Laser Processing of Materials: J Dutta Majumdar and I Manna
Laser Processing of Materials: J Dutta Majumdar and I Manna
Laser Processing of Materials: J Dutta Majumdar and I Manna
© Printed in India
1. Introduction
∗ References in this paper have not been cited or prepared in journal format
495
496 J Dutta Majumdar and I Manna
computer), and life saving (surgery) to life threatening (weapons/guide). Laser is useful in
metrology (length/velocity/ roughness measurement), entertainment (laser light show), med-
ical diagnostics and surgery/therapy and optical communication/computation. From printer
to pointer, surgery to spectroscopy, isotope separation to invisible surveillance and medical
to material treatment, laser finds a ubiquitous presence mainly for some unique combination
of properties. These important properties that justify the use of laser in such a wide spectrum
of applications are (a) spatial and temporal coherence (i.e., phase and amplitude are unique),
(b) low divergence (parallel to the optical axis), (c) high continuous or pulsed power density,
and (d) monochromaticity [1–10].
Figure 1 presents a brief overview of the application of laser in different fields with diverse
objective [1]. Though the list is not exhaustive, it serves to show the diversity of applica-
tion of laser. In some applications, the power output is of main concern, e.g. atomic fusion
and isotope separation. Sometimes, the main reason for using laser lies in its spectral purity
and coherence (pollution detection, length/velocity measurement, interferometry, etc.), low
divergence (laser show, pointer/guide, audio-player), or a combination of all of them (com-
munication, holography, metrology). Accordingly, a host of lasers capable of delivering a
wide variety of wavelength, energy, temporal/spectral distribution and efficiency have been
developed over the last several decades [1].
In the present contribution, we would confine ourselves to only laser material process-
ing. The intense heat that laser may produce on solid matter enables several types of ultra-
fast, novel and economical processing of material that are distinctly advantageous from the
quality, productivity and efficiency point of view than that possible with their conventional
counterparts. We will, at first, review the history of laser and enlist the main types of commer-
cial laser used in material processing before introducing the working principle of the most
Applications of lasers
Heat
Communi- Enter- source
cation Metrology Reprography tainment Military Chemical Medical (LMP)
commonly used ones. Before embarking upon reviewing the current status of laser material
processing, we will discuss the physics of laser–matter interaction and classify the differ-
ent types of laser processing of materials. Finally, we will present a comprehensive update
of the studies on different types of laser material processing and highlight the scientific and
technological aspects of importance. In order to confine ourselves to the prescribed limit, we
have deliberately reviewed the literature published from 1995 onwards. This cut-off, even
though arbitrary, was unavoidable due to restriction on the length of the paper. However, this
restriction applies only to the cited literatures but not to discussing the fundamentals of the
subject. For further details on laser material processing, the textbook by Steen [1] is the most
comprehensive source of information.
Laser is surely one of the greatest innovations of 20th century. Its continued development has
been an exciting chapter in the history of science, engineering and technology. As a versatile
source of pure energy in a highly concentrated form, laser has emerged as an attractive
tool and research instrument with potential for applications in an extraordinary variety of
fields.
The initial foundation of laser theory was laid by Einstein [11]. Subsequently, Kopfer-
mann & Ladenburg [12] presented the first experimental confirmation of Einstein’s predic-
tion. In 1960, Maiman [13] developed a ruby laser for the first time. This was followed by
much basic development of lasers from 1962 to 1968. Almost all important types of lasers
including semiconductor lasers, Nd:YAG lasers, CO2 gas lasers, dye lasers and other gas
lasers were invented in this era. After 1968, the existing lasers were designed and fabricated
with better reliability and durability. By mid 1970s more reliable lasers were made avail-
able for truly practical applications in the industrial applications such as cutting, welding,
drilling and marking. During the 1980s and early 1990s the lasers were explored for sur-
face related applications such as heat treatment, cladding, alloying, glazing and thin film
deposition.
Table 1 summarises commercially available lasers and their main areas of application.
Depending on the type of laser and wavelength desired, the laser medium is solid, liquid or
gaseous. Different laser types are commonly named according to the state or the physical
properties of the active medium. Consequently, we have crystal, glass or semiconductor, solid
state lasers, liquid lasers, and gas lasers. The latter (gas lasers) can be further subdivided into
neutral atom lasers, ion lasers, molecular lasers and excimer lasers. The typical commercially
available lasers for material processing are (a) solid state crystal or glass laser – Nd:YAG,
Ruby, (b) semiconductor laser – AlGaAs, GaAsSb and GaAlSb lasers, (c) dye or liquid lasers-
solutions of dyes in water/alcohol and other solvents, (d) neutral or atomic gas lasers – He–Ne
laser, Cu or Au vapour laser, (e) ionized gas lasers or ion lasers – argon (Ar+ ) and krypton
(Kr+ ) ion lasers, (f) molecular gas lasers – CO2 or CO laser, and (g) excimer laser – XeCl,
KrF, etc. Wavelengths of presently available lasers cover the entire spectral range from the
far-infrared to the soft X-ray.
3. Generation of laser
Laser is a coherent and amplified beam of electromagnetic radiation or light. The key element
in making a practical laser is the light amplification achieved by stimulated emission due to the
498 J Dutta Majumdar and I Manna
Year of Commercialised
Laser discovery since Application
incident photons of high energy. A laser comprises three principal components, namely, the
gain medium (or resonator), means of exciting the gain medium into its amplifying state and
optical delivery/feed back system. Additional provisions of cooling the mirrors, guiding the
beam and manipulating the target are also important. The laser medium may be a solid (e.g.
Nd:YAG or neodymium doped yttrium–aluminum–garnet), liquid (dye) or gas (e.g. CO2 , He,
Ne, etc.). For gas and diode lasers, the energy is usually introduced directly by electric-current
flow, whereas, an intense flash of white light produced by incandescent lamps introduces the
excitation energy in solid state crystal lasers. The sudden pumping of energy causes the laser
medium to fluoresce and produce intense monochromatic, unidirectional (parallel/convergent)
and coherent rays [1,2]. Among the commercially available lasers, CO2 -laser seems one of the
earliest developed and most popular lasers for material processing because they are electrically
more efficient (15–20%) and produce higher powers (0·1–50 kW) than other lasers in the
continuous mode. Despite being less efficient in energy coupling with metals due to longer
wavelength (10·6 µm), the higher wall plug (∼ 12%) and quantum (∼ 45%) efficiency and
output power level of CO2 lasers more than compensate for the poor laser–matter energy
coupling capability. On the other hand, Nd:YAG and Ruby lasers possess shorter wavelength
and are more suited to pulsed mode of applications requiring deeper penetration, smaller area
coverage and precision treatment of materials for specific purposes.
As illustrated in figure 2a, the CO2 -laser device consists of three main parts – a gain or
laser medium, an optical resonator or cavity with two mirrors, and an energizing or pumping
source that supplies energy to the gain medium. The chemical species in the gain medium
determines the wavelength of the optical output. Between the two mirrors, one is a fully
reflecting and the other a partially reflecting one. From the quantum mechanical principle,
when an external energy is supplied to an atom, the irradiated atom attains an excited state
Laser processing of materials 499
Figure 2. Schematic set-up of continuous wave CO2 laser. (a) The major constituents of the machine,
(b) initial stage of energy pumping, (c) excitation and de-excitation of the atoms in the medium leading
to emission of laser and (d) stimulated emission and formation of laser beam.
(figure 2b). The excited atom spontaneously returns to the ground state (E1 ) from the higher
energy state (E2 ) by emitting the energy difference as a photon of frequency (ν):
ν = (E2 − E1 )/ h, (1)
where, h is the Planck’s constant. This phenomenon is known as spontaneous emission (fig-
ure 2c). A spontaneously emitted photon may in turn excite another atom and stimulate it to
emit a photon by de-exciting it to a lower energy level. This process is called stimulated emis-
sion of radiation (figure 2c). The latter is coherent with the stimulating radiation so that the
wavelength, phase and polarization between the two are identical. A photon interacting with
an unexcited atom may get absorbed by it and excite it to higher energy state. This situation,
called ‘population inversion’ is created by the pumping source. The photons moving along the
optic axis interact with a large number of excited atoms, stimulate them and by this process
get amplified. They are reflected back and forth by the resonator mirrors and pass through
the excited medium creating more photons. In each round trip, a percentage of these photons
exit through the partially transmitting mirror as intense laser beam (figure 2d). Finally, the
500 J Dutta Majumdar and I Manna
laser beam is either guided on to the work-piece by using reflecting mirrors or delivered at
the desired site through optical fibres.
Figure 3 shows a schematic outline of a solid state neodymium doped yttrium aluminum
garnet (Nd:YAG). The generation of high average power in Nd–YAG laser systems is accom-
plished by combining several individually pumped laser rods in a single resonator. Pumping
is performed with arc lamps mounted in a close coupling optical geometry that ensures the
maximum possible absorption of visible pump radiation by the laser rod. This optimizes both
pumping efficiency and energy extraction efficiency. Energy pumping selectively energizes
the Nd ions that subsequently lead to a cascading effect and stimulated emission of light.
These days, energy pumping is also done with diode lasers of appropriate frequency. Nd:YAG
laser has 40% quantum efficiency. However, the overall electrical efficiency of YAG lasers is
low. The ratio of laser output power to electrical input power lies in the range 0·5–3%. The
major advantages of Nd–YAG laser over CO2 laser lie in its smaller wavelength (1·06 µm)
and ability to deliver laser radiation through optical fibers.
The input of energy or energy deposition process from a pulsed/continuous wave laser beam
into the near-surface regions of a solid involves electronic excitation and de-excitation within
an extremely short period of time [8–10]. In other words, the laser–matter interaction within
the near-surface region achieves extreme heating and cooling rates (103 –1010 K/s), while the
total deposited energy (typically, 0·1–10 J/cm2 ) is insufficient to affect, in a significant way,
the temperature of the bulk material. This allows the near-surface region to be processed under
extreme conditions with little effect on the bulk properties.
incident laser beam promoting electrons within the metal to states of higher energy. Electrons
that have been excited in this manner can divest themselves of their excess energy in a variety of
ways. For example, if the photon energy is large enough, the excited electrons can be removed
entirely from the metal. This is the photoelectric effect and usually requires photon energies
greater than several electron volts. Most laser processing applications, however, utilize lasers
emitting photons with relatively low energy. The energy of CO2 laser photons is only 0·12 eV
while the photons obtained from the Nd:YAG laser have about 1·2 eV of energy. Electrons
excited by absorption of CO2 or Nd:YAG laser radiation do not therefore have enough energy
to be ejected from the metal surface. Such electrons must, nevertheless, lose energy to return to
an equilibrium state after photon excitation. This occurs when excited electrons are scattered
by lattice defects like usual non-crystalline regions in a crystal such as dislocations and grain
boundaries such as the lattice deformation produced by photons. In either case, the overall
effect is to convert electronic energy derived from the beam of incident photons into heat. It
is this heat that is useful (indeed necessary) in all surface treatment applications.
Figure 4. Schematic diagram depicting electron excitation and carrier relaxation process in materials
subjected to intense laser irradiation.
502 J Dutta Majumdar and I Manna
where, Io is the incident intensity, t is time, R and α are the reflectivity and absorption coef-
ficients, respectively. Since α is very high (∼ 106 cm−1 ) for metals, light is totally absorbed
within a depth of 100–200 Å. The efficiency of optical coupling is determined by the reflec-
tivity (R). R for metals is relatively low at short wavelengths, rises abruptly at a critical
wavelength (related to the plasma frequency of the free electron plasma), and then remains
very high at long wavelength [8].
For comparison, the deposited energy profile from the other two important directed-energy-
sources, namely electron and ion beams, are also shown in figure 5b and figure 5c, respectively.
The energy deposition profile for electron beam irradiation of matter is given by a gaussian
function,
where, RE is the reflectivity for e-beam, xP is the distance (x) that coincides with the peak
intensity and fE (x/xP ) is the spatial energy deposition profile. The deposition profile depends
on the energy loss hence on incident energy and atomic number. Thus, electron beam is
more suited to deep penetration welding than surface engineering applications. Similarly, the
concentration of the implanted species in ion beam irradiation does not coincide with the top
surface but lies underneath the surface (4):
Laser processing of materials 503
( " #)
z − RP 2
C(z) = QT /(2π ) 1/2
1RP exp − √ , (4)
21RP
Here, C(z) is the concentration of a given species at a vertical distance z, Rp is the projected
range/distance and QT is the dose.
