill, R.A. and Chrisey, D.B. (2003). Laser Processing of Polymer
Thin Films for Chemical Sensor Applications, Surf. Coat. Techn., 163–
164: 293–299.
68. Zeng, H. and Lacefield, W.R. (2000). XPS, EDX and FTIR Analysis of Pulsed
Laser Deposited Calcium Phosphate Bioceramic Coatings: The Effects of
Various Process Parameters, Biomaterials, 21: 23–30.
69. Clèries, L., Martı́nez, E., Fernández-Pradas, J.M., Sardin, G., Esteve, J. and
Morenza, J.L. (2000). Mechanical Properties of Calcium Phosphate Coatings
Deposited by Laser Ablation, Biomaterials, 21: 967–971.
70. Fernandez-Pradas, J.M., Cleries, L., Sardin, G. and Morenza, J.M. (2002).
Characterization of Calcium Phosphate Coatings Deposited by Nd : YAG
Laser Ablation at 355 nm: Influence of Thickness, Biomaterials, 23:
1989–1994.
71. Antonov, E.N., Bagratashvili, V.N., Popov, V.K., Ball, M.D., Grant, D.M.,
Howdle, S.M. and Scotchford, C.A. (2003). Properties of Calcium Phosphate
Coatings Deposited and Modified with Lasers, JOM: Materials in Medicine,
14: 151–155.
72. Hao, L. and Lawrence, J. (2003). Effects of CO2 Laser Irradiation on the
Wettability and Human Skin Fibroblast Cell Response of Magnesia Partially
Stabilized Zirconia, Mater. Sci. Eng. C, 23: 627–639.
73. Tosto, S., Bartolomeo, A.D. and Lazzaro, P.D. (1996). Surface Ablation
by Excimer Laser Irradiation of Ti and Ti6Al4V Alloy, Appl. Phys. A, 63:
385–389.
74. Preuss, S. (1995). Sub-picosecond UV Laser Ablation of Metals, Appl.
Phy. A, 61: 33–37.
75. Mele, A., Guidoni, A.G., Kelly, R., Flamini, C. and Orlando, S. (1997). Laser
Ablation of Metals: Analysis of Surface-heating and Plume-expansion
Experiments, Appl. Surf. Sci., 109–110: 584–590.
76. György, E., Mihailescu, I.N., Serra, P., Perez del Pino, A. and Morenza, J.L.
(2002). Single Pulse Nd : YAG Laser Irradiation of Titanium: Influence
of Laser Intensity on Surface Morphology, Surf. Coat. Technol., 154: 63–67.
77. Hallgren, C., Reimers, H., Chakarov, D., Gold, J. and Wennerberg, A. (2003).
An In-vivo Study of Bone Response to Implants Topographically Modified
by Laser Micromachining, Biomaterials, 24: 701–710.
78. Callewaert, K., Martelé, Y., Breban, L., Naessens, K., Vandaele, P.,
Baets, R., Geuskens, G. and Schacht, E. (2003). Excimer Laser Induced
Patterning of Polymeric Surfaces, Appl. Surf. Sci., 208–209: 218–225.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
48 A. KURELLA AND N. B. DAHOTRE