D = k/(ρCP ), (5)
where, ρ is the density. The vertical distance (z) over which heat diffuses during the pulse
duration (tp ) is given by, z = (2Dtp )1/2 . Here, z in comparison to α −1 determines the
temperature profile. The condition of α −1 z is applicable typically for laser irradiation of
metals.
Under the one dimensional heat flow condition, the heat balance equation may be expressed
as [5]:
∂T (z, t) ∂ ∂T (z, t)
ρcp = Q(z, t) + k (6)
∂T ∂z ∂z
where, T and Q are the temperature and power density at a given vertical distance of depth
(z) and time (t), respectively. Q follows a functional relation with z same as (2). The heat
balance equation (6) may be solved analytically if the coupling parameters (α and R) and
materials parameters (ρ, k and cP ) are not temperature and phase dependent. However, phase
changes are unavoidable except in solid state processing. Thus, the heat balance equation is
solved by numerical techniques like finite difference/element methods.
Depending on the temperature profile, the irradiated material may undergo only heating,
melting or vapourization. For surface melting and subsequent re-solidification, the solid-liquid
interface initially moves away from and then travels back to the surface with the velocity
as high as 1–30 m/s. The interface velocity is given by v ∝ (Tm − Ti ), where Tm and Ti
are the melting and interface temperatures, respectively [8]. Further details on mathematical
modelling of heat transfer in laser material processing may be obtained in several textbooks
[5,6].
The increasing demand of laser in material processing can be attributed to several unique
advantages of laser namely, high productivity, automation worthiness, non-contact process-
ing, elimination of finishing operation, reduced processing cost, improved product quality,
greater material utilization and minimum heat affected zone [1–10]. Figure 6 shows a gen-
eral classification of the laser material processing techniques. In general, application of laser
to material processing can be grouped into two major classes, (a) applications requiring lim-
ited energy/power and causing no significant change of phase or state, and (b) applications
504 J Dutta Majumdar and I Manna
requiring substantial amount of energy to induce the phase transformations. The first category
includes semiconductor annealing and etching, polymer curing, scribing/marking of inte-
grated circuit substrates, etc. The second type of application encompasses cutting, welding,
fusion, heat treatments, etc. The average power and efficiency of lasers are not that important
for the former category that involves no change in phase or state. Lasers suitable for this group
of applications include (but not limited to) excimer lasers (KrF, ArF), ion lasers (Ar+ , Kr+ ),
metallic vapour lasers (cadmium, selenium, copper, gold), solid state lasers (Nd–YAG, Nd–
glass), semiconductor lasers (gallium aluminum arsenide, etc.), and molecular lasers (CO2 ,
CO, etc.). For the second category, laser power/efficiency and interaction-time are crucial as
the processes involve single or multiple phase changes within a very short time. Because of
high-energy requirement, for this class of operations, CO2 and Nd–YAG lasers are practically
the only choice.
The classification based on phase changes or no phase changes is too academic to be of real
use to the end users. From the true application point of view, laser material processing can be
broadly divided into four major categories, namely, forming (manufacturing of near net-shape
or finished products), joining (welding, brazing, etc.), machining (cutting, drilling, etc.) and
surface engineering (processing confined only to the near-surface region) [1–20]. Figure 6
presents this classification in the lower half of the figure mentioning a few representative
examples from each category of application. However, this classification is based on the
general definition and scope of the processes as understood in conventional practice, but is
certainly not sacrosanct.
Laser processing of materials 505
Surface
amorphization
Colouring
Figure 7. Process map (schematic) in terms of laser power density as a function of interaction time
for different examples of laser material processing.
The domain for different laser material processing techniques as a function of laser power
and interaction time is illustrated in figure 7 [1]. The processes are divided into three major
classes, namely involving only heating (without melting/vapourizing), melting (no vapour-
izing) and vapourizing. Obviously, the laser power density and interaction/pulse time are so
selected in each process that the material concerned undergoes the desired degree of heat-
ing and phase transition. It is evident that transformation hardening, bending and magnetic
domain control which rely on surface heating without surface melting require low power den-
sity. On the other hand, surface melting, glazing, cladding, welding and cutting that involve
melting require high power density. Similarly, cutting, drilling and similar machining oper-
ations remove material as vapour, hence need delivery of a substantially high power density
within a very short interaction/pulse time. For convenience, a single scalar parameter like
energy density (power density multiplied by time, J/mm2 ) is more useful for quantifying
different laser assisted processes. However, the practice is not advisable as the specific com-
bination of power and time (rather than their product) can only achieve the desired thermal
and material effect.
In the following sections, we review the individual classes of laser material processing and
the current status of understanding.
6. Laser forming
One of the major goals of material processing is to produce finished products of correct
design, shape, geometry and dimension. Manufacturing a finished product is seldom a one-
506 J Dutta Majumdar and I Manna
step process. On the contrary, developing a final product involves several primary (procur-
ing, winning/extraction, selection, blending), secondary (melting, casting, compaction, sin-
tering) and tertiary (machining, polishing, shaping) steps that are all inter-related, complex
and time/energy/manpower intensive. Laser material processing offers a unique possibility
of manufacturing finished products directly from the raw materials without any elaborate
intermediate operation [1–4,15]. A one-step fabrication is most attractive, obviously for the
tremendous economy in time, cost, material and manpower than that necessary for the usual
route of fabrication. Though such possibility is not unlimited and rather confined to only a
few types of materials and operations, nevertheless, direct fabrication of components using
laser as a non-contact tool is obviously a breakthrough that must be vigorously pursued.
Among the several types of laser assisted forming or manufacturing processes in vogue,
the major and successful ones include laser assisted bending, colouring, rapid prototyping,
fabrication, deposition, and laser reclamation/repairing [1–4]. These processes distinguish
themselves from other laser material processing methods in their proclaimed objective of
single-step manufacturing of a finished or semi-finished product than serving to any other
intermediate processing aim like machining, joining or surface engineering. For brevity, we
will address all these laser-assisted versions of otherwise conventional manufacturing pro-
cesses as laser forming.
Table 2 summarizes the major and representative studies carried out in the broad area of
laser forming in the recent past (1995 onwards) [21–38]. These studies are selected primarily
to emphasize the variety of possibilities and their status in laser forming of materials.
Table 2. Summary of selected studies on laser forming of materials in the recent past (1995 onwards).
Laser bending
Bending 2001 Al–2024 and Pulsed laser Study the effect of The smaller the [21]
15–20% SiCp reinforcement on reinforcement, the
composite bending angle and higher the bending
compare the angle. A single
predicted results model cannot
account for all
regimes
Bending 2000 Stainless steel Pulsed Study the effect of Bending varies [22]
sheet Nd:YAG process parameters inversely with
on bending angle sheet thickness and
directly with power
(below a minimum
or threshold)
Bending 1999 Stainless steel Nd:YLF, Finite element Reflectivity and [23]
sheet line-shaped modelling of thermal expansion
pulsed thermoelastoplastic coefficient
mode of influence the
deformation bending more than
any other parameter
Bending 1998 AlCuMg-and CW–CO2 Study the effect of Bend rate/angle [24]
α/β–Ti alloy and Nd:YAG laser parameters primarily depends
and analytically on temperature and
determine plain decreases with
strain pulses due to
material accumu-
lation at bend
Ceramic 1995 Cr2 O3 coating CW–CO2 Study the interfacial Up to 200 µm [25]
coating on SAF 2205 bonding strength thick Cr2 O3
on metals steel and compatibility cladding on steel
between Cr2 O3 and possible by laser
steel cladding. Stress at
the interface is
very high
Laser manufacturing
Table 2. (Continued).
Laser metal 1999 Ni-based CW–CO2 Utilize electron Close control of [27]
forming superalloy back scattered solidification
image for micro-structure and
orientation orientation
determination of distribution is
laser formed layer possible in epitaxi-
ally grown layer
Laser aided 1996 Hydroxyapatite CW–CO2 Develop funtionally Functionally + [28]
thixotropic + AISI 316 graded clad of compositionally
casting stainless steel ceramic-metal layer graded layers
by laser aided (ceramic to metal)
thixotropic casting developed by laser
thixo-casting under
Laser rapid prototyping vibration
Laser rapid 2001 Pulsed-CO2 Polyvinyl Develop thick Cu on rotating Pt [29]
prototyping chloride (130 µm) masks for disc and NiFe
electrodeposition of criss-cross pattern
double metallic on cylindrical rods
layers on were deposited by
cylinder/rod pattern transfer
Stereo- 2001 He–Cd laser Alumino- Stereolithographic The green was [30]
lithography (325 nm) slicate ceramic fabrication of free successfully
powder standing ceramic developed from
shapes ceramics and
sintered at 1600◦ C
Composite 2000 CW–CO2 Cu–Ti–C and Develop a TiC Addition of Ni helps [31]
surfacing Cu–Ti–Ni–C dispersed surface in better melting
composite layer and wetting of TiC
in the composite
Laser rapid 2000 Q-switched Li–niobate Rapid prototyping SHG, that turns [32]
prototyping Nd:YAG and K–titanyl by second harmonic liquid photo-
phosphate generation (SHG) in polymer into solid,
suspended is a function of
nonlinear crystals particle size and
density. SHG is
useful in rapid
prototyping and 3-D
image formation
Laser rapid 1997 Pulsed laser Al2 O3 Develop photonic 3-dimensional [33]
prototyping band gap structures photonic band gap
by laser rapid structure was
prototyping created by vapour
deposition of FCT-
Al2 O3 into rods
3-D micro- 1995 Pulsed laser Al + Al2 O3 Develop 3-D Thermal expansion [34]
strcture microstructure by by laser irradiation
laser driven allows 1-step direct-
movement write prototyping
(Continued)
Laser processing of materials 509
Table 2. (Continued).
Laser colouring
Colouring 2000 Pulsed KrF Amorphous Colouring of laser Brown (photo- [35]
bleaching excimer and WO3 film deposited thin WO3 chemical activation)
Nd:YAG laser film by laser to purple (photo-
thermal oxidation)
irradiation and study
the mechanism colours obtained by
colouring/bleaching
action
Colouring 2000 Femtosecond Nano-Ag Study mechanism Time frame for [36]
deforming pulsed laser embedded of colouring by transient extinction
glass laser induced dynamics changes
deformation of (along with colour)
nano-Ag particles due to surface
plasmon resonance
Colouring 1996 Excimer laser Stainless steel Restore colour (and Thermochemical [37]
avoid reaction between Fe
discolouration) of and O2 produce
stainless steel different
oxides/colours
Colouring 1995 Femtosecond Copper Study the Three-(red) and [38]
red/UV laser photoemission two-photon (UV)
process in emission process
ultra-short pulses occur when Cu-
cathode is irradiated
by red/UV pulses
may generate a large residual stress gradient and cause delaminating or cracking of Cr2 O3
ceramic cladding on steel sheet [25].
Laser bending is possible only above a threshold heat input. With sufficient thermal input,
bending angle decreases significantly with increasing material thickness. However, bend-
ing angle no longer increases with increasing heat input beyond an upper critical value of
energy input. The decreasing bend rate with increasing irradiation over the same track may be
attributed to increase in elastic modulus due to the thickening of the material along the bending
edge [24]. A two-dimensional plane strain numerical analysis to calculate the bending angle
in pulsed laser irradiation of stainless steel sheet has shown that both optical reflectivity and
thermal expansion coefficient constitute the most important considerations that influence the
precision of the predicted bending angle [23]. However, suitable correlation between bend-
ing dimension and laser parameters would require proper estimation of the effect of relevant
material properties at high temperature on the laser bending.
Figure 8. Schematic set-up for laser rapid prototyping by (a) stereolithography and (b) selected laser
sintering.
controlled laser head scans the surface and cuts out the outline of the desired object. As the
base plate moves down, the whole process starts again. At the end of the build process, the
little crosshatched columns are broken away to free the object. In fused deposition process,
the object is made by squeezing a continuous thread of the material through a narrow nozzle
(heated by laser) that is moved over the base plate (figure 9b). As the thread passes through
the nozzle, it melts only to harden again immediately as it touches (and sticks to) the layer
below. For certain shapes, a support structure is needed, and this is provided by a second
nozzle squeezing out a similar thread, usually of a different colour to make separating the two
easier. At the end of the build process, the support structure is broken away and discarded,
freeing the object/model. The models made from wax or plastics in this method are physically
robust. This new fabrication concept allows construction of complex parts, starting from a
3D–CAD model without a mould.
Figure 9. Schematic set-up for laser rapid prototyping by (a) thin laminated object manufacturing
(for laminates or sheets), and (b) fused laser deposition technique (for solid objects).
512 J Dutta Majumdar and I Manna
Most of these additive processes produce polymeric objects and only recently laser sintering
of metal powders has been commercially introduced. In a similar laser based additive rapid
prototyping approach, it is possible to fabricate free form alumino-silicate ceramic parts
by stereolithography starting from the UV curable pre-ceramic suspension [30]. The final
components are obtained by pyrolysis of the organic binder and sintering at 1600◦ C.
Laser can be a useful tool for in situ rapid prototyping fabrication of composite components
like cutting tools, shear blades, etc. Lu et al, [31] have fabricated TiC dispersed Cu–Ti–C
and Cu–Ni–Ti–C composites by laser scanning of ball milled powder mixtures. It is felt that
addition of Ni improves the integrity and surface quality of the laser-fabricated parts because
of improved melting and wettability of Cu with in situ TiC.
Second harmonic generation using a 1·06 mm Q-switched Nd:YAG beam in powdered
nonlinear crystals suspended in a photopolymeric solution could be useful in high reso-
lution rapid prototyping [32]. Since efficient second harmonic generation occurs for very
small powder grain size, this technique may provide a way of realizing high resolution three
dimensional imaging in which the feature size could be only a few microns in dimension.
Laser rapid prototyping enables fabrication of 3-D solid freeforms by material deposition
in successive layers made of adjacent beads. One such structure developed in this method
was a 3-D periodic photonic band-gap structure of aluminum oxide that consisted of lay-
ers of parallel rods forming a face-centered tetragonal lattice with lattice constants of 66
and 133 µm [33]. A similar laser-driven direct-write deposition technique (from trimethy-
laminealane and oxygen precursors) was successfully utilized to fabricate a 3-D microstruc-
ture consisting of aluminum oxide and aluminum [34]. These laser deposited rapid proto-
type ceramic components are useful as micromechanical actuators like microtweezers and
micro-motors.
7. Laser joining
One of the earliest and most widely practiced applications of laser material processing was
joining of metallic sheets using a continuous wave laser [1,16,17]. Today, the automobile and
aerospace industry relies on lasers for a clean and non-contact source of heating and fusion
for joining of sheets. More than on any other conventional process. Laser joining is appli-
cable to inorganic/organic and similar/dissimilar materials with an extremely high precision,
versatility and productivity that can only be matched by electron beam welding. Moreover,
laser welding can be done in air, unlike the vacuum processing needed in electron beam weld-
ing. In comparison to conventional or arc welding, laser welding scores several advantages
like narrow welds with controlled bead size, faster welding with a higher productivity, less
distortion, narrow heat affected zone, amenability to welding Al/Mg alloys and dissimilar
materials, and minimum contamination [39,40].
Laser joining encompasses welding, brazing, soldering and even, micro welding, sintering,
etc. Joining of materials on a commercial basis requires a laser source of a high power level,
high reliability, easy operation and low cost. Hence, pulsed or continuous wave Nd:YAG or
514 J Dutta Majumdar and I Manna
CO2 laser (very seldom ruby laser, too) are the commonly used lasers for joining. The main
process variables in laser welding are laser power, beam diameter, beam configuration, travel
speed of the work-piece, substrate condition (roughness, temperature), filler type/feed rate,
alloy composition and thermophysical properties of the work piece. Table 3 presents a ready
reference for the most recent and representative studies on laser joining of materials (1995
onwards) [41–70]. These studies are selected primarily to emphasize recent advances and
outline the outstanding issues in using laser as a tool for joining materials.
ε = [vdW 1Hm /P ] .
Equation (7) relates the rate of melting (ε) to incident laser power, P , where v is welding
speed, d is sheet thickness, W is beam width and 1Hm is the heat content of the metal at
the melt temperature. The maximum value of ε is 0·48 for penetration welds and 0·37 for
conduction welds [17]. It is apparent that ε never approaches unity even when η ' 1. Both h
and ε can be enhanced under the keyhole welding condition if the absorption coefficient can be
increased. This can be accomplished by application of absorbent coating, surface roughening
or texturing, preheating, tailoring of temporal irradiation profile and/or oxidation/nitriding.
Among various process parameters, the quality and properties of laser weld depend on laser
pulse time and power density, laser spot diameter/penetration, melt area, melting ratio and
material properties like absorptivity, specific heat, density, etc. Wang et al [41] have demon-
strated the versatility of laser welding by carrying out in-situ weld-alloying and laser beam
welding to join SiC reinforced 6061Al metal matrix composite with titanium. Microstructural
Laser processing of materials 515
Table 3. Summary of selected studies on laser joining of materials in the recent past (1995 onwards).
(Continued)
516 J Dutta Majumdar and I Manna
Table 3. (Continued).
Bright 2000 AISI 304 stain- Photolytic Study welding Extremely narrow [49]
welding less steel iodine laser characteristics of welding seam with
new PIL laser very fine fully
(1315 nm) austenitic
microstructure is
produced with
minimum HAZ
Penetration 1999 High carbon CW–CO2 Study the influence CO2 laser welding [50]
welding steel and diode of laser parameters gives crack free,
laser on weld quality stronger and wider
weld pool
Welding 1997 Austenitic CW–CO2 Study the effect of Microstructure was [51]
stainless steel welding parameters mostly austenitic
on fusion zone (2–3% ferrite).
Higher speed and
lower power
produce better
welding
Welding 1997 Stainless steel CW–CO2 Study the plasma Plasma plume [52]
and titanium plume maintains local
characteristics in thermal equilibrium
welding and reaches 11000 K
Spot 1996 Stainless steel, Semiconductor Study the defect Defect/hole and [53]
welding Kovar, Gold laser formation center line cracks
mechanism in disappear below a
packaging given power density
and air gap,
respectively
Micro- 1995 Stainless steel 70W Study the welding Significant variation [54]
gra-vity CW–CO2 characteristics in of Cr-distribution is
welding varying gravity noted in different
gravity conditions
Laser welding of Ti-alloys
Welding 2001 TiNi shape CW–CO2 Study corrosion, Decrease in Ms - [55]
memory alloys mechanical and start temperature
shape memory and ductility, and
properties of increase in amount
weldments of B2 phase and
strength, but no
change in shape
memory effect are
observed
Melting 2001 Ti–6Al–4V Pulsed Study (in-situ Keyhole formation [56]
alloy Nd:YAG X-ray) the key hole is time dependent
laser formation and and its bottom
correlate melt depth matches with melt
with laser power pool. Melt depth
depends on power
density
(Continued)
Laser processing of materials 517
Table 3. (Continued).
Welding 1997 Ti–6Al–4V CW–CO2 Study fatigue and Crack initiates at [57]
tensile properties of base metal due to
weldments martensite. Aging
reduces crack
growth rate and
produces mixed
mode
Welding 1995 SiC-fibre rein- CW–CO2 Study feasibility Butt and scarf [58]
forced Ti-alloy and mechanical joints were
property of successful. Scarf
weldment angle < 12◦
produced fracture
Laser welding of Mg-alloys
Key-hole 2001 AZ91 and 6 kW Study the feasibility Welding [59]
welding AM50 alloys CW–CO2 and welding morphology and
laser characteristics quality are
correlated to
energy/heat input
Laser brazing
Hard sol- 2001 Diamond film High power Micro-thermal Hard soldering on [60]
dering diode laser management of high chemical vapour
power diode lasers deposited diamond
film is possible
Joining 2001 Ni + Au–Ni Pulsed Study brazing Au/Ni braze [47]
plated Al, Nd:YAG characteristics, improves the
kovar, steel microstructure and adhesion of Au/Ni-
inter-diffusion prod- plating on Ni and
ucts other base metals
(Al, Kovar, steel)
Brazing, 1999 Metals High power Study the capability Diode lasers are [61]
cladding 808 nm diode of diode lasers in useful for brazing
laser material joining and cladding of
metallic thin sheets
Micro- 1997 Si3 N4 ceramic KrF excimer Study the effect of The optimum [62]
patterning sheet laser laser parameters on power level for
micro-patterning smooth surface
Laser sintering finish is determined
Sintering 2001 AISI 304 stain- High power Mathematical Energy transfer [63]
less steel laser modelling to predict through plume and
residual stress molten metal
considered, and
strength of sinter
joints determined
Sintering 2000 Nano zirconia High power Study the Different [64]
particles lasers microstructure, crystalline phases
densification and evolve during
grain growth fast/slow sintering
(Continued)
518 J Dutta Majumdar and I Manna
Table 3. (Continued).
studies show that the detrimental needle-like aluminum carbides are completely eliminated.
The central fusion weld joint consists of TiC, Ti5 Si3 and Al3 Ti along with some large pores.
Figure 11. Schematic view of (a) conduction melt pool (semi-circular), and (b) deep-penetration
(key hole) welding mode (after [1]). The surface boiling and marangoni effect are more in (a).
Penetration depths of 17–35 µm were obtained in deep penetration welding of C95800 nickel–
aluminum–bronze using a 3 kW diode pumped Nd:YAG laser [42]. The softened zone in
laser welding of 6061-T6 Al-alloy could be 1/7th of that obtained in tungsten inert gas
welding [43].
Both conduction-mode and keyhole-mode welding are possible in aluminum [44]. Weld
pool shapes in aluminum depend on the mean power density of the laser beam and the laser
pulse time. The transition from conduction- to keyhole-mode welding occurred in aluminum
at a power density of about 10 GW/m2 , compared to about 4 GW/m2 for stainless steel. In
both materials, large occluded vapour pores near the root of keyhole-mode welds are common
at higher power density. The pores are due to hydrogen that can be significantly eliminated
by surface milling and vacuum annealing [44].
Autogenous “bead-on-plate” laser-beam welding of Al-alloys by a 3 kW CO2 laser under
Ar or N2 atmosphere is possible in the range 700 to 1300W power, 1500 to 9000 mm/min scan
speed and focus located at 1 to 3 mm below the surface, respectively [45]. The effects of using
different gases were evaluated in terms of weld-line appearance, fusion-zone dimension, solute
evapouration, microhardness, post-weld tensile properties, as well as porosity distribution. In
comparison to electron beam welding, laser welding yielded a higher fusion-zone depth/width
ratio, cooling rate and porosity amount, and a lower solute loss and post-weld tensile strain.
A similar investigation on microstructural evaluation following autogenous bead-on-plate
CO2 laser welding of an Al–8·5Fe–1·2V–1·7Si alloy (in wt. %) on 2 mm thick sheet showed
that the fusion zone microstructure consisted of faceted precipitates around 10 µm in size,
embedded in a cellular-dendritic α-Al matrix with a sub-micrometre intercellular phase [46].
Detailed electron microscopy showed that the faceted precipitates in the fusion zone have
the Alm Fe-type crystal structure (m ≈ 4) enriched in Si, Fe and V and a crystalline Fe- and
Si-rich phase formed at the cell boundaries.
Compositional variation or segregation and related temperature-dependent coefficient of
surface tension (Marangoni effect) have significant effect on the quality of the conduction
or deep-penetration welding geometry [48]. However, Ni and Au/Ni plating has marginal or
no influence on laser welding of thin steel sheets except raising the hardness of the weld
[47]. However, laser power, welding speed, defocusing distance and the type of shielding gas
combinations should be carefully selected so that weld joints having complete penetration,
minimum fusion zone size and acceptable weld profile are produced [51]. Heat input as a
function of both laser power and welding speed has almost no effect on both the type of
microstructure and mechanical properties of welds.
520 J Dutta Majumdar and I Manna
uration using a pulsed Nd:YAG laser and a range of weld process conditions. The strength
of the joint was equivalent to that of the annealed base material. Significant gas porosity was
observed at the interface between the Al weld pool and the unmelted Ni and Au/Ni plating
layers. However, porosity did not affect the tensile shear strengths of the Al joints. Au/Ni
braze increased the strength of the Au/Ni-plated Ni specimens to that of the base material.
Heitz et al [62] have reported a detailed investigation on KrF excimer-laser ablation and micro
patterning of Si3 N4 to identify the ablation threshold in air. The surface morphology was flat
or cone-type at 4 J/cm2 . Typical ablation rates for obtaining smooth surfaces free from pores,
scratches, and cracks lie between 0·1 to 0·2 µm/pulse.