79. Rizvi, N.H. and Apte, P. (2002). Developments in Laser Micro-machining


Techniques, J. Mater. Proc. Technol., 127: 206–210.
80. Rizvi, N.H. (1999). Production of Novel 3D Microstructures Using
Excimer Laser Mask Projection Techniques, In: Courtois, B., Crary, S.B.,
Ehrfeld, W., Fujita, H., Karam, J.E. and Markus, K.W. (eds), Proceedings
of SPIE, Design, Test, and Microfabrication of MEMS and MOEMS,
Vol. 3680, pp. 546–552, SPIE, Belligham, WA, USA.
81. Venkatakrishnan, K., Tan, B. and Sivakumar, N.R. (2002). Sub-micron
Ablation of Metallic Thin Film by Femtosecond Pulse Laser, Optics Laser
Technol., 34: 575–578.
82. Zhao, J., Huettner, B. and Menschig, A. (2001). Microablation with
Ultrashort Laser Pulses, Optics Laser Technol., 33: 487–491.
83. Bähnisch, R., Grob, W., Staud, J. and Menschig, A. (1999). Femtosecond
Laser-based Technology for Fast Development of Micromechanical Devices,
Sensors Actuators A: Physical, 74: 31–34.
84. Booth, H.J. (2004). Recent Applications of Pulsed Lasers in Advanced
Materials Processing, Thin Solid Films, 453–454: 450–457.
85. Dunsky, C. (2001). Beam Shaping Applications in Laser Micromachining
for the Microelectronics Industry, In: Dickey, F.M., Holswade, S.C. and
Shealy, D.L. (eds), Laser Beam Shaping II, SPIE, Vol. 4443, p. 135, SPIE,
Belligham, WA, USA.
86. Favret, E., Fuentes, N.O. and Yu, F. (2004). RIMAPS and Variogram
Analysis of the Surface Topography Induced by Laser Interference
Micropatterning, Appl. Surf. Sci., 230: 60–72.
87. Tan, B., Venkatakrishnan, K. and Tok, K.G. (2003). Selective Surface
Texturing Using Femtosecond Pulsed Laser Induced Forward Transfer,
Appl. Surf. Sci., 207: 365–371.
88. Yamada, H., Sano, T., Nakayama, T. and Miyamoto, I. (2002). Optimization
of Laser-induced Forward Transfer Process of Metal Thin Films, Appl. Surf.
Sci., 197–198: 411–415.
89. Karaiskou, A., Zergioti, I., Fotakis, C., Kapsetaki, M. and Kafetzopoulos, D.
(2003). Microfabrication of Biomaterials by the Sub-ps Laser-Induced
Forward Transfer Process, Appl. Surf. Sci., 208–209: 245–249.
90. Wu, P.K., Ringeisen, B.R., Callahan, J., Brooks, M., Bubb, D.M., Wu, H.D.,
Piqué, A., Spargo, B., McGill, R.A. and Chrisey, D.B. (2001). The Deposition,
Structure, Pattern Deposition, and Activity of Biomaterial Thin-films by
Matrix-assisted Pulsed-Laser Evaporation (MAPLE) and MAPLE Direct
Write, Thin Solid Films, 398–399: 607–614.
91. Piqué, A., Auyeung, R.C.Y., Stepnowski, J.L., Weir, D.W., Arnold, C.B.,
McGill, R.A. and Chrisey, D.B. (2003). Laser Processing of Polymer Thin Films
for Chemical Sensor Applications, Surf. Coat. Technol., 163–164: 293–299.
92. Harris, J.M., Dust, J.M., McGill, R.A., Harris, P.A., Edgell, M.J., Sedaghat-
Herati, R.M., Karr, L.J. and Donnelly, D.L. (1991). Water-Soluble Polymers,
In: Shalaby, S.W., McCormick, C.L. and Butler, G.B. (eds), ACS Symposium
Series, Vol. 467, p. 418, ACS, Washington DC, USA.
93. Suggs, L.J., Kao, E.Y., Palombo, L.L., Krishnan, R.S., Widmer, M.S. and
Mikos, A.G. (1998). Preparation and Characterization of Poly(Propylene

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Surface Modification by Laser for Bioimplants 49