The strain at the onset of tertiary creep for Cu- and Ag-reinforced composite solder joints was
typically lower compared to non-composite solder joints. The activation energies for creep
were similar for all the solder materials. Brandner et al [67] have explored soldering of thin
or narrow Cu-based electrical joints with solid state (1064 nm) and diode (808 nm) lasers to
identify the mechanism of energy coupling, mode the temperature rise and determine the pro-
cess window. Laser soldering may be more beneficial for secondary flux-less re-flow solder
bumping than that in a furnace.
Berkowitz & Walvoord [68] have studied laser soldering of fine pitch printed wiring boards
using a continuous wave diode laser. The success of laser soldering of such semiconduc-
tor devices depends on selection of laser, optimization of laser parameters, surface prepa-
ration/cleaning, lead form configuration, solder selection/ application and soldering process
control. It may be noted that solder inter-diffusion in die bonding is important for good bond-
ing and hence, high power devices must be mounted in the epitaxy-side down configuration
for good heat transfer in the well-controlled, high yield and void-free die-attach method.
demand for laser welding or joining. Apart from routine joining, laser is useful in joining
dissimilar materials like steel-Al, steel-alumina, polymer-metal and so on. Even, joining of
tissues and organic substances is now commonplace using laser. The main issues for future
research concern joining materials with dissimilar physical (melting point, density, diffusivity)
and mechanical (hardness, strength) properties and bonding (e.g., metallic to covalent). While
several attempts have been made to develop mathematical models to predict the microstructure
and width of the joint with similar materials, similar approaches now need to be extended for
dissimilar materials. In this regard, capability to predict the microstructure and strength of the
joints would be the core issues. In particular, investigations on the changes in microstructural
and mechanical properties across the weldment as a function of the selected process/laser
parameters are needed. Perhaps, using filler rods can be dispensed with if mechanism for
brittleness of the joints in certain combinations is well understood. Apart from welding,
attempts must be made to develop useful localized joining methods like sintering and brazing
to fabricate finished products of greater variety and challenges. For further details about the
technology and mechanism of laser joining, several recently published text books may be
consulted [16,17,39].
8. Laser machining
Laser machining refers to controlled removal of material by laser induced heating from the sur-
face or bulk of the work piece and includes laser assisted drilling, cutting, cleaning, marking,
scribing and several other forms of material removal/shaping [1,2,6]. Laser cutting is the most
common industrial application of laser in material machining. Metals, ceramics, polymers
and composites may be laser cut or drilled irrespective of the hardness. Processing is easily
automated for speed and accuracy giving clean edges with minimum heat affected zone. The
advantages of laser cutting over other techniques are: flexibility and automation-worthiness,
easy control of depth of cut, cleanliness, non-contact processing, speed, amenability to a
wide variety of materials (ductile/brittle, conductor/non-conductor, hard/soft), negligible heat
affected zone, narrow kerf, and so on [1].
Table 4 provides a summary of the most recent (1995 onwards) and representative studies
on laser machining of materials [71–91]. The areas covered under laser machining include
cutting, drilling, cleaning (or paint stripping), marking and scribing. These processes are
applicable to very soft polymers to most hard ceramics, normal incidence to oblique/inclined
irradiation, ultra-thin semiconductor chips to multi-layer metallic films/sheets, and sim-
ple/curved surfaces to complex geometry. The discussion in this section will highlight the
scope/versatility of laser machining and emphasize the recent advances and outstanding
issues in using laser as a non-contact and non-contaminating tool for machining all kinds of
materials.
Table 4. Summary of selected studies on laser machining of materials in the recent past (1995 onwards).
Laser cutting
Cutting 2001 Microelectronic CO2 and YAG Direct pattern LM is useful for [71]
packaging (frequency processing, image fine scale direct
materials multiplied) transfer, contour patterning and
cutting/trimming drilling of Cu-clad
glass fiber
reinforced epoxy
laminates
Modelling 2000 Metals Theoretical Finite element two Cutting is efficient [72]
of laser study – pulsed stage laser cut in a specific energy
cutting lasers simulation model window. Upper and
that considers stress lower corner stress
relief effect and cut depends on
mechanism passivation break-
through due to
upper corner crack
Modelling 1998 Metals CW–CO2 Model laser Effect of [73]
of laser machining as a absorptivity, mass
cutting process of reaction diffusion rate,
and energy- exothermic
absorption reaction, cutting
speed, and geometry
are considered
Cutting 1996 Al–Li + SiC Pulsed Predict empirical Proper choice of [74]
metal matrix Nd:YAG relation between laser parameters
composite laser parameters minimize HAZ,
and cut shape/depth improve cut quality
and HAZ and efficiency, and
surface finish
Modelling, 1995 Mild and CW–CO2 Study the laminar Cutting includes [75]
cutting stainless steel boundary layer of reaction/ evapoura-
O2 -assisted LM tion. The model
excludes shock-
effects
Laser drilling
Drilling 2001 Stainless steel Dual pulse Improve drilling Drilling improves [76]
Nd:YAG quality by two due to melting by
synchronized laser the first and
pulses without evaporation and
coaxial gas flow recoil process
during the second
pulse
Drilling 1999 Al,W,Mo,Ti, Femtosecond Study the effect of 800 nm short pulses [77]
Cu,FeAg,Au Ti-sapphire laser parameters on produce good
drill quality quality holes. A
model is proposed
(Continued)
Laser processing of materials 525
Table 4. (Continued).
Precision 1999 Stainless steel Pulsed laser Create photonic Cut-off frequency [78]
machin- band gap metal lies in 8–18 GHz
ing crystals by precision that can be tuned by
laser machining varying the hole
size and interlayer
distance
Machining/ 1997 Al-nitride Excimer laser Drill high aspect A bottom substrate [79]
Metal- ratio 60–300 µm can considerably
lization via-holes in AlN reduce back-surface
without / with damage. Shock-
metallization wave analysis and
resistance reported
Laser cleaning
Cleaning 2000 Stainless Pulsed Study the Laser ablation [80]
steel – 3 Nd:YAG mechanism and expels the oxide
compositions influence of laser laser without
/history. parameters on oxide damaging/removing
removal the underlying
metal layer
Polymer 1998 Polymer on Pulsed Study the influence Sub-threshold [81]
coating, TiN coated 248 nm of laser parameters ablation by oblique
removal/ Al–Cu alloy excimer in removing irradiation may
cleaning (23 ns) and polymer layer on improve cleaning
Nd:YAG sub-micron TiN efficiency and
(7 ns) lasers. coated Al–Cu alloy depth. YAG causes
more surface
damage
Paint 1996 Metal surfaces Pulsed Explore complete Surface condition is [82]
stripping TEA–CO2 removal of important for
laser resin/paints from effective paint
metal surface removal
Laser marking
Marking 2001 Polypropylene Pulsed Use frequency Laser marking on [83]
Nd:YAG doubled YAG laser polymers offers
(532 nm) for surface marking more benefit than
usual processes
Marking 2000 Thin sheets CO2 laser Use hollow glass The system is [84]
Cutting waveguide or capable of cutting,
Ag-halide fibers for heating and marking
marking
Etching 1999 Polyethylene Pulsed Explore non-contact Reaction of laser [85]
Polypropylene Nd:YAG and dry etching of pulses with
(532 nm) polymers polymers and
compounds
investigated
(Continued)
526 J Dutta Majumdar and I Manna
Table 4. (Continued).
Data stor- 1997 Polyethylene Infrared laser Use laser Marking is based on [86]
age terephthalate lithography for radiation induced
optical storage of crystallization,
data melting and ablation
Marking 1996 Organo- Ar+ ion laser Explore marking Optimum [87]
metallic films (514 nm) with organo-metal power/time, etc. for
film on marking by
ceramics/plastics photothermal
deposition outlined
Cracking 1995 Sodalime/boro– CW–CO2 Investigate Marking occurs by [88]
Marking silicate glass laser marking/cracking of surface crazing and
glass by laser boiling. Residual
ablation stress causes cracks
Laser scribing
Scribing 2001 Textured Si– KrF excimer To reduce core-loss Core loss reduces [89]
steel laser of transformer steel due to domain
(248 nm) by scribing refinement, stress
relaxation and
domain wall pinning
Scribing 2000 CdTe, ZnO, YAG, Cu- Investigate the The optimum [90]
CuInGaSe2 , vapour, feasibility and conditions for
etc Excimer mechanism of scribing avoiding
scribing plastics ridge formation are
defined
Scribing 1998 Soft-magnetic Excimer and To reduce magnetic Scribing at [91]
ribbon YAG lasers losses of amorphous optimum distances
ribbons reduces core losses
by 29–50%
Scribing 1997 Al–nitride Excimer laser Machining and Straight wall [79]
(AlN) metallization of through hole vias
high aspect ratio (60–300 µm)
vias in AlN drilled with back up
substrate
device that measures the input power. During cutting, the mirror rapidly moves out and allows
the beam to be directed on to the work piece after passing through the beam guide that directs
the beam to center on a focussing optic. The focussed beam then passes through a nozzle from
which a coaxial jet flows. The gas jet is needed both to aid the cutting operation and to protect
the optics from spatter. For cutting processes which rely on melt removal by the gas jet there
is a problem for the metal optics system. To achieve a gas jet suitable for cutting (> 20 m/s
and reasonably well focussed) without interposing a transmissive elements, a set of centrally
directed nozzles or a ring jet can be used. For cutting non-conducting materials like wood,
carbon and plastics, the focussed beam heats up the surface to boiling point and generates
a keyhole. The keyhole causes a sudden increase in absorptivity due to multiple reflections
and the hole deepens quickly [14]. The parameters controlling the laser cutting operation are
Laser processing of materials 527
Figure 12. General arrangement for laser assisted cutting using (a) transmissive optics, and (b)
reflective optics (after [1]). Selection of the optics is based on considerations related to beam power
vis-à-vis thermal stress limit and operational safety.
beam diameter, laser power, traverse speed, gas composition, material thickness, reflectivity
and thermo-physical properties.
Laser cutting does have a diversified application starting from thin sheet metal cutting for
general purpose equipment, such as household appliances, electrical cabinets, automotive
components, thick section metal cutting for trucks, buildings, stoves, construction equipment,
shipbuilding etc. Titanium alloys cut in an inert atmosphere are used in airframe manufacture.
Aluminum alloys have similar advantages in cutting by using the laser, which has to be
well turned and of higher power. Cutting of radioactive material is another important area of
application of laser cutting. Cutting of wood up to 1" thick for the die-board industry, furniture
industry, puzzle and gift industry, crafts and trophies, etc. Textile cutting examples include
plastics, rubbers, composites, cloth, ceramics, etc. Hard brittle ceramics such as SiN can be
cut ten times faster by laser than by diamond saw.
Laser cutting is equally useful in manufacturing special materials including laser cut-
ting of circuit boards, resistance trimming of circuits, functional trimming of circuits and
microlithography. The growing use of the excimer laser is of current interest. Hole drilling
thorough circuit boards to join circuits mounted on both sides has advantages. The excimer
laser can do this without risk of some form of conductive charring.
The microelectronics industry is moving toward smaller feature sizes so as to improve
performance and lower cost. Small distances between chips together with the short intercon-
nection routes are conducive for faster operation. Laser processing for via generation, direct
pattern processing, image transfer, contour cutting and trimming now find increasing applica-
tion in microelectronics packaging industry. On the other hand, smaller spaces between con-
ductive patterns increases the risk of short circuits (caused by pattern faults, solder bridges,
migration, etc.), that emphasizes the need to ensure reliability of laser processing. Illyefaalvi-
Vitez (2001) has attempted utilization of CO2 and frequency-multiplied Nd:YAG lasers (using
five wavelengths, i.e. 10600, 1064, 532, 355 and 266 nm) for drilling and direct patterning
of copper clad glass fiber reinforced epoxy laminates, polyester foils and similar packaging
structures. Laser processing was combined with through contacting of the generated vias by
screen printing with polymer thick films, by wet chemical direct plating and by evapouration
of thin metal layers. The results show promising opportunities for laser processing of metal
layers and polymeric materials in microelectronics packaging.
Analysis of laser metal-cut energy process window is important to predict or develop a
useful strategy for cutting or machining operation for any engineering material (Bernstein
528 J Dutta Majumdar and I Manna
et al 2000). A laser-energy window exists for each cut structure under a specified laser pulse.
Experimental observations showed that the differences between upper and lower corner stress
is temporarily dependent on the passivation breakthrough caused by upper corner cracks. In
a recent model on metal cutting with a gas assisted CO2 laser, laser cutting is considered
as a surface reaction and absorption process that needs an adjusting parameter to represent
the absorptivity for different materials at different incident angles [73]. The computation of
the mass diffusion rate at the gas/solid boundary of the cutting front includes the exother-
mic heat released during cutting. It is shown that a very small level of impurity in oxygen
exerts a significant influence on the cutting performance. Earlier, the combined effect of
chemical reactions taking place between a gas jet and molten metal was considered adopt-
ing a laminar boundary layer approach [75]. These models seem to work well for cutting
speed of up to 30 mm/s and all jet velocities up to sonic speed (as the effect of shock is
ignored).
Yue & Lau [74] have studied the pulsed laser cutting of an Al–Li/SiC metal matrix com-
posite to examine the influences of laser cutting parameters on the quality of the machined
surface. Proper process control may minimize the heat-affected zone, improve the quality of
the machined surface and predict the maximum depth-of-cut for the composite. Finally, the
optimum condition for achieving high cutting efficiency with minimum material damage was
recommended.
slow at 58 s/hole. Electron beam drilling is fast at 0·125 s/hole but needs a vacuum chamber
and is more expensive than a YAG laser processing. In comparison, a YAG laser takes 4 s/hole
to outsmart all other methods [1].
The ability to machine very small features like holes into a metal or polymer sheet/film
by laser ablation with an unmatched precision, accuracy and speed has opened a very useful
scope of application of laser material processing in microelectronic industry. For instance,
holes with a diameter of 300 nm and depth of 52 nm could be drilled in metal films with
minimum distortion and heat affected zone using 200 fs and 800 nm pulses from a Ti:sapphire
laser focused to a spot size of 3000 nm. Lehane & Kwok [76] have developed a novel method
for improving the efficiency of laser drilling using two synchronized free-running laser pulses
from a tandem-head Nd:YAG laser capable of drilling through 1/8-in-thick stainless-steel
targets at a standoff distance of 1 m without gas-assist. The combination of a high-energy
laser pulse for melting with a properly tailored high-intensity laser pulse for liquid expulsion
results in the efficient drilling of metal targets. The improvement in drilling is attributed to
the recoil pressure generated by rapid evapouration of the molten material by the second laser
pulse. Similarly, Zhu et al [77] have carried out a detailed experimental study of drilling sub-
micron holes in thin aluminum foils with thickness ranging from 1·5 to 50 µm, and W, Mo,
Ti, Cu, Fe, Ag, Au and Pb foils of 25 µm thickness with femtosecond Ti:sapphire laser pulses
of 800 nm width. The influence of laser parameters and material properties on hole drilling
processes at sub-micron scale has been examined and a simple model to predict the ablation
rate for a range of metals has been developed.
Laser precision machining has been applied to fabricate metallic photonic band-gap crystals
(consisting of stainless steel plates with a tetragonal lattice of holes and a lattice constant
of 15 mm) operating in the microwave frequency [78]. Transmission measurements showed
that the periodic crystals exhibited a cutoff frequency in the 8–18 GHz range allowing no
propagation below this level. Furthermore, the cutoff frequency could be easily tuned by
varying the interlayer distance or the filling fraction of the metal. Combinations of plates with
different hole-diameters create defect modes with relatively sharp and tunable peaks.
Figure 14. Mechanism of laser cleaning of solid surface with a thin oxide or undesirable layer (a)
Formation of plasma plume due to ionization of the vapour (at very high laser power for a short time),
and (b) spallation of the oxidized layer when surface residual stress changes from compressive to
tensile.
density ultralarge-scale integrated devices depends on the cleanliness of via holes. The side
wall and bottom polymers resulting from reactive ion etching of via holes can be removed
by a non-contact dry laser-cleaning technique using pulsed excimer laser irradiation [81].
Similarly, laser cleaning is capable of removing the polymers by sub-threshold ablation, even
at fluences limited by the damage threshold (= 250–280 mJ/cm2 ) of the underlying Al–
Cu metal film with titanium nitride (TiN) antireflective coating. Comparing ablation results
obtained using Nd–YAG laser and excimer laser shows that although the shorter 7 ns Nd–
YAG laser pulse gives a greater etch thickness than the 23 ns excimer laser pulse, it also tends
to damage the metal films and the silicon substrates of the via wafers more easily.
Tsunemi et al [82] have demonstrated that pulsed laser irradiation of oxidized metallic sur-
faces in an electrolytic cell under proper voltage conditions could be a promising new approach
for effective removal of oxide films. Systematic measurements on simulated corrosion-product
films by optical reflectance profile and energy dispersive X-ray spectroscopy showed that the
utilization of a basic electrolyte solution and imposition of a certain cathodic potential prior
to laser irradiation were essential for a high removal efficiency. This new technique should
find potential applications in paint removal metallurgy, semiconductor fabrication technology,
de-contamination of nuclear power plants and mask-less patterning of oxidized surfaces.
Buckley & Roland [86] have developed a thermal method for lithography on polymer films
based on selective exposure of the films to infrared laser radiation passing through a mask. A
high contrast between the image and background is essential in optical data storage processes.
In this regard, the non-linear response of laser/thermal-marking is inherently advantageous.
Laser irradiation leads to crystallization, melting and ablation of the polymer and produces
high-resolution images with excellent edge acuity and minimal interference from diffraction.
The absence of diffraction effects is due to the nonlinear response of the polymer film to the
radiation. In this technique, the best resolution achievable is limited by the size of the smallest
features present on the masks used to create the pattern.
Recently, attempts have been made to develop a dual-laser-writing scheme in which an
un-modulated short-wavelength read laser augments the writing process effected by a longer-
wavelength laser. Apart from increasing the thermal efficiency of the laser marking process
itself, the dual-beam-writing scheme may decrease the mark width and the recorded mark
length variability. Coupled with the increased resolution of the short wavelength read spot,
these enhancements could improve the performance.
drilling, scribing, marking or cleaning. In all these processes, material removal without dam-
aging the surrounding is a challenge. The recent advances are now based on selecting appropri-
ate wavelength, using multiple beams, allow inclined/oblique incidence and material removal
in stages. A large variety of materials starting from human/animal tissues to diamond can
be laser machined, however, an appropriate choice of laser power and wavelength is crucial
for the success of the operation. Due to diversity of materials, geometry and conditions for
machining, laser machining now often relies on more than one laser for the same operation.
Use of advanced optics and better control of the sample stage are the other concerns with
regards to improving the quality of the cut. Future challenges include increasing the capa-
bility to machine thicker sections, curved surfaces and dissimilar/ heterogeneous materials.
Similarly assessment of material damage will need more close control and monitoring of
the microstructural change/damage across the cut. Development of intelligent machines for
machining diverse materials would require interfacing a vast database with the hardware.
Thus, continued efforts are needed to model laser machining processes with suitable experi-
mental validation of the predicted results.
Failure of engineering materials due to corrosion, oxidation, friction, fatigue and wear/abrasion
is most likely to initiate from the surface because: (i) free surface is more prone to envi-
ronmental degradation, and (ii) intensity of externally applied load is often highest at the
surface [19]. The engineering solution to minimize or eliminate such surface initiated failure
lies in tailoring the surface composition and/or microstructure of the near surface region
of a component without affecting the bulk [2,3,18–20]. In this regard, the more commonly
practiced conventional surface engineering techniques like galvanizing, diffusion coating,
carburizing, nitriding and flame/induction hardening possess several limitations like high
time/energy/material consumption, poor precision and flexibility, lack in scope of automa-
tion/ improvisation and requirement of complex heat treatment schedule. Furthermore, the
respective thermodynamic and kinetic constraints of restricted solid solubility limit and slow
solid state diffusivity impose additional limitations of these conventional or near-equilibrium
processes [18,19].
In contrast, the surface engineering methods based on application of electron, ion and laser
beams are free from many of the limitations of equilibrium surface engineering methods.
A directed energy electron beam is capable of intense heating and melting the surface of
the most refractory metals and ceramics [4]. However, the energy deposition profile in the
irradiated zone under electron beam is gaussian, and hence, the latter is more suitable for
deep penetration welding or cladding of similar or dissimilar solids (figure 5). Moreover, the
scope of generation of X-ray by rapid deceleration of high-energy electrons impinging on
a solid substrate poses additional disadvantage of a possible health hazard. As an alterna-
tive, ion beam processing offers practically an unlimited choice and flexibility of tailoring
the surface microstructure and composition with an implant which has otherwise no or very
restricted solid solubility in a given substrate [8,10]. However, the peak concentration of
implanted species, like the energy deposition peak in electron beam irradiation, lies under-
neath and does not coincide with the surface (figures 5b,c). Furthermore, the requirements
of an expensive ionization chamber, beam delivery system and ultra-high vacuum level are
serious impediments against large-scale commercial exploitation of ion beam assisted sur-
face engineering methods. In comparison, laser circumvents majority of the limitations cited
above with regards to both conventional and electron/ion beam assisted surface engineering
Laser processing of materials 533
methods and offers a unique set of advantages in terms of economy, precision, flexibility
and novelty of processing and improvement in surface dependent properties concerned [1–
4]. One of the major advantage of using laser in surface engineering is its exponential energy
deposition profile vis-à-vis the gaussian profile of that in electron or ion beam irradiation
(figure 5).
Among the notable advantages, laser surface engineering (LSE) enables delivery of a con-
trolled quantum of energy (1–30 J/cm2 ) or power (104 –107 W/cm2 ) with precise temporal and
spatial distribution either in short pulses (10−3 to 10−12 s) or as a continuous wave (CW). The
process is characterized by an extremely fast heating/cooling rate (104 –1011 K/s), very high
thermal gradient (106 –108 K/m) and ultra-rapid resolidification velocity (1–30 m/s) [18–20].
These extreme processing conditions very often develop an exotic microstructure and com-
position in the near surface region with large extension of solid solubility and formation of
metastable even amorphous phases.
Figure 15 presents a brief classification of different LSE methods that involve mainly two
types of processes. The first type is meant for only microstructural modification of the surface
without any change in composition (hardening, melting, remelting, shocking, texturing and
annealing), while the other requires both microstructural as well as compositional modification
of the near-surface region (alloying, cladding etc.).
Among the various LSE methods, laser surface alloying (LSA) involves melting of a
deposited layer along with a part of the underlying substrate to form an alloyed zone for
improvement of wear, corrosion and oxidation resistance. Figure 16a illustrates the scheme
of LSA with a continuous wave laser. It includes three major parts: a laser source with a beam
focusing and delivery system, a lasing chamber with controlled atmosphere and a micro-
processor controlled sweeping stage where the specimen is mounted for lasing. The process
includes melting, intermixing and rapid solidification of a thin surface layer with pre/co-
deposited alloying elements (figure 16b). The coating material may be pre-deposited by any of
the conventional means like electro-deposition, plasma spray and physical/chemical vapour
deposition or may be injected in the form of powder or powder mixture into the melt at the time
of laser treatment and is termed as co-deposition. In LSA with pre- or co-deposition, a 20–30
% overlap of the successive melt tracks is intended to ensure microstructural/compositional
homogeneity of the laser treated surface. The sweeping stage (x-y or x-y-z-θ) allows laser
irradiation of the intended area of the sample-surface at an appropriate rate and interaction
time/frequency. The irradiation results into transient melting of the deposit with a part of the
underlying substrate, rapid mass transfer by diffusion/convection in the melt pool, and ultra-
534 J Dutta Majumdar and I Manna
Figure 16. (a) Schematic hardware set-up for laser surface alloying (LSA), (b) the processes of
heating/melting, intermixing and solidification in LSA, and microstructure of (c) a typical alloyed zone
and (d) solid-liquid interface formed in LSA of Cu with Cr [134]. Note that convection dominates
mass transfer in the alloyed zone (c), and epitaxial growth marks solidification of the melt pool (d).
fast solidification to form an alloyed zone (figures 16c,d). The depth, chemistry, microstructure
and associated properties of the alloyed zone depend on the suitable choice of laser/process
parameters i.e. incident power/energy, beam diameter/profile, interaction time/pulse width,
pre or co-deposition thickness/ composition and concerned physical properties like reflectiv-
ity, absorption coefficient, thermal conductivity, melting point and density.
Table 5. Summary of selected studies on laser surface engineering of materials in the recent past (1995
onwards).
Table 5. (Continued).