Fumarate-co-Ethylene Glycol) Hydrogels, J. Biomater. Sci. Polym. Ed.,


9(7): 653–666.
94. Kaneko, Y., Sakai, K. and Okano, T. (1998). Temperature-responsive
Hydrogels as Intelligent Materials, In: Okano, T. (ed.), Biorelated Polymers
and Gels, pp. 29–69, Academic, New York.
95. Chong, C. and Lu, Y.-F. (2002). An Overview of Laser Microprocessing in
Data Storage Industry, In: Thomas, D.T., Keirstead, M.S. and Hodgson,
Norman (eds), Proceedings of SPIE, Vol. 4426, p. 17, SPIE, Belligham, WA,
USA.
96. Jersch, J. and Dickmann, K. (1996). Nanostructure Fabrication Using
Laser Field Enhancement in the Near-field of a Scanning Tunneling
Microscope Tip, Appl. Phys. Lett., 68: 868–870.
97. Gerardino, A., Notargiacomo, A. and Morales, P. (2003). Laser Assisted
Deposition of Nanopatterned Biomolecular Layers, Microelectronic
Engineering, 67–68: 923–992.
98. Ito, Y. (1999). Surface Micropatterning to Regulate Cell Functions,
Biomaterials, 20: 2333–2342.
99. Brunette, D.M. and Chehroudi, B. (1999). The Effects of the Surface
Topography of Micromachined Titanium Substrata on Cell Behavior
In-vitro and In-vivo, J. Biomech. Eng., 121(1): 49–57.
100. Wilkinson, C.D.W., Riehle, M., Wood, M., Gallagher, J. and Curtis, A.S.G.
(2002). The Use of Materials Patterned on a Nano- and Micro-Metric
Scale in Cellular Engineering, Mater. Sci. Eng. C, 19: 263–269.
101. Webster, T.J., Ergun, C., Doremus, R.H., Siegel, R.W. and Bizios, R.
(2001). Enhanced Functions of Osteoblasts on Nanophase Ceramics,
Biomaterials, 21: 1803–1810.
102. Ji, B. and Gao, H. (2004). Mechanical Properties of Nanostructure of
Biological Materials, J. Mech. Phy. Solids, 52: 1963–1990.
103. Dan, N. (2000). Synthesis of Hierarchical Materials, Trends Biotechnol.,
18: 370–374.
104. Mann, S. (1995). Biomineralization and Biomimetic Materials Chemistry,
J. Mater. Chem., 5: 935–946.
105. Kurella, A. and Dahotre, N.B. (2004). Unpublished Work.
106. György, E., Perez del Pino, A., Serra, P. and Morenza, J.L. (2002).
Growth of Surface Structures on Titanium through Pulsed Nd : YAG
Laser Irradiation in Vacuum, Appl. Surf. Sci., 197–198: 851–855.
107. György, E., Mihailescu, I.N., Serra, P., Pérez del Pino, A. and Morenza, J.L.
(2002). Single Pulse Nd : YAG Laser Irradiation of Titanium: Influence
of Laser Intensity on Surface Morphology, Surf. Coat. Tech., 154: 63–67.
108. Guillemot, F., Prima, F., Tokarev, V.N., Belin, C., Porté-Durrieu, M.C.,
Gloriant, T., Baquey, Ch. and Lazare, S. (2003). Ultraviolet Laser
Surface Treatment for Biomedical Applications of -Titanium Alloys:
Morphological and Structural Characterization, Appl. Phys. A: Mater. Sci.
Proc., 77: 899–904.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
50 A. KURELLA AND N. B. DAHOTRE

BIOGRAPHICAL SKETCHES

Anil Kurella

Anil Kurella did his BSc in Metallurgical Engineering from Andhra


University, India. He later worked in International Advanced Research
Centre for Powder Metallurgy and New Alloys (ARCI) India as a
Research Fellow. Currently, he is a graduate student in the Department
of Materials Science and Engineering, University of Tennessee,
Knoxville, USA pursuing doctoral studies in Materials Science.

Narendra B. Dahotre

Narendra B. Dahotre is a Professor with joint appointment with


Oak Ridge National Laboratory and Department of Materials Science
and Engineering of the University of Tennessee-Knoxville. He is also
a senior faculty member of the Center for Laser Applications at the
University of Tennessee Space Institute-Tullahoma. Dr Dahotre is
the author and co-author of over 80 technical articles and editor of 11
technical books. He holds 15 US patents in laser materials processing.
He has organized 12 symposia and conferences in the area of Surface
Engineering and High Temperature Coatings. He has successfully
conducted several research projects funded by government and private
industry in the field of laser surface engineering. His current research
continues to be in laser based surface engineering. He is a member of
TMS, ASM, SME, ASME, and AAAS. He is a joint Chair of the Surface
Engineering Committee of TMS and a member of ASM International
Surface Engineering Task Force. He has been elected to the 2004 Class
of ASM International Fellows. He received his MSc and PhD degrees
in metallurgical engineering and materials science and engineering
from Michigan State University.

Downloaded from http://jba.sagepub.com at PENNSYLVANIA STATE UNIV on April 15, 2008


© 2005 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.