AISI 304 2000 LSA Corrosion Investigate the role Si turns the matrix [98]
stainless of Si in improving ferritic and
steeel (Si) corrosion resistance segregates. Post
LSA homo-
genization improves
corrosion resistance
AISI 304 1999 LSA Pitting, Attain AISI 316-SS Mo improves [99]
stainless erosion equivalent corrosion pitting and erosion
steeel (Mo) property on 304-SS corrosion resistance
of 304-SS
AISI 316L 1998 LSM Pitting corro- De-sensitization of LSM eliminates the [100]
sion nitrogen bearing sensitized zones and
stainless steel significantly
improves pitting
corrosion resistance
ASTM 1997 LSC Corrosion Improve pitting Pits following LSC [101]
S31254 corrosion resistance are smaller in size
stain-less of mild steel by LSC and number
steel on mild
steel
AISI 304 1995 LSMLSA Corrosion, Improve corrosion LSM produces [102]
stainless steel wear and wear resistance δ-ferrite and
(Mo, Ta) by LSM or LSA deteriorates corro-
sion. LSA with Mo
is useful. Not much
change in wear
Mild steel 1995 LSA Corrosion Utilize LSA to LSA with Fe–Cr– [103]
(Fe,Cr,Si,N) improve corrosion Si–N produces a
resistance of mild fine duplex
steel microstructure and
greatly increases
corrosion resistance
Oxidation properties
Steel (Al) 2001 LSA Oxidation Improve oxidation LSA with Al forms [104]
resistance by LSA several aluminides
with predeposited Al that imparts good
oxidation resistance
at 600◦ C up to 200 h
Stainless 2000 LC Cleaning Remove oxide layers Thin oxide layers [105]
steel by laser assisted could be removed
vapourization irrespective of
chemical
composition and
history in a narrow
energy band
(Continued)
Laser processing of materials 537
Table 5. (Continued).
Plain carbon 2000 LSA High Impart oxidation Complex oxide [106]
steel (TiB2 ) temperature resistance by layers develop on
oxidation alloying with borides steel surface
exposed to
600–1000◦ C
following parabolic
growth rate
AISI 304 1998 LSR Oxidation Improve oxidation Double remelting [107]
stainless resistance of 304-SS produces better
steel (Ni–Cr– by LSR of prior twin oxidation resistance
Al–Y and (bond + top) coated at 1200◦ C than
ZrO2 +Y2 O3 ) ceramic layers single-
remelted/plasma-
coated sample
Inconel 1997 LSA Oxidation Improve high LSA with Al [108]
800H (Al) temperature develops an Al-rich
oxidation resistance surface that
considerably
improves resistance
to oxidation up to
1000◦ C
AISI 316L 1996 LSC Oxidation Develop thermal Rhombohedral- [109]
(Fe–Cr–Al– barrier coating for Al2O3 and mixed
Y) enhanced oxidation Fr + Cr or Ni + Cr
resistance oxides offer
enhanced oxidation
resistance at
1100–1200◦ C
Wear properties
S 31603 2001 LSA Cavitation Enhance erosion Erosion resistance [110]
stainless steel erosion resistance by improves
(CrB2 , Cr3 C2 , resistance developing a ceramicconsiderably for all
SiC,TiC,WC, dispersed composite carbides and borides
Cr2 O3 ) surface layer except Cr2 O3
Austenitic 2000 LSA Hardness, Develop amorphous Hardness and [111]
stainless steel Erosion dispersed composite wear/erosion
(Nano-Zr) layer to improve resistance improves
significantly due to
resistance to erosion
and wear dispersion of Zr-rich
amorphous phase
Austempered 2001 LSALSH Hardness, Improve LSH (than LSA) is [112]
ductile iron Wear adhesive/abrasive more effective in
(Cr) wear resistance of improving wear
austempered ductile resistance and
iron by LSA or LSH developing
compressive
residual stress
(Continued)
538 J Dutta Majumdar and I Manna
Table 5. (Continued).
AISI 1040 2000 LSA Tribology, Develop boride LSA improves [113]
(TiB2 ) Wear coated/dispersed resistance to
surface layer and adhesive/ abrasive
improve wear wear and reduces
resistance of friction coefficient
low-carbon steel
Mild steel 2000 LSR,SHS Wear Utilize SHS and LSR homogenizes [114]
(FeCr–TiC) LSR to develop a the microstructure
TiC dispersed and improves wear
surface composite resistance
Mild steel 1999 LSC Wear Improve hardness, LSC improves wear [115]
(Hadfield, wear and bulk resistance and bulk
Fe–Mn–C) mechanical mechanical
properties properties of the
clad
Pearlitic rail 1998 LSM Wear Improve mechanical LSM produces a [116]
steel and tribological thin glazed layer
properties by LSM with better hardness
and lower friction
rate
EN31 1997 LSH Wear, Improve wear and Single or double [117]
bearing steel Friction friction properties by glazed LSH tracks
LSH have better wear and
friction property
A 7 tool steel 1997 LSA Wear, LSA with excimer LSA reduces [118]
(Ti) Friction laser to improve friction coefficient
wear/friction but does not affect
property wear properties
Medium 1996 LSC Wear Improve wear Wear against [119]
carbon steel resistance by LSC 4140/4340 steels
(Stellite 6) with stellite coating considerably
improves due to
LSC
Mild steel 1995 LSR, SHS Hardness Improve hardness [120]
(WC) and wear resistance
by SHS and LSR
2. LSE of superalloys and special steels
Cr–Mo steel 2000 LSA Oxidation Improve high LSA enhances [139]
(Cr) temperature oxidation resistance
oxidation resistance in 800–1000◦ C due
to Cr2 O3 rich scale
Martensitic 1999 LSC Hardness, Improve wear and LSC significantly [140]
steel Wear erosion resistance of increased hardness
(Ni-alloy) the base steel and erosion
resistance
(Continued)
Laser processing of materials 539
Table 5. (Continued).
AISI 304 1998 LSR Oxidation Improve oxidation Double remelting [107]
stainless resistance by LSR of produces better
steel (Ni–Cr– bond (Ni–Cr–Al–Y) oxidation resistance
Al–Y and and top at 1200◦ C than
ZrO2 +Y2 O3 ) (ZrO2 + Y2 O3 ) coat single-remelted/
layers plasma-coated
sample
Si-steel 1998 LSC Oxidation Improve oxidation LSC with high [141]
(Ni + Cr) resistance Ni–Cr alloy (with
Si) improves
oxidation resistance
at 900◦ C. Si content
is important
Inconel-600 1997 LSM Oxidation Enhance oxidation LSM improves [142]
resistance oxidation resistance
due to
microstructural
homogeneity
Inconel 1997 LSA Oxidation Improve high Al-rich surface by [108]
800H (Al) temperature LSA improves
oxidation resistance oxidation resistance
up to 1000◦ C
35 NCD 16 1996 LSA Hardness, Enhance hardness Hardness increased, [143]
ferritic steel oxidation and high temperature Oxidation
(Cr3 C2 /SiC) oxidation resistance resistance increased
due to Si containing
complex oxides
3. LSE of non-ferrous alloys
Al and its alloys – Corrosion properties
Al–6013 + 1999 LSM Corrosion Improve pitting and Rapid solidification [121]
SiCp general corrosion of LSM refines the
composite properties by LSM surface
microstructure and
improves the
corrosion resistance
2014 Al alloy 1998 LSA Corrosion Study the corrosion Overlapping regions [122]
(Cr, W, behaviour of Al-alloy are more prone to
Zr–Ni,Ti–Ni) surface after LSA pitting corrosion
due to segregation
Al-alloy 1997 LSCLSR Corrosion Surface Amorphous phase [123]
(Zr60Al15 Ni25 ) amorphization of Al dispersion (function
by LSC/LSR to of LSC/LSR
improve pitting parameters)
corrosion resistance produces an
improved corrosion
resistance
(Continued)
540 J Dutta Majumdar and I Manna
Table 5. (Continued).
2014 Al alloy 1998 LSA Corrosion Study the corrosion Overlapping regions [122]
(Cr, W, behaviour of Al-alloy are more prone to
Zr–Ni,Ti–Ni) surface after LSA pitting corrosion
due to segregation
Al-alloy 1997 LSCLSR Corrosion Surface Amorphous phase [123]
(Zr60Al15 Ni25 ) amorphization of Al dispersion (function
by LSC/LSR to of LSC/LSR
improve pitting parameters)
corrosion resistance produces an
improved corrosion
resistance
Al–Si (Ni– 1997 LSR Micro- Study Ultrafine Ni3Al and [124]
Cr–B–Si) structure microstructural amorphous phase
evolution in LSR of with very high
plasma coating on hardness form by
Al–Si LSR
Al–SiC 1996 LSM Corrosion Improve corrosion Microstructural [125]
composite resistance by LSM homogeneity by
with excimer laser LSM improves
corrosion resistance
Al and its alloys – Oxidation properties
6061 Al alloy 2001 LSCLSA Oxidation Improve oxidation TiC + Al composite [126]
(Al + TiC) resistance of Al-alloy coating improves
by LSC/LSA oxidation resistance
in 200–600◦ C
Al–Cu–Li 1997 LSM Oxidation Improve oxidation LSM produces [127]
resistance by LSM adherent scale and
assisted surface improves oxidation
treatment resistance at 450◦ C
AlGaAs and 1996 LSM Oxidation Study wet oxidation Oxidation of [128]
AlAs layers characteristic of AlGaAs provides
buried thin film for suitable apertures
laser device for surface lasers
Al and its alloys – Wear properties
Al + SiC 1999 LSS Hardness, Improve oscillating Both hardness and [129]
wear wear property by wear resistance
LSS of HVOF improve by LSS
coated composite due to residual
surface layer compressive stress
Al (Al3 Ti) 1999 LSC Wear Improve wear Composite [130]
resistance intermetallic layer
on surface enhances
wear resistance
(Continued)
Laser processing of materials 541
Table 5. (Continued).
Al (AlN) 1998 LSA Hardness Synthesize AlN layer LSA produces [131]
by excimer laser irra- adherent AlN layer
diation in nitrogen on Al with high
hardness
AlSi 1997 LSC Hardness Develop Microstructure of [132]
(Ni–WC) carbide/amorphous cladded layer
dispersed high consists of
hardness layer aluminides +
amorphous phases
and has high
hardness
Cu and its alloys
Cu–Cr–Fe 2000 LSR Hardness, Improve tribological LSR improves [133]
Wear properties of powder hardness and wear
compacts by LSR resistance and
reduces friction
Cu (Cr) 1999 LSA Wear, erosion Improve LSA enhances [134]
wear/erosion resistance to
resistance of Cu by adhesive/ abrasive
LSA with Cr wear and erosion
due to solid solution
and dispersion
hardening
Mg and its alloys
Mg + SiC 2001 LSC Corrosion Improve corrosion LSC improves [135]
(Al–Si) resistance by LSC corrosion
with Al + Si alloy resistance. LSC
parameters have
strong influence
AZ91D and 2001 LSM Corrosion Improve corrosion Uniform and refined [136]
AM60B Mg resistance by LSM microstructure
alloys improves corrosion
resistance
AZ91 Mg 1999 LSM Corrosion Enhance corrosion Pulsed excimer laser [137]
alloy resistance irradiation improves
corrosion resistance
Mg − 1997 LSM Corrosion Enhance corrosion Uniform and refined [138]
ZK60 + SiC resistance microstructure
composite produced by
excimer laser
improves corrosion
resistance
(Continued)
542 J Dutta Majumdar and I Manna
Table 5. (Continued).
stainless hard-facing NiCoCrB alloy coated mild steel have shown that LSM could markedly
improve the resistance to corrosion and cavitation erosion-corrosion of the substrate [94].
However, attempts to simultaneously improve electrochemical and mechanical properties by
LSE may be counter-productive as presence of ceramic or intermetallic phases on the surface
may provide initiation sites for pitting [97].
Dutta Majumdar & Manna [99] have investigated the effect of LSM and LSA of plasma
spray deposited Mo on AISI 304 stainless steel (304-SS). Figure 17a shows the optimum
conditions (shaded region) for the formation of a homogeneous microstructure and composi-
tion in this study for improvement in pitting corrosion and mechanical property. Potentiody-
namic anodic polarization tests of the substrate and laser surface alloyed samples (SS(Mo))
in 3·56 wt. % NaCl solution (both in forward and reverse potential) showed that the crit-
ical potential for pit formation (EP P 1 ) and growth (EP P 2 ) have significantly (2–3 times)
improved from 75 mV(SCE) in 304-SS to 550 mV(SCE) (figure 17b). EP P 2 has also been
found to be nobler in as lased specimens than that in 304-SS. The poor pitting resistance
of the plasma sprayed 304-SS samples (without laser remelting) was probably due to the
presence of surface defects present in plasma deposited layer. Standard immersion test was
conducted in a 3·56 wt. % NaCl solution to compare the effect of laser surface alloying on
Figure 17. (a) Process optimization diagram for selecting the necessary energy density (E) for LSA
of 304-SS with Mo to achieve the desired composition (XMo ) and hardness (Hvav ) in the alloyed zone
(shaded region), (b) cyclic potentiodynamic polarization behaviour of 304-SS and SS(Mo) in 3·56 wt.
% NaCl solution, (c) variation of pit density in 304-SS and SS(Mo) as a function of time (t) in a
3·56 wt. % NaCl solution, and (d) comparison of material loss per unit area (1m) due to erosion as a
function of t for 304-SS and SS(Mo). For details, please see [99,197].
544 J Dutta Majumdar and I Manna
the pitting corrosion resistance. Figure 17c compares the kinetics of pit formation in terms of
area fraction of pits determined by standard immersion test in a 3·56 wt.% NaCl solution as
a function of time (t) between 304-SS and SS(Mo) lased with 1210 MW/m2 power density
and 31·7 mm/s scan speed for deposit thickness of 250 µm (corresponding to highest EP P 1 ).
It is evident that both the extent and rate of pitting were significantly reduced in the SS(Mo)
as compared to that in 304-SS. Furthermore, the process of pitting in 304-SS follows a sig-
moidal nature marked by a substantially rapid initial stage than that of the later stage with no
incubation time. In comparison, pits were noticed in SS(Mo) only after 50 h of immersion,
and the number increases linearly following a much slower kinetics as compared to that in
304-SS. Continuous circulation of the samples at 750 rpm for 10 to 75 h in a medium con-
taining 20 wt. % sand in 3·56 wt. % NaCl solution showed significant decrease in the kinetics
of erosive-corrosion loss in SS(Mo) than that in 304-SS. It was thus concluded that LSA is
capable of imparting an excellent superficial microhardness and resistance to corrosion and
erosion-corrosion properties to 304-SS due to Mo both in solid solution and as precipitates.
In an attempt to develop stainless mild steel by coatingASTM S31254 stainless steel powder
on plain carbon steel, Anjos et al [101] have noted that the anodic polarization behaviour
following LSE is similar to the bulk stainless steel even in very aggressive solution. Similar
efforts of surface alloying of Fe–Cr and Fe–Cr–Si–N layers on plain carbon steel to improve
corrosion resistance led to development of a Fe–Cr–Si–N surface layer with a fine duplex
microstructure that showed a higher pitting potential than that of the Fe–Cr layer [103]. The
passive film resistance increased and passive current density decreased with the increasing
Cr content.
9.1b Oxidation resistance by LSE: Oxidation is another serious mode of surface degradation
that gets aggravated under unabated counter ionic transport of cations and anions at elevated
temperature. Unlike electrochemical corrosion, oxidation occurs through dry reaction and
solid state ionic transport through the oxide scale. In the past, several attempts have been
made to enhance resistance to oxidation by LSA, LSC and similar LSE techniques [104–109].
Recently, Pillai et al [104] have obtained enhanced oxidation resistance (at 873 K for up to
200 h) of plain carbon steel following LSA with Al due to several intermetallic phases like
Al13 Fe4 and Al2 Fe2 . Agarwal et al [106] used a composite boride (TiB2 ) coating to enhance
oxidation resistance of steel in the range 600–1000◦ C. Thermal barrier coatings could also be
effective for improving oxidation resistance of stainless steel [107]. However, such coatings
are brittle and hence are applied with a favorable composition gradient like applying a bond
coat (Ni–22Cr–14Al–1Y) between the topcoat (ZrO2 + 7·5 wt%Y2 O3 ) and stainless steel
substrate before single or multi pass LSM treatments. Oxidation tests at 1200◦ C indicated that
double pass LSM was more effective to impart a better oxidation resistance [107]. Similar
attempts of improving oxidation resistance have been made with Incoloy 800 H by LSA
with Al [108] and by LSC of 316 L stainless steel with Fe–Cr–Al–Y alloy coatings [109].
In all these cases, it appears that the degree of enhancement of oxidation resistance by LSE
primarily depends on stability, adherence, imperviousness and strength of the complex oxide
scale comprising multiple oxide on top of the base metal.
Manna et al [139] attempted to enhance the high temperature oxidation resistance (above
873 K) of 2·25Cr–1Mo ferritic steel by laser surface alloying (LSA) with co-deposited Cr
using a 6 kW continuous wave CO2 laser. The main process variables chosen for optimizing
the LSA routine were laser power (from 2 to 4 kW), scan speed of the sample-stage (150
to 400 mm/min) and powder feed rate (16 to 20 mg/s). Isothermal oxidation studies in air
by thermogravimetric analysis at 973 and 1073 K for up to 150 h revealed that LSA had
Laser processing of materials 545
significantly enhanced the oxidation resistance of ferritic steel during exposure to 973 and
1073 K (figures 18a,b). Post oxidation microstructural analysis suggests that an adherent and
continuous Cr2 O3 layer is responsible for the improvement in oxidation resistance [139].
Similar improvement in oxidation resistance has been obtained by LSR of bond (Ni–Cr–
Al–Y) and top (Zr O2 + Y2 O3 ) coated stainless steel [107], LSC of Si-steel with Ni + Cr
[141], LSM of inconel 600 [142] and LSA of inconel 800 H with Al [108].
9.1c Wear resistance by LSE: Attempt to improve wear resistance of steel by LSE seems
to be more effective than the attempts to enhance the resistance to corrosion and oxidation.
Cheng et al [110] have added a mixture of WC–Cr3 C2 –SiC–TiC–CrB2 and Cr2 O3 to produce
a metal matrix composite surface on stainless steel UNS-S31603. Following LSM, cavitation
erosion resistance improved in all cases except for Cr2 O3 . Wu & Hong [111] have attributed
the improvement in hardness and corrosion/wear resistance of stainless steel to the pres-
ence of amorphous phase in the Zr-rich surface (with 7·8–14·5 at. % Zr) following LSA of
stainless steel with Zr nano-particles. Roy & Manna [112] have demonstrated that laser sur-
face hardening (LSH), instead of LSA or LSM is more effective in enhancing hardness and
wear resistance of unalloyed austempered ductile iron (ADI). Figures 19 a,b show the typical
martensitic microstructure developed by LSH and significant improvement in adhesive wear
of laser hardened vis-à-vis as-received and laser surface melted ADI samples, respectively.
Adhesive wear of austempered ductile iron consists of three distinct stages: the initial rapid,
subsequent steady state and final accelerated (abrasive) wear. The improvement in wear resis-
tance following LSH is attributed to the martensitic surface with residual compressive stress
[112].
546 J Dutta Majumdar and I Manna
Agarwal & Dahotre [113] have reported a substantial improvement in resistance to adhe-
sive/abrasive wear of steel following LSA with TiB2 . The surface composite layer containing
about 69 vol. % TiB2 particles recorded an elastic modulus of 477·3 GPa. Similar improve-
ment in wear resistance of mild steel was reported by Tondu et al [114] due to formation of
a FeCr + TiC composite coating formed by laser assisted self propagating high temperature
synthesis. Earlier, Zhukov et al [120] achieved a similar carbide dispersed composite coating
on steel by laser assisted self-propagating high temperature synthesis.
Instead of composite coating, Pelletier et al [115] applied a Fe–Mn–C hadfield steel coating
by LSC on steel and achieved significant improvement in hardness (over 800VHN) elastic
modulus (210 GPa) and yield strength (1200 MPa) mostly due to deformation induced twin-
ning transformation. A signification mitigation of subsurface crack propagation in pearlitic
rail steel was achieved following LSM without any change in surface chemistry [116]. Simi-
lar improvement in wear and friction properties of En 31 steel was obtained by LSH without
melting or any change in surface chemistry [117]. However, the methods that involve change
in surface composition seem more popular or effective in enhancing wear resistance of fer-
rous alloys. For instance, LSA of A7 tool steel with Ti was reported to reduce the dry sliding
friction coefficient due to the formation of a low-friction transfer film [118].
Similarly, Stellite coating by LSC is a standard method of reducing wear loss of ferrous
substrate [119]. Besides providing with a harder and tougher surface, stellite coating develops
Laser processing of materials 547
a tougher oxide scales and reduces wear under severe condition. Improvement in hardness
and wear resistance has been achieved by LSC of martensitic steel with Ni alloy [140] and
LSA of ferritic steel with Cr3 C2 + SiC [143]. Several other examples are cited in table 5.
than that in Cu under comparable conditions. Though the extent of material loss increases with
an increase in T for both pure Cu and Cu(Cr), the rate of erosion loss for Cu(Cr) is negligible
as compared to a substantial change in 1m with T for pure Cu, especially beyond 370 K.
Uniform and refined surface microstructure by LSM seems quite effective in improving
corrosion resistance in AZ91D/AM60B [136], AZ91 [137], Mg–ZK60 [138] and other com-
mercial Mg-based alloys. Recently, Wang & Wue [135] have achieved significant improve-
ment in corrosion resistance of SiC dispersed Mg by LSC with Al–12Si alloy layer.
Laser surface alloying of Ti with Si, Al and Si + Al (with a ratio of 3:1 and 1:3 respec-
tively) was conducted to improve the wear and high temperature oxidation resistance of Ti by
LSA [145,146]. Figure 22a reveals a typical hyper-eutectic microstructure on the top surface
of the alloyed zone in Ti with Si consisting of faceted Ti5 Si3 uniformly distributed in a two-
phase eutectic aggregate of α-Ti and Ti5 Si3 [146]. The high volume fraction of the primary
phase and degree of fineness of the eutectic products signify complete dissolution and uni-
form intermixing of Si in the alloyed zone, and a rapid quenching experienced by the latter,
respectively. Subsequent oxidation studies conducted at 873–1023 K showed that LSA of Ti
with Si and Si + Al significantly improved the isothermal oxidation resistance (figure 22b).
In addition to oxidation, the effect of LSA of Ti with Si or Si + Al on wear resistance was
also studied. Figure 22c shows the variation of depth of scratching (zw ) with load (L) due to
scratching of pure Ti, Ti(Si), Ti(Al) and Ti(3Si + Al) with a hardened steel ball. It may be
noted that zw varies linearly with L for all the cases. The effect of L on zsc is more prominent
at higher number of scratching (nsc ≥ 1000) than that at a lower value of the same (= 25).
Under comparable conditions of scratching, Ti undergoes the most rapid wear loss followed
Laser processing of materials 549
by that in Ti(Al), Ti(3Si + Al) and Ti(Si). Ti(Si) undergoes the minimum wear loss. The
improved wear resistance of laser surface alloyed Ti with Si was attributed to the formation
of a hard Ti5 Si3 precipitates in the alloyed zone [145].
Manna et al [199–201] made a novel attempt to develop the material for neural stimulation
electrode by LSA of Ti with Ir that can mimic the normal spatio-temporal pattern of neuronal
activation by reversible charge transfer. The usual electrode made of iridium is expensive,
brittle and not amenable to miniaturization by plastic deformation. On the other hand, titanium
is cheaper, bio compatible and amenable to drawing/etching. Figure 23a shows the indigenous
set-up used for fabricating the electrode by LSA. Intelligent combination of laser parameters,
powder composition and post LSA etching was used to develop the desired microstructure
(figure 23b). Though charge density could not be measured due to exceedingly uneven surface
intentionally developed by special etching (meant for increasing the surface area), the total
charge was comparable to that of pure iridium in appropriate solution [201].
(a)
10 µm
explicit finite difference method to predict the thermal history (i.e. temperature profile, thermal
gradient, cooling rate and solid–liquid interface velocity) and hence, the microstructure of
the alloyed zone developed by laser surface alloying. Figure 24a shows the temperature (T )
profile as a function of time (t) during LSA of AISI 304 stainless steel with 100 µm thick
pre-deposited Mo using a CW–CO2 laser delivering 1800 MW/m2 power irradiation with a
Laser processing of materials 551
(b)
Tip
(a)
Laser
Ti Ti + Ir powder
Tilr
Ti
1 µm
SEM
Figure 23. (a) Schematic diagram showing the set-up used for LSA of Ti with Ir (or Ti + Ir) by
CO2 laser pulse for developing neural stimulation electrode, and (b) microstructure of the alloyed zone
showing a 3 fold increase in surface area following special etching [199,200].
25 ms interaction time. The calculation considered the effect of intermixing between the bi-
metallic layer after melting and temperature dependence of concerned material properties.
The corresponding thermal quenching rate has been shown in figure 24b. The model allows
calculation of other thermal parameters like thermal gradient, solidification velocity, etc. that
are useful in predicting the microstructure [204]. Similar model could be extended to two-
dimensional radially symmetric heat transfer condition [205].
Roy & Manna [191] have used a simple analytical approach, based on the treatment of
Ashby & Easterling [188], to predict the thermal profile in LSH of austempered ductile iron
and explain the phenomenon of partial or complete ‘localized melting’ of graphite nodules
without liquefaction of the surrounding ferritic matrix. This phenomenon was first reported by
Fiorletta et al [206]. Figure 25a reveals that a graphite nodule has undergone partial melting
during LSH of austempered ductile iron with 650W power and 60 mm/s scan speed. Note
that melting initiates at the graphite-matrix interface and assumes only a part of the nodule
leaving the core unaffected. The extent or width of this incipient fusion primarily depends on
the thermal cycle and concomitant carbon diffusion profile from the nodule into the matrix.
The mathematical model to predict the thermal and composition profile, and hence, the width
of annular molten region by Roy & Manna [191] could establish a fair-correlation between
the melt width (ym ) and laser parameters used for LSH. Figure 25b shows the variation of ym
as a function of depth (z) from the surface predicted for two predetermined conditions of laser
surface hardening. It is evident that ym decreases as z increases bearing a linear relationship
between them. The experimental data (open symbols) are fairly close to the predicted trend
of the model, particularly for higher laser power.
Figure 24. (a) Temperature (T ) distribution as a function of time (t) for SS(Mo) at different levels
of depth (z), and (b) variation of corresponding cooling rate (dT /dt)C as a function of time (t) at
different z during LSA of AISI 304 stainless steel with Mo. For details, please see [198,204].
to review the recent developments and highlight the important issues concerning them. An
important aspect purposely avoided in this contribution, obviously to avoid exceeding the
prescribed length, concerns mathematical modelling of LSE. For this, readers may see refer-
ences [5–6,185–186] and obtain most of the necessary data on material properties from the
references [189–190]. The current trend appears to suggest that the excimer and diode lasers
with shorter wavelengths may soon substitute CO2 even YAG lasers for LSE applications.
Sustained efforts will then be needed to establish the microstructural evolution and scope of
improvement following LSE with those new lasers.
Apart from structural applications, LSE could be equally useful in enhancing functional
properties like magnetism, emission/absorption characteristics, sensors, microelectronic
Laser processing of materials 553
100 (b)
P = 700 W, P = 1000 W,
60
40
20
80 100 120 140
Depth from the top surface z (µm)
Figure 25. (a) Partial melting of a graphite nodule embedded in the ferritic/martensitic matrix follow-
ing LSH with 650W power and 60 mm/s scan speed. Note that melting initiated at the graphite-matrix
interface and consumed nearly half the nodule from the circumference, and (b) variation of predicted
melts widths (ym ) around graphite nodules as a function of depth (z) from the surface. Open and solid
symbols represent experimental and predicted data, respectively [191].
It is known that environmental degradation by corrosion and oxidation alone accounts for more
than 30% discard and loss of engineering components of all dimensions from bridges/railway-
carriages to needles/bolts made of metals and alloys. While replacing a bolt/structural member
in a bridge or painting a carriage is neither too expensive nor difficult, an early malfunction
of a heart valve, orthopedic implant or aeroturbine engine component may pose threat to the
human life, cause tremendous trauma and lead to catastrophic failure respectively.
One or higher dimensional structural defects in a polycrystalline aggregate like disloca-
tions, homo/heterophase boundaries, voids and inclusions constitute the higher energy hence
preferred nucleation sites for materials degradation by oxidation and corrosion. On the other
hand, an amorphous state is devoid of both crystalline anisotropy and intercrystalline defects,
and thus, does not provide the nucleation sites and short-circuiting diffusion path for such
environmental degradation. However, an amorphous or glassy material, more often than not,
is brittle and not amenable to material processing/shaping to develop a large component
of complex geometry. Thus, a crystalline solid with an amorphous surface or over-layer is
554 J Dutta Majumdar and I Manna
and Nb-alloys. Borodina [158] met with similar success of amorphizing the surface of several
ternary and quaternary Fe-metalloid (B/C/Si) compositions up to 7–20 µm depth. Affolter
& von Allmen [159] attempted to establish the criteria for surface amorphization by laser
irradiation with Au–Ti, Co–Ti, Cr–Ti and Zr–Ti binary systems. While surface amorphization
was achieved in Au–Ti, Co–Ti and Cr–Ti systems, failure to convert Zr–Ti couple into the
glassy state was attributed to the scope of easy partitionless crystallization enabled by complete
mutual solubility both in liquid and solid state in Zr–Ti.
Lin & Spaepen [160] extended their earlier approach to produce amorphous layers in Ni–
Nb [160], and Mo–Ni, Mo–Co and Co–Nb couple [161]. A systematic study on the genesis
of surface amorphization appears to suggest that impurity stabilization of short-range order
in the liquid state is primarily responsible to prevent diffusion controlled or partitionless
crystallization during laser quenching. For instance, the formation of the metallic glass in Cu–
Zr by den Broeder et al [162] is a typical case of impurity stabilized surface amorphization.
Hashimoto et al [163] have reviewed a number of experimental studies [164–170] by their
own group to emphasize that laser assisted surface amorphization is a feasible method of
improving corrosion resistance of bulk crystalline alloys.
Thus, a sizable number of experimental studies seem to evidence that surface amorphization
of laser irradiation is feasible under a chosen composition range and optimum LSE condition.
In this regard, the extreme heating/cooling rates, thermal gradient and resolidification-velocity
may aid the collision controlled partitionless amorphization of the melt. However, Kear et al
[172] and Bergmann & Mordike [156,157] pointed out that suppression of epitaxial nucleation
and prevention of growth of crystallites from the underlying solid substrate must be insured
to achieve this laser assisted surface amorphization.
Spaepen [173] has worked out the thermodynamic and kinetic criteria for surface amor-
phization for picosecond pulse laser irradiation of metals. It is suggested that partitionless
crystallization may occur at an interface velocity (vi ) of 100 m/s so long as the isotherm
velocity (vT ) coincides with vi . When vi < vT , the liquid may be quenched as glass. The
time (t) for a monolayer (say, z = 0·3 nm) crystallization is approximately 3 ps. The cor-
responding diffusion distance (Dl t)1/2 is less than an interatomic distance (Dl = liquid
diffusivity, ∼ 10−8 m2 /s). Hence, the liquid may undergo only partitionless solidification
either as a crystal or glass.
Thermodynamically, partitionless solidification occurs only below the T0 -curve, as shown
in figure 26. The solidified structure is crystalline at either A-rich or B-rich ends of the
hypothetical phase diagram. Since the T0 -curves are of ‘deep-plunging’ type [9], it is likely
that the atomic transport rate at sufficiently low temperature (say, below Tg ) is too sluggish
to nucleate a crystalline phase. As a result, the liquid may be configurationally frozen to a
supercooled liquid or glassy structure. Suppression of crystallization is likely in the shaded
composition range. However, the criterion illustrated in figure 26 is only an essential but not
sufficient condition for surface amorphization.
Thus, interface velocity in metals for heat flow limited condition (vi,th ) is given by:
vi,th = nz(Tm − Ti )/Ti ,
where, n is atomic jump frequency across the solid–liquid interface, z is the distance or
depth, and Tm and Ti are melting and interface temperatures. The resolidification rate is also
governed by the rate of removal of down the thermal gradient across the interface. Thus, vi,th
may be obtained as:
vi,th = (kVm 1T )/1Hc ,
556 J Dutta Majumdar and I Manna
where k is the thermal conductivity, 1T is the thermal gradient, Vm is the molar volume, and
1Hc is the latent heat of crystallization.
The solidification is ‘heat flow limited’ when vi,th nz and Ti ' Tm . This is the case for
usual solidification and crystal growth. However, vi,th nz and Tm > Ti in LSE such that the
growth is ‘interface-limited’ leading to the formation of metastable phases and glassy state.
Furthermore, depending on the magnitude of the product nz, solidification may either belong
to collision controlled (when n ' thermal vibration frequency) or diffusion controlled (when
n = diffusion jump frequency) regime. While the former process (applicable to pure metals,
dilute alloys and intermetallic compounds) is difficult (or impossible) to suppress, the latter
mechanism may easily be overridden if 1T is large or Ti Tm and Ti < Tg . This criterion
may be applicable for amorphization at Ti < T0 < Tg even for systems not having a plunging
T0 -curve if, and only if, the concerned partitionless solidification is diffusion controlled and
considerable change in short range order in the liquid is necessary for crystallization.
The theoretical analysis presented above is primarily applicable to surface amorphization
by picosecond pulsed laser treatment. For practical applications as an industrial process,
particularly for large-sized and complex-shaped components, pulsed laser is not quite suitable.
Instead, a CW–CO2 laser with suitable scope of surface scanning/integration is required for
that purpose. If CW–CO2 laser is to be utilized for laser assisted surface amorphization, the
following difficulties and hurdles are likely to be encountered:
(a) Epitaxial nucleation and growth of crystalline phases from the well compatible liquid-
substrate interface as a competitive process to partitionless amorphization.
(b) Recrystallization or nucleation of crystalline phase at the overlap regions between adjacent
laser tracks due to thermal activation.
(c) Possibility of diffusion-controlled partial crystallization from the melt or adjacent amor-
phous regions due to a relatively longer interaction time necessary for a CW–CO2 laser
assisted LSE process.
(d) Deviation from the intended melt composition due to a possible compositional dilution
effect in the melt arising out of a higher interaction time and hence higher melt depth.
To achieve LSV, it is necessary to suppress the scope of epitaxial nucleation/growth, and
overcome the difficulty of maintaining collision controlled interface limited growth. It is
predicted (by the applicant) that kinetic barrier at Ti < To < Tg may suppress nucleation
Laser processing of materials 557
of crystalline phases due to poor atomic mobility and high viscosity. However, attaining this
glassy state will crucially depend upon the melt composition, heat and mass transfer condition
and suppression of epitaxial nucleation that primarily depends on the ability of maintain
the condition: Ti < To < Tg . This is usually not possible through any of the known LSE
techniques/routines.
Lasers are a clean source of heating with a unique set of optical properties that allow a wide
range of material processing methods from mere heating to synthesis of finished components.
In this article, we have reviewed the major material processing routines that are either rou-
tinely used in the industry or are slated for future exploitation. The processes discussed are
broadly categorized into laser-assisted forming (bending, colouring, rapid prototyping etc.),
joining (welding, soldering, brazing etc.), machining (cutting, drilling, cleaning etc.) and
surface engineering (hardening, annealing, alloying etc.). The materials considered include
metallic, polymeric, ceramic, semiconductor and various combinations thereof. Compre-
hensive lists of notable and current studies in the relevant areas are documented in separate
tables for ready reference. The focus of this review centres on the basic principles, scope and
mechanism/methodology of a given process. Conscious effort has been made to outline the
outstanding issues and define the future scope of research and development in some selected
areas. However, the discussion is intentionally made succinct in order to restrict the length
of the article.
The major hurdles that restrict wider use of lasers in routine material processing appli-
cations are limitation of beam size with respect to the component size/dimension, high
installation and replacement cost, additional and expensive accessories, and need for skilled
manpower. However, the high productivity, precision and versatility of laser material pro-
cessing can easily overcome the above limitations, if areas are identified where laser offers
unmatched advantages in terms of end properties and product quality in comparison to those
achieved by other conventional techniques. It is hoped that the present review would provide
an impetus in that direction.
The authors wish to record their deep appreciation and gratitude to their collaborators in
India (Drs A K Nath, G L Goswami, S V Joshi, A Bharti) and abroad (Profs W M Steen, B
L Mordike, K G Watkins, N B Dahotre). Useful discussion with their colleagues (Profs U
K Chatterjee, S K Roy and S K Pabi) and contributions of the former students are sincerely
acknowledged. Partial financial support from the Council of Scientific and Industrial Research
and Department of Science and Technology, New Delhi is duly acknowledged. One of the
authors (I M) would like to thank the Alexander von Humboldt Foundation, Bonn for financial
support during the preparation of the manuscript.
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